Method using fluoropolymer emulsions

A method of providing oil repellency, water repellency, and dynamic water repellency to a substrate comprising contacting the substrate with a polymer composition comprising

• A) a first polymer comprising, on a water free basis,
• (a) from about 0.1% to about 1.0% by weight hydrophobized nanoparticles;
• (b) from about 89% to about 99.8% by weight of one or more monomers of C1 to C18, straight, branched, or cyclic alkyl (meth)acrylate;
• (c) from about 0.1% to about 10.0% by weight of one or more monomers selected from the group consisting of N-methylol (meth)acrylamide and monomers of formula (I)
• R—(OCH2CH2)a—O—C(O)—C(R1)═CH2 (I)
• wherein a is 1 to from about 10;
• R is hydrogen, C1-C4 alkyl, or —C(O)—C(R1)═CH2, and R1 is H or —CH3;
• said first polymer in contact with
• B) a second polymer comprising, on a water free basis,
• (d) from about 70% to about 90% by weight fluorinated monomer of formula (II)
• Rf1-L-X—C(O)—C(R)═CH2 (II)
• wherein Rf1 is a monovalent, partially or fully fluorinated, linear or branched, alkyl radical having 2 to about 7 carbon atoms;
• optionally interrupted by 1 to about 6 catenary oxygen atoms;
• wherein the ratio of carbon atoms to oxygen atoms is at least 2:1 and no oxygen atoms are bonded to each other;
• L is a bond or a linear or branched divalent linking group having 1 to about 20 carbon atoms, said linking group optionally interrupted by 1 to about 4 hetero-radicals selected from the group consisting of —O—, —NR6—, —S—, —SO—, —SO2—, and —N(R6)C(O)— wherein R6 is H or C1 to C6 alkyl, and said linking group optionally substituted with CH2Cl;
• X is —O—, —N(R)—, or —S—, wherein R is H or CH3;
• (e) from about 10% to 30% by weight of one or more monomers of C1 to C18, straight, branched, or cyclic alkyl (meth)acrylate;
• and
• (f) from about 0.1% to about 10% by weight of one or more monomers selected from the group consisting of N-methylol (meth)acrylamide and monomers of formula (I)
• R—(OCH2CH2)a—O—C(O)—C(R1)═CH2 (I)
• wherein R is hydrogen, C1-C4 alkyl, or —C(O)—C(R1)═CH2, and R1 is H or —CH3;
• provided that the first polymer comprises from about 20% to about 75% by weight of the polymer composition;
• wherein the hydrophobized nanoparticles is dispersed within the first polymer (A);
• wherein the nanoparticles are a surface modified inorganic oxide particle comprising an oxide of M atoms independently selected from the group consisting of Si, Ti, Zn, Zr, Mn, Al, and combinations thereof;
• and
• wherein at least one inorganic oxide particle has a surface covalently bonded to at least one group represented by formula (IV)
• (-L2-)d(-L3)c(—Si—R7(4-d)) (IV)
• wherein:
• L2 represents an oxygen covalently bonded to M;
• and each L3 is independently selected from the group consisting of H, a C1-C2 alkyl, and OH;
• d and c are integers such that:
• d is greater than or equal to 1, c is greater than or equal to 0, and the sum (d+c) is less than or equal to 3;
• and
• R7 is a linear, branched, or cyclic alkyl group containing 1 to 18 carbon atoms.