Stock material or miscellaneous articles – Composite – Of fluorinated addition polymer from unsaturated monomers
Reexamination Certificate
1998-01-12
2001-03-06
Chen, Vivian (Department: 1773)
Stock material or miscellaneous articles
Composite
Of fluorinated addition polymer from unsaturated monomers
C526S242000, C526S245000, C524S366000, C524S462000, C524S792000, C524S795000
Reexamination Certificate
active
06197426
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a fluorochemical copolymer and fluorochemical copolymer compositions that can be used to impart oil and/or water repellency properties to a substrate, in particular a fibrous substrate. The invention also relates to a method of preparing the fluorochemical copolymer and the use of the fluorochemical copolymers as an oil and/or water repellency treatment.
BACKGROUND OF THE INVENTION
Organofluorine, or fluorochemical compounds, are substances containing portions that are fluorocarbon in nature (e.g., hydrophobic, oleophobic, and chemically inert) and portions that are hydrocarbon in nature (e.g., chemically reactive in organic reactions). Some fluorochemicals are familiar to the general public, such as SCOTCHGARD™ carpet protector, which imparts oil and water repellency and stain and soil resistance to carpet. Other such substances have various industrial uses, such as reducing the surface tension of liquids, reducing evaporation and flammability of volatile organic liquids, and improving the leveling of organic polymer coatings.
The utility of certain organofluorine compounds as surface-active agents (i.e., surfactants) and surface-treating agents is due in large part to the extremely low free-surface energy of a C
6
-C
12
fluorocarbon group, according to H. C. Fielding, “
Organofluorine Compounds and Their Applications
,” R. E. Banks, Ed., Society of Chemical industry at p. 214 (1979). Generally, such organofluorine substances are those which have carbon-bonded fluorine in the form of a monovalent fluoroaliphatic radical such as a perluoroalkyl group, typically C
n
F
2n+1
, where n is at least 3, and the terminal part of the group is trifluoromethyl, —CF
3
.
Fluorochemical-based water and/or oil repellent compositions for treating substrates, in particular textiles and leather, are of substantial commercial importance. Amongst water and/or oil repellent compositions known in the art for the treatment of substrates are certain compositions containing fluorochemical polymers.
For example, U.S. Pat. No. 4,791,166 discloses certain copolymers soluble in odorless mineral spirits. These copolymers are prepared by polymerization of monomer mixtures comprising: perfluoroalkyl vinyl monomer; higher alkyl vinyl monomer; and a third monomer selected from the group consisting of: vinylamidoglycolate, vinyl diketoester, and vinyl ester monomer containing hydroxy and halide groups.
U.S. Pat. No. 4,791,167 discloses certain solvent-based, auto-oxidizable fluorocarbon compositions. The copolymers are prepared from the following monomers: perfluoroalkyl-containing-vinyl monomer, higher alkyl vinyl monomer and an acrylate ester containing one or more unsaturated olefinic bonds.
U.S. Pat. No. 5,132,028 discloses certain water- and oil-repellent compositions useful as fabric treatments. The compositions contain a fluorochemical water and oil repellent agent, a carbodiimide compound, and at least one of the following: plasticizer, metal alcoholate or ester, zirconium salt, alkylketene dimer, aziridine, and alkenyl succinic anhydride. The compositions may also contain a silicone water repellent.
U.S. Pat. No. 5,308,511 discloses certain solvent-based, water- and oil-repellent treating agent compositions. The compositions contain a mineral spirits solution of a fluorochemical water and oil repellent agent, zirconium carboxylic acid ester, and alkenyl succinic anhydride.
U.S. Pat. No. 5,516,578 discloses certain oil- and water-repellent compositions comprising: a fluoroaliphatic radical containing agent; and a polymer comprising cyclic carboxylic anhydride groups. Additionally the composition may also comprise a softener and/or a plasticizer. The patent discloses that the compositions provide water- and oil-repellent properties to fibrous and other substrates treated therewith and show high compatibility with commonly used softeners.
U.S. Pat. No. 5,475,070 discloses certain water- and oil-repellent agent compositions comprising, as main component, units derived from a copolymer comprising polyfluoro-oxyalkyl-containing (meth)acrylate and units derived from a dicarboxylic acid anhydride-containing (meth)acrylate.
U.S. Pat. No. 5,536,304 describes oil- and water-repellency imparting compositions that comprise: a fluoroaliphatic radical containing agent; and a cyclic carboxylic anhydride containing polysiloxane. Additionally, the composition may comprise: an extender and/or a plasticizer. The patent discloses that the compositions provide water- and oil-repellent properties and a soft hand to fibrous and other substrates treated therewith.
EP 0 756 033 discloses water- and oil-repellent compositions consisting essentially of a copolymer comprising polymeric units “A”, “B”, “C” and “D”, and an organic solvent. Polymeric units A are derived from a polyfluoroalkyl group, and/or a polyfluoroalkyl-group-containing methacrylate; polymeric units B are derived from a hydrocarbon-group-containing acrylate, and/or a hydrocarbon-group-containing methacrylate; polymeric units C are derived from an acid anhydride having an unsaturated group; and polymeric units D are derived from triallyl cyanurate.
Fluorochemical polymers used to impart water- and/or oil-repellency to fibrous substrates are typically applied in the form of a solution using spray, aerosol or pad application or during the dry cleaning rinse cycle. Many of the solvents used to prepare such solutions are flammable, ozone depleting or dry slowly. Despite the existence of known fluorochemical compositions for these applications, there continues to be a demand for better performing fluorochemical compositions that can meet more demanding applications and be applied using a wide variety of solvents.
Accordingly, the present invention seeks to provide new fluorochemical compositions that can meet the requirements of more demanding applications and that are preferably based on a solvent that is non-ozone depleting, non-flammable and fast drying. Further, in case of application during dry cleaning, the fluorochemical composition should be compatible with the dry cleaning solvents.
SUMMARY OF THE INVENTION
The present invention provides a method for treatment of a substrate comprising applying to said substrate a fluorochemical composition comprising a fluorochemical copolymer derived from at least one fluorochemical monomer A, at least one monomer B, at least one monomer C and at least one monomer D. Fluorochemical monomer A has a fluoroaliphatic group and is an ester of an &agr;,&bgr;-ethylenically unsaturated carboxylic acid, monomer B is an ester of an &agr;,&bgr;-ethylenically unsaturated carboxylic acid, monomer C is an ethylenically unsaturated dicarboxylic acid anhydride and monomer D is an ester of an &agr;,&bgr;-ethylenically unsaturated carboxylic acid. Fluorochemical monomer A and monomers B and C contain only one polymerizable group and monomer D contains, as a further polymerizable group, an ethylenically unsaturated group that has a higher affinity to copolymerize with monomer C than with monomers A, B or D.
Further provided is a fluorochemical copolymer derived from at least one fluorochemical monomer A, at least one monomer B, at least one monomer C and at least one monomer D, said fluorochemical monomer A having a fluoroaliphatic group and being an ester of an &agr;,&bgr;-ethylenically unsaturated carboxylic acid, said monomer B being an ester of an &agr;,&bgr;-ethylenically unsaturated carboxylic acid, said monomer C being an ethylenically unsaturated dicarboxylic acid anhydride and said monomer D being an ester of an &agr;,&bgr;-ethylenically unsaturated carboxylic acid, said fluorochemical monomer A and said monomers B and C containing only one polymerizable group and said monomer D containing as a further polymerizable group an ethylenically unsaturated group that has a higher affinity to copolymerize with said monomer C than with any of said monomers A, B or D.
The present invention also provides a method of preparing the fluorochemical copolymer, a fluorochemical compositio
3M Innovative Properties Company
Chen Vivian
Jordan Robert H.
Maki Eloise J.
LandOfFree
Fluorochemical copolymer and fluorochemical copolymer... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Fluorochemical copolymer and fluorochemical copolymer..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Fluorochemical copolymer and fluorochemical copolymer... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2474973