Patent GB-1040035-A (GB)
Title: Oil- and water-repellent fluorine-containing compositions
IPC: D21H17/34
Filed: 1964-09-23
Abstract: A composition for conferring oil- and water-repellency upon substrate materials comprises (1) from 3 to 60% of a polymer of a methacrylate ester having the formula CH2=C(CH3)CO2CH2CH2Cn F2n+1 in which n has a value of from 3 to 14, and (2) from 40 to 97% of a copolymer of a monovinylidene compound and a non-conjugated divinylidene compound, both of which are free from non-vinylidene fluorine, the divinylidene compound constituting 0.05 to 10% of the copolymer. Alternatively, the polymer (1) may be replaced by a copolymer containing from 25 to 99.8% of the fluorinated methacrylate and from 0.2 to 75% of a monovinylidene compound free of non-vinylidene fluorine, the resulting mixture containing at least 3% of the fluorinated methacrylate.  The monovinylidene monomers used are selected from acrylic and methacrylic esters, N-methylol acrylamide, styrene and its derivatives, vinyl and allyl esters, vinyl and vinylidene halides, vinyl alkyl ketones and (considered as monovinylidene monomers) butadiene and derivatives thereof.  Divinylidene compounds used are selected from esters of alkanediols and acrylic acids, vinyl and allyl esters of acrylic acids, vinyl esters of dicarboxylic acids, and divinyl substituted aromatic compounds.  The compositions are preferably made by mixing latices of the two polymers, and to the resulting mixtures may be added other materials, e.g. polyethylene emulsions, melamine resins, petroleum wax and non-ionic emulsifiers. The Examples describe (1) polymerizing heptadecafluorodecyl methacrylate in an aqueous medium containing acetone, trimethyloctadecylammonium bromide and azodiisobutyramidine dihydrochloride, (2) copolymerizing mixed C6-C14 perfluoroalkyl methacrylates, n-butyl acrylate and N-methylol acrylamide in an aqueous medium containing acetone, dimethyloctadecylamine, acetic acid and azodiisobutyramidine dihydrochloride, (3) copolymerizing in an aqueous medium as in (2) 2-ethylhexyl methacrylate, N-methylol acrylamide and (a) ethylene dimethacrylate, (b) propylene dimethacrylate, (c) pentylene dimethacrylate, (d) vinyl acrylate, (e) allyl acrylate, and (f) divinyl benzene, and (4) blending emulsions formed in (3) and (4), the resulting compositions containing also a melamine resin and a polyethylene emulsion.ALSO:Oil- and water-repellency is conferred upon textile materials by impregnating them, with an aqueous composition comprising (1) from 3 to 60% of a polymer of a methacrylate ester of the formula <FORM:1040035/D1-D2/1> in which n has a value from 3 to 14, and (2) from 40 to 97% of a copolymer of a monovinylidene compound and a non-conjugated divinylidene compound both of which are free from non-rinylidene fluorine, the divinylidene compound constituting 0.05 to 10% of the copolymer.  Alternatively, the polymer (1) may be replaced by a copolymer containing from 25 to 99.8% of the fluorinated methacrylate and from 0.2 to 75% of a monovinylidene compound free of non-vinylidene fluorine, the resulting mixture containing at least 3% of the fluorinated methacrylate (see Division C3).  After being impregnated with the composition, excess liquid is expressed from the textiles which are then heated at 155-195 DEG C. for at least 15 secs.  Textiles specified for treatment are those made from silk, cotton, regenerated cellulose, cellulose acetate, polyacrylonitrile nylon linear polyesters.  The Examples describe impregnating cotton poplin fabric and a fabric made from a mixture of cotton and polyethylene terephthalate with mixed aqueous dispersions of a copolymer of 1H, 1H, 2H, 2H-per-fluoralkyl methacrylate n-butyl acrylate and N-methylol acrylamide with copolymers of 2-ethylexyl with acrylate, N-methylolacrylamide and (a) ethylene dimethacrylate, (b) propylene dimethacrylate, (c) pentylene dimethacrylate, (d) divinyl benzene, (e) vinyl acrylate, and (f) alkyl acrylate, the compositions containing also a melamine resin and a polyethylene emulsion.