Patent GB-1058955-A (GB)
Title: Oil-and water-repellent compositions and process for their application
IPC: C14C9/00
Filed: 1965-08-11
Abstract: An oil- and water-repellent composition consists essentially of (I) from 0.5 to 50% of solids comprising (A) 5 to 97% of a copolymer of (a) 25 to 99% of at least one monomer RfCH2CH2O2CC(CH3)=CH2 where Rf is a perfluoralkyl group containing 4 to 14 carbon atoms, (b) 0.1 to 20% of at least one monomer of formula CH2=C(R)CO2R1OH, CH2=C(R)CONHCH2OH or CH2=C(R)CO2R11 wherein R is H. or methyl, R1 is an alkylene group containing at least 2 carbon atoms and R11 is an epoxy alkyl group containing at least 3 carbon atoms, the balance if any, being (c) at least one vinylidene monomer free of non-vinylic fluorine and different from monomers (b); (B) 0 to 75% of a melamineformaldehyde condensation product, (B) being present in amount 3 to 75% when component (C) is not present, and vice versa; (C) 0 to 75% of at least one extender polymer which is (1) a copolymer of an alkyl methacrylate and a dialkylaminoalkyl methacrylate, (2) a chlorosulphonated hydrocarbon polymer, (3) a polyurethane containing free isocyanate groups or (4) a copolymer containing the group <FORM:1058955/C3/1> R being H or methyl; and (II) 99.5 to 50% of an organic solvent which is a hydrocarbon, halogenated hydrocarbon, ketone or ester having a b.p from 25 DEG  to 180 DEG  C., the polymers (A) and (C) and the condensation product (B) each being soluble or dispersible in the organic solvent to the extent of 0.03 to 20% by weight of the solvent.  Comonomer (c) is e.g. an alkyl (meth)acrylate, styrene, an alkyl styrene, a vinyl alkyl ketone or ether, a vinyl ester, butadiene or a substituted butadiene.  The preferred solvents are trichloroethylene, 1,2 -difluorotetrachloroethane, 1,1,2 - trichlorotrifluoroethane, trichloromonofluoromethane and dichlorodifluoromethane.  Up to 50% of the solids content may be a natural or synthetic wax, e.g. paraffin wax.  In the examples polymer (A) is a copolymer of (a) F(CF2)nCH2CH2O2CC(CH3)= CH2 wherein n=6, 8 and 10 in the ratio 3:2:1 and up to 10% has n=12 to 14, and (b) glycidyl (meth)acrylate, N-methylol acrylamide or 2-hydroxypropyl mathacrylate and in some cases (c) n-butyl (meth)acrylate or 2-ethylhexyl methacrylate.  (A) is prepared by either solution polymerization in trichlorotrifluoroethane and 1,2-difluorotetrachloroethane with portion-wise addition of azobisisobutyronitrile as catalyst or suspension polymerization in an aqueous medium containing dimethyloctadecylamine and acetic acid, using azobis(isobutyramidine dihydrochloride) as catalyst.  Lauryl mercaptan may be present during the polymerizations. The resulting polymers are incorporated in compositions containing in addition (B) hexamethylol melamine or a reaction product thereof with stearic or behenic acid, and in some cases (C) a chlorosulphonated polyethylene, an ethylene-vinyl acetate-methacrylyl chloride copolymer or a polyurethane derived from polytetramethylene ether glycol.  Reference has been directed by the Comptroller to Specification 1,011,612.ALSO:A composition for rendering textiles oil- and water-repellent contains (I) solids comprising (A) a fluorinated copolymer of (a) a monomer Rf CH2 CH2 O2 CC(CH3)=CH2 where Rf is a perfluoroalkyl group of 4 to 14 carbon atoms, (b) a monomer CH2=C(R) CO2R1OH, CH2=C(R)CONH CH2 OH or CH2=C(R)CO2 R11 where R is H or CH3, R1 is an alkylene group of at least 2 carbon atoms and R11 is an epoxy alkyl group of at least 3 carbon atoms and, optionally, (c) a vinylidene monomer other than (a) or (b); (B) a melamine-formaldehyde condensation product and/or (C) a copolymer of an alkyl methacrylate and a dialkylaminoalkyl methacrylate, a chlorosulfonated hydrocarbon, a polyurethane containing free isocyanate groups or a copolymer containing the group <FORM:1058955/D1-D2/1> , R being H or methyl; and (II) an organic solvent which is a hydrocarbon, halogenated hydrocarbon, ketone or ester of b.p. 25 DEG  to 180 DEG C.  In examples (A) is a copolymer of (a) F(CF2)n CH2 CH2O2 CC(CH3)=CH2 where n=6, 8 and 10 and, in amount, up to 10%, n=12 to 14, (b) glycidyl (meth)acrylate, N-methylol acrylamide or 2-hydroxypropyl methacrylate and (c) n-butyl (meth)acrylate or 2-ethylhexyl methacrylate, (B) is hexamethylol melamine or a reaction product thereof with stearyl or behenic acid and (c) is a chlorosulfonated polyethylene, an ethylene-vinyl acetate-methacryloyl chloride repolymer or a polyurethane.  (A) and (B) are mixed, optionally with (C) and/or paraffin wax, and dissolved in trichloroethylene, 1,1,2-trichlorotrifluoroethane, or 1,2-difluorotetrachloroethane, or mixtures thereof, and sprayed on to cotton poplin, rayon and rayon-polypropylene fabrics and then cured by heating.  In an aerosol application the solvent used is a mixture of 1,2-difluorotetrachloroethane, 1,1,2-trichlorotrifluoroethane, trichloromonofluoromethane and dichlorodifluoromethane.  Reference has been directed by the Comptroller to Specification 1,011,612.