Fluoropolymer compositions and treated substrates

A method of providing water repellency, oil repellency and soil resistance to a substrate comprising contacting said substrate with a composition of an aqueous solution or dispersion of at least one polyurethane having at least one urea linkage prepared by:

• (i) reacting (a) at least one diisocyanate, polyisocyanate, or mixture thereof, having isocyanate groups, and (b) at least one fluorinated compound selected from the formula (I):
• Rf1-L-X (I)
• wherein
• Rf1 is a monovalent, partially or fully fluorinated, linear or branched, alkyl radical having 2 to 100 carbon atoms;
• optionally interrupted by 1 to 50 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—, —NR1—, —S—, —SO—, —SO2—, and —N(R1)C(O)— wherein R1 is H or C1 to C6 alkyl, and said linking group optionally substituted with CH2Cl;
• X is an isocyanate-reactive group selected from the group consisting of —OH, —N(R)H, and —SH;
• and thereafter
• (iii) reacting with (c) water and (d) 0.05 to about 2.0% by weight of an isocyanate-reactive fluorinated particulate component, based on a total dry-weight of the composition;
• wherein the isocyanate-reactive fluorinated particulate component comprises inorganic oxides of Si, Ti, Zn, Mn, Al, and Zr having at least one particle having a surface covalently bonded to at least one group represented by formula (IV)
• (L2)d(L3)cSi—(CH2)n—(Z1)a—[C(X1)]x—(Z2)l-Q1-Rf (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 each integers such that d is greater than or equal to 1, c is greater than or equal to 0, and d+c is 3;
• n is independently an integer from 1 to 12;
• a, x, and l are each integers such that the moiety of Formula (IV) represented by —(Z1)a—[C(X1)]x—(Z2)l— is at least one of the following moieties:
• i) a first moiety wherein a=1, x=1, and l=1;
• ii) a second moiety wherein a=1, x=0;
• and l=0;
• and
• iii) a third moiety wherein a=1, x=0, and l=1;
• Rf is a C2-C12 perfluoroalkyl optionally interrupted by oxygen or methylene,
• Q1 is selected from the group consisting of a C2-C12 hydrocarbylene optionally interrupted by at least one divalent organic group;
• X1 is O or S;
• wherein in said first moiety Z1 and Z2 are chosen such that:
• a) Z1 is —NH— and Z2 is selected from the group consisting of —NH—, —O—, —S—, —NH—S(O)2—, —N[C(O)H]—, —[HC(COOH)(R14)]CH—S—, and —(R14)CH[HC(COOH)]—S—;
• wherein
• each R14 is independently hydrogen, phenyl, or a monovalent C1-C8 alkyl optionally terminated by —C6H5, or
• b) Z2 is —NH— and Z1 is selected from the group consisting of —O—, —S—, —N[-Q2-(Rf)]—, or
• wherein Q2 is independently selected from the group consisting of a C2-C12 hydrocarbylene optionally interrupted by at least one divalent organic group;
• c) provided that when Z1 or Z2 is O, Q1 is interrupted by at least one divalent moiety selected from the group consisting of —S—, —S(O)—, —S(O)2—, —NH—S(O)2—, —N(CH)3S(O)2—, and
• and
• wherein in said second moiety
• a) Z1 is —N(-Q3-Rf)—;
• and
• b) Q1 and Q3 are independently chosen from the group consisting of a C2-C12 hydrocarbylene interrupted by at least one of —C(O)—O— or —O—C(O)—, and optionally further interrupted by at least one divalent organic group;
• and
• wherein in said third moiety
• a) Z1 and Z2 are mutually exclusive and are selected from the group consisting of —N(Q4)- and —S(O)2—;
• and
• b) Q4 is a monovalent moiety selected from the group consisting of C2-C12 alkyl, —C6H5, and —(CH2)g—NH—S(O)2—(CH2)g—Rf where g is 1 or 2, and Rf is as defined above.