Method using fluoropolymer emulsions

1. 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 C 1 to C 18 , 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—(OCH 2 CH 2 ) a —O—C(O)—C(R 1 )═CH 2   (I)

wherein a is 1 to from about 10; R is hydrogen, C 1 -C 4 alkyl, or —C(O)—C(R 1 )═CH 2 , and R 1 is H or —CH 3 ;

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)

R f 1 -L-X—C(O)—C(R)═CH 2   (II)

wherein R f 1 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—, —NR 6 —, —S—, —SO—, —SO 2 —, and —N(R 6 )C(O)— wherein R 6 is H or C 1 to C 6 alkyl, and said linking group optionally substituted with CH 2 Cl;

X is —O—, —N(R)—, or —S—, wherein R is H or CH 3 ;

(e) from about 10% to 30% by weight of one or more monomers of C 1 to C 18 , 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—(OCH 2 CH 2 ) a —O—C(O)—C(R 1 )═CH 2   (I)

wherein R is hydrogen, C 1 -C 4 alkyl, or —C(O)—C(R 1 )═CH 2 , and R 1 is H or —CH 3 ;

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)

(-L 2 -) d (-L 3 ) c (—Si—R 7 (4-d) )  (IV)

wherein:

L 2 represents an oxygen covalently bonded to M; and each L 3 is independently selected from the group consisting of H, a C 1 -C 2 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

R 7 is a linear, branched, or cyclic alkyl group containing 1 to 18 carbon atoms.

2. The method of claim 1 wherein R f 1 is F(CF 2 ) n , F(CF 2 ) n (CH 2 ) x [(CF 2 CF 2 ) p (CH 2 CH 2 ) q ] m , F(CF 2 ) n O(CF 2 ) n , F(CF 2 ) n OCFHCF 2 , or F(CF 2 ) n [OCF 2 CF(CF 3 )] p [OCF 2 CF 2 ] q , wherein n is 1 to about 6; x is 1 to about 6; and p, q, and m are each independently 1 to about 3.

3. The method of claim 1 wherein L is a bond, R 5 , R 6 -A, A, or ethylene oxide, wherein

A is C 1 -C 6 alkyl and R 5 is a divalent radical selected from the group consisting of —S(CH 2 ) u —,

u is an integer of from about 2 to about 4;

s is an integer of 1 to about 50; and

R 2 , R 3 , and R 4 are each independently hydrogen or an alkyl group containing 1 to about 6 carbon atoms.

4. The method of claim 1 wherein the hydrophobized nanoparticles have an average size of from about 10 to about 500 nm.

5. The method of claim 1 wherein in the first polymer the nanoparticles are present at from about 0.2% to about 0.8% by weight.

6. The method of claim 1 wherein the substrate, after contacting with the polymer, has a fluorine content of from about 0.05% to about 0.5% by weight.

7. The method of claim 1 wherein the substrate is a fibrous substrate.

8. A substrate comprising a fibrous substrate having been treated according to the method of claim 1 .

9. The substrate of claim 8 which is selected from the group consisting of fibers, yarns, fabrics, fabric blends, textiles, nonwovens, paper, leather, rugs and carpets.

10. The substrate of claim 9 which is comprised of cotton, cellulose, wool, silk, polyamide, polyester, polyolefin, polyacrylonitrile, polypropylene, rayon, nylon, aramid, acetate, spunlaced nonwovens, and spunbonded-meltblown-spunbonded nonwovens.