Polymer-fluorosurfactant associative complexes

A method for preparing a treated article comprising the steps of:

• 1. providing a substrate;
• and
• 2. applying to at least one surface of said substrate a treatment composition that comprises:
• (a) an associative complex comprising:
• i. a water soluble and/or water dispersible polymer;
• ii. at least one polymeric fluorosurfactant wherein said polymeric fluorosurfactant comprises a fluorosurfactant derived from polymerization of a fluorinated oxetane and is selected from the group consisting of anionic, cationic, zwitterionic and/or ionizable fluorinated polymeric surfactants, and/or mixtures thereof wherein said fluorosurfactant forms an associative complex with said polymer;
• (b) optionally, a dispersant, and;
• (c) optionally, a liquid carrier;
• and
• 3. removing said treatment composition from said substrate to leave a treated article whereby said associative complex is deposited on said surface of said substrate;
• wherein said water soluble and/or water dispersible polymer comprises a charged and/or polarizable first constituent and said polymeric fluorosurfactant comprises a charged and/or polarizable second constituent, wherein said second constituent bears an opposite charge to each other;
• wherein the associative complex forms an invisible film upon said surface of said substrate wherein said film is less than 500 nanometers in average thickness;
• wherein the associative complex molar ratio parameter, R, is greater than 0 to about 20.0.

A method for preparing a treated article comprising the steps of:

• (1) providing a substrate;
• and
• (2) applying to at least one surface of said substrate a first treatment composition that comprises:
• a. a water soluble and/or water dispersible polymer,
• b. a liquid carrier;
• c. optionally, a dispersant and/or cleaning agent, and
• (3) removing said first treatment composition from said substrate, and;
• (4) applying to said surface a second treatment composition comprising:
• a. a polymeric fluorosurfactant wherein said polymeric fluorosurfactant comprises a fluorosurfactant derived from polymerization of a fluorinated oxetane,
• b. a second liquid carrier;
• and;
• (5) removing said second treatment composition from said substrate, whereby an associative complex comprising said polymer and said fluorosurfactant is formed on said surface of said substrate;
• wherein said water soluble and/or water dispersible polymer comprises a charged and/or polarizable first constituent and said polymeric fluorosurfactant comprises a charged and/or polarizable second constituent, wherein said second constituent bears an opposite charge to each other;
• wherein the associative complex forms an invisible film upon said surface of said substrate wherein said film is less than 500 nanometers in average thickness;
• and
• wherein the associative complex molar ratio parameter, R, is greater than 0 to about 20.0.

A composition comprising:

• a. an associative complex comprising:
• i. a water soluble and/or water dispersible polymer;
• ii. at least one polymeric fluorosurfactant capable of forming an associative complex with said polymer;
• wherein said polymeric fluorosurfactant comprises a fluorosurfactant derived from polymerization of a fluorinated oxetane and comprises at least one radical independently selected from the group consisting of —CF3, —CF2CF3, —(CF2)pCF3, —R′CF3, —R′(CF3)p, —R″(CF3)q, perfluorinated alkyl radical, perfluorinated aryl radical, partially fluorinated alkyl radical, partially fluorinated aryl radical, derivatives thereof, and/or combinations thereof, wherein R′ is a C1 to C20 linear or branched, alkyl or alkylene moiety, optionally substituted with and/or terminated with at least one —CF3 group, R″ is radical comprising a benzyl, phenyl and/or aryl group with q degrees of —CF3 substitution, wherein p is 1 to about 10, wherein q is between 1 and 5;
• b. optionally, a dispersant, and;
• c. optionally, a liquid carrier,
• wherein the associative complex forms an invisible film upon a surface of a substrate wherein said film is less than 500 nanometers in average thickness;
• wherein the associative complex molar ratio parameter, R, is greater than 0 to about 20, and wherein said associative complex is selected from
• I) (A) said polymer comprising a charged polyelectrolyte;
• and
• (B) said polymeric fluorosurfactant comprising at least one monomer bearing a permanent charge opposite to the charge upon said polyelectrolyte.

A method for preparing a treated article comprising the steps of:

• (a) providing a substrate;
• (b) applying to at least one surface of said substrate a first treatment composition that comprises a water soluble and/or water dispersible polymer;
• (c) applying to the same one surface of said substrate a second treatment composition that comprises at least one polymeric fluorosurfactant wherein said polymeric fluorosurfactant comprises a fluorosurfactant derived from polymerization of a fluorinated oxetane and is selected from the group consisting of, anionic, cationic, zwitterionic and/or ionizable fluorinated polymeric surfactants, and/or mixtures thereof;
• (d) optionally, allowing the surface of said substrate to dry between said step (b) of applying said first treatment composition and said step (c) of applying said second treatment composition;
• (e) allowing said surface of said substrate treated with said first treatment composition to interact with said second treatment composition to form an associative complex between said water soluble and/or water dispersible polymer and said polymeric fluorosurfactant on said surface of said substrate;
• and
• (f) removing said first and second treatment compositions from said substrate to leave a treated article whereby said associative complex is deposited on at least one surface of said substrate;
• wherein said water soluble and/or water dispersible polymer comprises a charged and/or polarizable first constituent and said polymeric fluorosurfactant comprises a charged and/or polarizable second constituent, wherein said second constituent bears an opposite charge to each other;
• wherein the associative complex forms an invisible film upon a surface of a substrate wherein said film is less than 500 nanometers in average thickness;
• and
• wherein the associative complex molar ratio parameter, R, is greater than 0 to about 20;
• wherein said step (b) and step (c) may be reversed in respect to the order of application of respective said first treatment composition and said second treatment composition onto the surface of said substrate.