Water-dispersible polyester stabilized fluoroalkyl compositions
View Patent ↗In this invention, an aqueous dispersion is provided to improve the oil and water repellency of materials. The aqueous dispersion comprises a polymer, at least one water dispersible polyester, and water; wherein the polymer comprises the repeating units from at least one fluoroalkyl monomer and optionally, at least one ethylenically unsaturated monomer. This invention also provides an article coated with the aqueous dispersion.
1. A pre-emulsion comprising at least one fluoroalkyl monomer, at least one water-dispersible polyester, water and optionally an ethylenically unsaturated monomer; wherein the fluoroalkyl monomer is represented by the formula: Rf-Q-OCOCR═CH 2 ; wherein Q is a bivalent organic group, and R is hydrogen atom or methyl group; wherein Q is selected from the group consisting of —(CH 2 ) p+q —; —(CH 2 ) p CONH(CH 2 ) q —; —(CH 2 ) p OCONH(CH 2 ) q —; —(CH 2 ) p SO 2 NR′(CH 2 ) q —; —(CH 2 ) p NHCONH(CH 2 ) q —; or —(CH 2 ) p CHOH—(CH 2 ) q —; wherein R′ is a hydrogen or an alkyl group, and each of p and q is an integer of at least 0, provided that p+q is an integer of from 1 to 22.
2. A pre-emulsion according to claim 1 wherein said fluoroalkyl monomer is selected from the group consisting of:
F(CF 2 ) 5 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 6 CH 2 CH 2 OCOCR═CH 2 ,
H(CF 2 ) 6 CH 2 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 8 CH 2 CH 2 OCOCR═CH 2 ,
i-C 3 F 7 (CF 2 ) 5 CH 2 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 8 SO 2 N(C 3 H 7 )CH 2 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 8 (CH 2 ) 4 OCOCR═CH 2 ,
F(CF 2 ) 8 SO 2 N(CH 3 )CH 2 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 8 SO 2 N(C 2 H 5 )CH 2 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 8 CONHCH 2 CH 2 OCOCR═CH 2 ,
i-C 3 F 7 (CF 2 ) 5 (CH 2 ) 3 OCOCR═CH 2 ,
i-C 3 F 7 (CF 2 ) 5 CH 2 CH(OCOCH 3 )OCOCR═CH 2 ,
i-C 3 F 7 (CF 2 ) 5 CH 2 CH 2 CH(OH)CH 2 OCOCR═CH 2 ,
F(CF 2 ) 9 CH 2 CH 2 OCOCR═CH 2 , and
F(CF 2 ) 9 CONHCH 2 CH 2 OCOCR═CH 2 ; wherein R represents a hydrogen or a methyl group, and i-C 3 F 7 represents a perfluoroisopropyl group [(CF 3 ) 2 CF—].
3. A pre-emulsion according to claim 1 wherein said fluoroalkyl compound is perfluoroalkylethyl acrylate or perfluoroalkylmethyl acrylate; wherein the alkyl group has about 6 to about 14 carbon atoms.
4. A pre-emulsion according to claim 1 wherein said ethylenically unsaturated monomer is at least one selected from the group consisting of styrenic compounds, ethylenically unsaturated compounds, nitrogen-containing compounds, vinyl chloride, and vinylidene chloride.
5. A pre-emulsion according to claim 4 wherein said styrenic compound is at least one selected from the group consisting of styrene, α-methyl styrene, vinyl naphthalene, vinyl toluene, and chloromethyl styrene.
6. A pre-emulsion according to claim 4 wherein said ethylenically unsaturated compounds is at least one selected from the group consisting of methyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate ethylhexyl acrylate, ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, isodecyl acrylate, isodecyl methacrylate, lauryl methacrylate, lauryl acrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate, stearyl methacrylate glycidyl methacrylate, alkyl crotonates, vinyl acetate, di-n-butyl maleate, di-octylmaleate, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetopropryl acrylate, diacetone acrylamide, acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, allyl methacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, isodecyl methacrylate, isodecyl acrylate, 2-methoxy acrylate, 2-methoxy methacrylate, 2-(2-ethoxyethoxy) ethylacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, caprolactone acrylate, caprolactone methacrylate, polypropyleneglycol monoacrylate, polypropyleneglycol monomethacrylate, poyethyleneglycol(400) acrylate, polypropyleneglycol(400) methacrylate, benzyl acrylate, benzyl methacrylate, sodium 1-allyloxy-2-hydroylpropyl sulfonate, and acrylonitrile.
7. A pre-emulsion according to claim 4 wherein said nitrogen containing compounds is at least one selected from the group consisting of Nitrogen-containing compounds include, but are not limited to, t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, N,N-dimethylaminopropyl ethacrylamided, methacrylamide, t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylated, N,N-dimethylaminopropyl methylcrylamide, 2-t-butylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid, N-(2-methacryloyloxy-ethyl)ethylene urea, methacrylamidoethylethylene urea.
8. A pre-emulsion according to claim 6 wherein said ethylenically unsaturated monomer is lauryl methacrylate.
9. A pre-emulsion according to claim 1 wherein said water-dispersible polyester is a polyethylene glycol polyester.
10. A miniemulsion comprising at least one fluoroalkyl monomer, at least one water-dispersible polyester, water, and optionally an ethylenically unsaturated monomer; wherein the fluoroalkyl monomer is represented by the formula: Rf-Q-OCOCR═CH 2 ; wherein Q is a bivalent organic group, and R is a hydrogen atom or methyl group; wherein Q is selected from the group consisting of —(CH 2 ) p+q —; —(CH 2 ) p CONH(CH 2 ) q —; —(CH 2 ) p OCONH(CH 2 ) q —; —(CH 2 ) p SO 2 NR′(CH 2 ) q —; —(CH 2 ) p NHCONH(CH 2 ) q —; or —(CH 2 ) p CHOH—(CH 2 q —; wherein R′ is a hydrogen or an alkyl group, and each of p and q is an integer of at least 0, provided that p+q is an integer of from 1 to 22.
11. A miniemulsion according to claim 10 wherein Q is selected from the group consisting of —(CH 2 ) p+q —; —(CH 2 ) p CONH(CH 2 ) q —; —(CH 2 ) p OCONH(CH 2 ) q —; —(CH 2 ) p SO 2 NR′(CH 2 ) q —; —(CH 2 ) p NHCONH(CH 2 ) q —; or —(CH 2 ) p CH(OH)—(CH 2 ) q —; wherein R′ is a hydrogen or an alkyl group, and each of p and q is an integer of at least 0, provided that p+q is an integer of from 1 to 22.
12. A miniemulsion according to claim 11 wherein said fluoroalkyl monomer is selected from the group consisting of:
F(CF 2 ) 5 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 6 CH 2 CH 2 OCOCR═CH 2 ,
H(CF 2 ) 6 CH 2 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 8 CH 2 CH 2 OCOCR═CH 2 ,
i-C 3 F 7 (CF 2 ) 5 CH 2 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 8 SO 2 N(C 3 H 7 )CH 2 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 8 (CH 2 ) 4 OCOCR═CH 2 ,
F(CF 2 ) 8 SO 2 N(CH 3 )CH 2 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 8 SO 2 N(C 2 H 5 )CH 2 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 8 CONHCH 2 CH 2 OCOCR═CH 2 ,
i-C 3 F 7 (CF 2 ) 5 (CH 2 ) 3 OCOCR═CH 2 ,
i-C 3 F 7 (CF 2 ) 5 CH 2 CH(OCOCH 3 )OCOCR═CH 2 ,
i-C 3 F 7 (CF 2 ) 5 CH 2 CH 2 CH(OH)CH 2 OCOCR═CH 2 ,
F(CF 2 ) 9 CH 2 CH 2 OCOCR═CH 2 , and
F(CF 2 ) 9 CONHCH 2 CH 2 OCOCR═CH 2 ; wherein R represents a hydrogen or a methyl group, and i-C 3 F 7 represents a perfluoroisopropyl group [(CF 3 ) 2 CF—].
13. A miniemulsion according to claim 10 wherein said fluoroalkyl compound is perfluoroalkylethyl acrylate or perfluoroalkylmethyl acrylate; wherein the alkyl group has about 6 to about 14 carbon atoms.
14. A miniemulsion according to claim 10 wherein said ethylenically unsaturated monomer is at least one selected from the group consisting of styrenic compounds, ethylenically unsaturated compounds, nitrogen-containing compounds, vinyl chloride, and vinylidene chloride.
15. A miniemulsion according to claim 14 wherein said styrenic compound is at least one selected from the group consisting of styrene, α-methyl styrene, vinyl naphthalene, vinyl toluene, and chloromethyl styrene.
16. A miniemulsion according to claim 14 wherein said ethylenically unsaturated compounds is at least one selected from the group consisting of methyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, isodecyl acrylate, isodecyl methacrylate, lauryl methacrylate, lauryl acrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl methacrylate, alkyl crotonates, vinyl acetate, di-n-butyl maleate, di-octylmaleate, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetopropryl acrylate, diacetone acrylamide, acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, allyl methacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, isodecyl methacrylate, isodecyl acrylate, 2-methoxy acrylate, 2-methoxy methacrylate, 2-(2-ethoxyethoxy) ethylacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, caprolactone acrylate, caprolactone methacrylate, polypropyleneglycol monoacrylate, polypropyleneglycol monomethacrylate, poyethyleneglycol(400) acrylate, polypropyleneglycol(400) methacrylate, benzyl acrylate, benzyl methacrylate, sodium 1-allyloxy-2-hydroylpropyl sulfonate, and acrylonitrile.
17. A miniemulsion according to claim 14 wherein said nitrogen containing compound is at least one selected from the group consisting of methacrylamide, t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, N,N-dimethylaminopropyl methacrylamide, 2-t-butylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid, N-(2-methacryloyloxy-ethyl)ethylene urea, methacrylamidoethylethylene urea.
18. A miniemulsion according to claim 14 wherein said ethylenically unsaturated monomer is lauryl methacrylate.
19. A miniemulsion according to claim 10 wherein said water-dispersible polyester is a polyethylene glycol polyester.
20. An aqueous dispersion comprising a polymer, at least one water-dispersible polyester, and water; wherein said polymer comprises repeating units from at least one fluoroalkyl monomer and optionally at least one ethylenically unsaturated monomer; wherein said fluoroalkyl monomer is a (meth)acrylate having a Rf group; wherein the Rf group is a group having at least two hydrogen atoms of an alkyl group substituted by fluorine atoms; wherein the fluoroalkyl monomer is represented by the formula Rf-Q-OCOCR═CH 2 ; wherein Q is a bivalent organic group, R is hydrogen atom or methyl group; wherein Q is selected from the group consisting of —(CH 2 ) p+q —; —(CH 2 ) p CONH(CH 2) q —; —(CH 2 )OCONH(CH 2 ) q —; —(CH 2 ) p SO 2 NR′(CH 2 ) q —; —(CH 2 ) p NHCONH(CH 2 ) q —; or —(CH 2 ) p CHOH—(CH 2 ) q —; wherein R′ is a hydrogen or an alkyl group, and each of p and q is an integer of at least 0, provided that p+q is an integer of from 1 to 22; and wherein the amount of water-dispersible polyester solids in the aqueous dispersion ranges from 3% to 5% based on the total weight of said aqueous dispersion.
21. An aqueous dispersion according to claim 20 wherein the carbon number of said Rf group is from 2 to about 20.
22. An aqueous dispersion according to claim 21 wherein the carbon number of said Rf group is from 6 to 14.
23. An aqueous dispersion according to claim 20 wherein the number of fluorine atoms in said Rf group is at least 60%, as represented by [(the number of fluorine atoms in the Rf group)/(the number of hydrogen atoms contained in an alkyl group having the same carbon number as the Rf group)]×100(%).
24. An aqueous dispersion according to claim 23 wherein the number of fluorine atoms in said Rf group is at least 80%, as represented by [(the number of fluorine atoms in the Rf group)/(the number of hydrogen atoms contained in an alkyl group having the same carbon number as the Rf group)]×100(%).
25. An aqueous dispersion according to claim 24 wherein said Rf group is a perfluoroalkyl group.
26. An aqueous dispersion according to claim 25 wherein the number of carbon atoms in said perfluoralkyl group is from 2 to about 20.
27. An aqueous dispersion according to claim 21 wherein the fluoroalkyl monomer is represented by the formula: Rf-Q-OCOCR═CH 2 ; wherein Q is a bivalent organic group, and R is a hydrogen atom or methyl group.
28. An aqueous dispersion according to claim 27 wherein Q is selected from the group consisting of —(CH 2 ) p+q —; —(CH 2 ) p CONH(CH 2 ) q —; (CH 2 ) p OCONH(CH 2 ) q —; —(CH 2 ) p SO 2 NR′(CH 2 ) q —; (CH 2 ) p NHCONH(CH 2 ) q —; or —(CH 2 ) p CH(OH)—(CH 2 ) q —; wherein R′ is a hydrogen or an alkyl group, and each of p and q is an integer of at least 0, provided that p+q is an integer of from 1 to 22.
29. An aqueous dispersion according to claim 28 wherein Q is selected from the group consisting of —(CH 2 ) p+q —; —(CH 2 ) p CONH(CH 2 ) q —; and —(CH 2 ) p SO 2 NR′(CH 2 ) q —; wherein q is an integer of at least 2; and p+q is from 2 to 6.
30. An aqueous dispersion according to claim 29 wherein Q is (CH 2 ) p+q , and wherein p+q is from 2 to 6.
31. An aqueous dispersion according to claim 28 wherein said fluoroalkyl monomer is selected from the group consisting of:
F(CF 2 ) 5 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 6 CH 2 CH 2 OCOCR═CH 2 ,
H(CF 2 ) 6 CH 2 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 8 CH 2 CH 2 OCOCR═CH 2 ,
i-C 3 F 7 (CF 2 ) 5 CH 2 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 8 SO 2 N(C 3 H 7 )CH 2 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 8 (CH 2 ) 4 OCOCR═CH 2 ,
F(CF 2 ) 8 SO 2 N(CH 3 )CH 2 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 8 SO 2 N(C 2 H 5 )CH 2 CH 2 OCOCR═CH 2 ,
F(CF 2 ) 8 CONHCH 2 CH 2 OCOCR═CH 2 ,
i-C 3 F 7 (CF 2 ) 5 (CH 2 ) 3 OCOCR═CH 2 ,
i-C 3 F 7 (CF 2 ) 5 CH 2 CH(OCOCH 3 )OCOCR═CH 2 ,
i-C 3 F 7 (CF 2 ) 5 CH 2 CH 2 CH(OH)CH 2 OCOCR═CH 2 ,
F(CF 2 ) 9 CH 2 CH 2 OCOCR═CH 2 , and
F(CF 2 ) 9 CONHCH 2 CH 2 OCOCR═CH 2 ; wherein R represents a hydrogen or a methyl group, and i-C 3 F 7 represents a perfluoroisopropyl group [(CF 3 ) 2 CF—].
32. An aqueous dispersion according to claim 27 wherein said fluoroalkyl compound is perfluoroalkylethyl acrylate or perfluoroalkylmethyl acrylate; wherein the alkyl group has about 6 to about 14 carbon atoms.
33. An aqueous dispersion according to claim 20 wherein said ethylenically unsaturated monomer is at least one selected from the group consisting of styrenic compounds, ethylenically unsaturated compounds, nitrogen-containing compounds, vinyl chloride, and vinylidene chloride.
34. An aqueous dispersion according to claim 33 wherein said styrenic compound is at least one selected from the group consisting of styrene, α-methyl styrene, vinyl naphthalene, vinyl toluene, and chloromethyl styrene.
35. An aqueous dispersion according to claim 33 wherein said ethylenically unsaturated compounds is at least one selected from the group consisting of methyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate ethylhexyl acrylate, ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, isodecyl acrylate, isodecyl methacrylate, lauryl methacrylate, lauryl acrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl methacrylate, alkyl crotonates, vinyl acetate, di-n-butyl maleate, di-octylmaleate, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetopropryl acrylate, diacetone acrylamide, acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, allyl methacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, isodecyl methacrylate, isodecyl acrylate, 2-methoxy acrylate, 2-methoxy methacrylate, 2-(2-ethoxyethoxy) ethylacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, caprolactone acrylate, caprolactone methacrylate, polypropyleneglycol monoacrylate, polypropyleneglycol monomethacrylate, poyethyleneglycol(400) acrylate, polypropyleneglycol(400) methacrylate, benzyl acrylate, benzyl methacrylate sodium 1-allyloxy-2-hydroylpropyl sulfonate, and acrylonitrile.
36. An aqueous dispersion according to claim 33 wherein said nitrogen containing compound is at least one selected from the group consisting of methacrylamide, t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, N,N-dimethylaminopropyl methacrylamide, 2-t-butylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid, N-(2-methacryloyloxy-ethyl)ethylene urea, methacrylamidoethylethylene urea.
37. An aqueous dispersion according to claim 33 wherein said ethylenically unsaturated monomer has up to about 18 carbon atoms.
38. An aqueous dispersion according to claim 37 wherein said ethylenically unsaturated monomer is lauryl methacrylate.
39. An aqueous dispersion according to claim 20 wherein the amount of fluoroalkyl monomer repeating units in said polymer ranges from about 50 to about 100 weight percent based on the total weight of monomer utilized to produce said polymer.
40. An aqueous dispersion according to claim 39 wherein the amount of fluoroalkyl repeating units in said polymer ranges from about 60 to about 80 weight percent based on the total weight of monomer utilized to produce said polymer.
41. An aqueous dispersion according to claim 20 wherein said water-dispersible polyester is a polyethylene glycol polyester.
42. An aqueous dispersion according to claim 20 wherein the amount of said water-dispersible polyester solids in the aqueous dispersion ranges from about 1% to about 20% based on the total weight of said aqueous dispersion.
43. An aqueous dispersion according to claim 20 further comprising at least one compound selected from the group consisting of other water repellents and oil repellents, anti-fungus agents, flame retardants, antistatic agents, crease-proofing agents, antimigrants, defoamers, binders, and other antifouling agents.
44. A substrate coated with said aqueous dispersion of claim 20 .
45. A substrate according to claim 44 wherein said substrate is selected from the group consisting of a fiber, yarn, thread, fabric, paper material, and carpet.
46. A fabric coated with said aqueous dispersion of claim 20 .