Polyelectrolyte Complexes

Abstract

The present invention relates to aqueous compositions of associative polyelectrolyte complexes (PECs), optionally containing surfactants, biocidal agents and/or oxidants, which can provide surface protection to treated articles including reduced soiling tendency, reduced cleaning effort and improved soil repellancy, as well as providing bacteriostatic properties to treated surfaces that thereby gain resistance to water, environmental exposure and microbial challenge. Treatment means and compositions are provided that employ associative polyelectrolyte complexes formed by combining a water soluble cationic first polyelectrolyte with a water soluble second polyelectrolyte bearing groups of opposite charge to the first polyelectrolyte under suitable mixing conditions where the one polyelectrolyte present in molar excess is added in the form of a first aqueous solution during a mixing step to a second aqueous solution comprising the oppositely charged polyelectrolyte present in molar deficiency. Also provided are means to form stable associative polyelectrolyte complexes in aqueous solutions having R values from about 0.10 to 20, including near stoichiometric R values approaching 1, being the ratio of charged groups present on the component polyelectrolytes employed.

1 . A method of forming a treated article, comprising:
 a. applying a treatment composition to at least one surface of an article comprising a suitable substrate material;   b. allowing said treatment composition to deposit at least one layer comprising a plurality of associative polyelectrolyte complexes on said surface;   c. removing said treatment composition from said surface by means selected from allowing the surface to drain, allowing the surface to dry, wiping the surface with a wiping implement, rinsing the surface with water, and combinations thereof;   wherein said treatment composition comprises:   (i) an aqueous composition comprising at least one associative polyelectrolyte complex formed by combining a water soluble cationic first polyelectrolyte; and a water soluble second polyelectrolyte bearing groups of opposite charge to said first polyelectrolyte; wherein the one polyelectrolyte present in molar excess is added in the form of a first aqueous solution during a mixing step to a second aqueous solution comprising the oppositely charged polyelectrolyte present in molar deficiency; wherein R, the molar ratio of charged groups present on said first polyelectrolyte to oppositely charged groups present on said second polyelectrolyte is between 0.10 to 20; and wherein said treatment composition further comprises:   (ii) a buffering agent;   (iii) optionally, a surfactant;   (iv) optionally, a biocidal agent; and   (v) optionally, an oxidant.   
     
     
         2 . The method according to  claim 1 , wherein said mixing step is accomplished without high shear mixing by means of a low energy mixing means selected from liquid-to-liquid addition, stirring, static mixing, paddle mixing, low-shear mixing, and combinations thereof; wherein said low energy mixing is accomplished at temperatures between 10 to 45° C. 
     
     
         3 . The method according to  claim 1 , wherein said plurality of associative polyelectrolyte complexes is formed at a concentration of less than or equal to about 100 millimolar with respect to the total concentration of charged associating groups present on said polyelectrolytes present in said plurality of associative polyelectrolyte complexes. 
     
     
         4 . The method according to  claim 1 , wherein said plurality of associative polyelectrolyte complexes have an average aggregate size in solution of less than about 500 nanometers. 
     
     
         5 . The method according to  claim 4 , wherein said plurality of associative polyelectrolyte complexes have an average R G  and average R H  value in solution of between about 20 nanometers to about 300 nanometers. 
     
     
         6 . The method according to  claim 1 , wherein said cationic first polyelectrolyte and said second polyelectrolyte are not selected from the group consisting of synthetic block copolymer, polymer fluorosurfactant derived from polymerization of a fluorinated oxetane, cross-linked polyacrylic acid, silicone polymer, anionic latex, water-insoluble anionic polysaccharide containing glucoronic acid, amphoteric derivatives of chitin or chitosan, including carboxymethyl N-acetyl chitosan, and a combination of chitosan and copolymers of acrylate and styrene monomers, and/or styrene derivatives, and/or combinations thereof. 
     
     
         7 . The method according to  claim 1 , wherein said layer formed on the surface of said article is non-permanent, invisible to the human eye, capable of sequestering moisture from the atmosphere, and is less than about 500 nanometers in thickness. 
     
     
         8 . The method according to  claim 1 , wherein said surfactant is selected from the group consisting of water soluble and/or water dispersible anionic, cationic, zwitterionic, nonionic or amphoteric surfactants. 
     
     
         9 . The method according to  claim 1 , wherein said biocidal agent is selected from the group consisting of alcohols, chlorinated hydrocarbons, organometallics, halogen-releasing compounds, metallic salts, pine oil, organic sulfur compounds, iodine, compounds, antimicrobial metal cations and/or antimicrobial metal cation-releasing compounds, chitosan, quaternary alkyl ammonium biocides, phenolics, germicidal oxidants, germicidal essential oils, germicidal botanical extracts, alpha-hydroxycarboxylic acids, and combinations thereof. 
     
     
         11 . The method according to  claim 1 , wherein said oxidant is selected from the group consisting of hydrogen peroxide, an alkaline metal salt and/or alkaline earth metal salt of hypochlorous acid, hypochlorous acid, solubilized chlorine, a source of free chlorine, solubilized chlorine dioxide, acidic sodium chlorite, an active chlorine generating compound, an active oxygen generating compound, a chlorine-dioxide generating compound, solubilized ozone, sodium potassium peroxysulfate, sodium perborate, and combinations thereof and wherein said first polyelectrolyte and said second polyelectrolyte are oxidant stable polymers. 
     
     
         12 . The method according to  claim 1 , wherein said plurality of associative polyelectrolyte complexes does not form a gel phase or macroscopic solid phase. 
     
     
         13 . The method according to  claim 1 , wherein said first polyelectrolyte and said second polyelectrolyte is completely soluble in water at a level of at least 10 g in 100 ml of water at a temperature of 25° C. 
     
     
         14 . The method according to  claim 1 , wherein said treated article is treated in a second treatment step comprising the step of applying to the surface of said article a disinfecting composition comprising a biocidal agent and optionally a cleaning adjunct; wherein said layer of said plurality of associative polyelectrolyte complexes on said surface of said treated article thereby incorporates a sufficient amount of said biocidal agent so as to provide an effective amount of the biocidal agent on the surface during said second treatment step. 
     
     
         15 . The method according to  claim 14 , wherein said biocidal agent is selected from the group consisting of alcohols, chlorinated hydrocarbons, organometallics, halogen-releasing compounds, metallic salts, pine oil, organic sulfur compounds, iodine, compounds, antimicrobial metal cations and/or antimicrobial metal cation-releasing compounds, chitosan, quaternary alkyl ammonium biocides, phenolics, germicidal oxidants, germicidal essential oils, germicidal botanical extracts, alpha-hydroxycarboxylic acids, and combinations thereof. 
     
     
         16 . The method according to  claim 1 , wherein said first and second polyelectrolytes are selected from the group consisting of natural and/or naturally-derived polymers. 
     
     
         17 . The method according to  claim 16 , wherein at least one of said first and second polyelectrolyte is selected from the group consisting of chitosans, alginates, cellulosics, guar gums; and derivatives thereof; and combinations thereof. 
     
     
         18 . An aqueous treatment composition for treating the surface of an article, comprising:
 (i) an aqueous composition comprising at least one associative polyelectrolyte complex formed by combining a water soluble cationic first polyelectrolyte; and a water soluble second polyelectrolyte bearing groups of opposite charge to said first polyelectrolyte; wherein the one polyelectrolyte present in molar excess is added in the form of a first aqueous solution during a mixing step to a second aqueous solution comprising the oppositely charged polyelectrolyte present in molar deficiency; wherein R, the molar ratio of charged groups present on said first polyelectrolyte to oppositely charged groups present on said second polyelectrolyte is between 0.10 to 20; wherein said treatment composition further comprises:   (ii) a buffering agent;   (iii) a surfactant;   (iv) optionally, a biocidal agent; and   (v) optionally, an oxidant.   
     
     
         19 . The treatment composition according to  claim 18 , wherein said cationic first polyelectrolyte comprises a cationic polymer with at least one monomer having a permanent cationic charge or capable of forming a cationic charge in solution upon protonation; wherein said cationic polymer is selected from the group consisting of chitosan and derivatives thereof, cationic guar, cationic hydroxypropyl guar, cationic starch, derivatives thereof, and combinations thereof; wherein said at least one monomer having a permanent cationic charge is selected from the group consisting of diallyl dimethyl ammonium salts, quaternary ammonium salts of substituted acrylamide, methacrylamide, acrylate and methacrylate, trimethyl-ammoniumethyl methacrylate, trimethylammoniumpropyl methacryl-amide, trimethylammoniumethyl methacrylate, trimethylammonium-propyl acrylamide, 2-vinyl N-alkyl quaternary pyridinium, 4-vinyl N-alkyl quaternary pyridinium, 4-vinylbenzyltrialkylammonium, 2-vinyl piperidinium, 4-vinyl piperidinium, 3-alkyl 1-vinyl imidazolium, ionenes, and combinations thereof; and wherein said monomer capable of forming a cationic charge in solution upon protonation is selected from the group consisting of acrylamide, N,N-dimethylacrylamide, N,N di-isopropyl-acryalmide, N-vinylimidazole, N-vinylpyrrolidone, ethyleneimine, dimethylamino-hydroxypropyl diethylenetriamine, dimethylaminoethyl methacrylate, dimethyl-aminopropyl methacrylamide, dimethylaminoethyl acrylate, dimethylaminopropyl acrylamide, 2-vinyl pyridine, 4-vinyl pyridine, 2-vinyl piperidine, 4-vinylpiperi-dine, vinyl amine, diallylamine, methyldiallylamine, vinyl oxazolidone; vinyl methyoxazolidone, and vinyl caprolactam, derivatives thereof, and combinations thereof. 
     
     
         20 . The treatment composition according to  claim 19 , wherein said second polyelectrolyte comprises an anionic polymer with a least one monomer having a permanent anionic charge or capable of forming an anionic charge in solution; wherein said anionic polymer is selected from the group consisting of alginates, xanthates, pectins, carrageenans, guar, carboxymethyl cellulose, scleroglucans, derivatives thereof, and combinations thereof; wherein said monomer having a permanent anionic charge or capable of forming an anionic charge in solution is selected from the group consisting of acrylic acid, alginic acid, maleic acid, methacrylic acid, ethacrylic acid, dimethylacrylic acid, maleic anhydride, succinic anhydride, vinylsulfonate, cyanoacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, fumaric acid, itaconic acid, sorbic acid, angelic acid, cinnamic acid, styrylacrylic acid, citraconic acid, glutaconic acid, aconitic acid, phenylacrylic acid, acryloxypropionic acid, citraconic acid, vinylbenzoic acid, N-vinylsuccinamidic acid, mesaconic acid, methacroylalanine, acryloylhydroxyglycine, sulfoethyl methacrylate, sulfopropyl acrylate, sulfoethyl acrylate, styrenesulfonic acid, acrylamide methyl propane sulfonic acid, 2-methacryloyloxymethane-1-sulfonic acid, 3-methacryloyloxypropane-1-sulfonic acid, 3-(vinyloxy)propane-1-sulfonic acid, ethylenesulfonic acid, vinyl sulfuric acid, 4-vinylphenyl sulfuric acid, ethylene phosphonic acid, vinyl phosphoric acid, derivatives therefore, and combinations thereof. 
     
     
         21 . The treatment composition according to  claim 20 , wherein said cationic first polyelectrolyte and said second polyelectrolyte are not selected from the group consisting of synthetic block copolymer, polymer fluorosurfactant derived from polymerization of a fluorinated oxetane, cross-linked polyacrylic acid, a silicone polymer, anionic latex, water-insoluble anionic polysaccharide containing glucoronic acid, amphoteric derivatives of chitin or chitosan, including carboxymethyl N-acetyl chitosan, and a combination of chitosan and copolymers of acrylate and styrene monomers, and/or styrene derivatives, and/or combinations thereof.