Method of preparing polymeric adhesive compositions utilizing the mechanism of interaction between the polymer components

Abstract

A method of selecting components for use in water-absorbing pressure-sensitive adhesive compositions is provided. The method involves selecting a film-forming polymer, a ladder-like non-covalent crosslinker that is capable of forming a ladder-like interpolymer complex with the film-forming polymer selected, and selecting a carcass-like non-covalent crosslinker that is capable of forming a carcass-like complex with at least one of the film-forming polymer selected or the ladder-like non-covalent crosslinker selected. The adhesive hydrogels provide high adhesion in a swollen state and bridge the gap between conventional pressure sensitive adhesives and bioadhesives. Methods for preparing and using the resulting compositions are also disclosed.

1 . An adhesive composition comprising: 
 a film-forming polymer selected from water-swellable water-insoluble polymers and water-soluble polymers;    a ladder-like non-covalent crosslinker that contains complementary reactive functional groups in the repeating units of the backbone, and is capable of forming a ladder-like interpolymer complex with the film-forming polymer; and    a carcass-like non-covalent crosslinker that contains complementary reactive functional groups at its ends, and is capable of forming a carcass-like complex with at least one of the film-forming polymer or the ladder-like non-covalent crosslinker;    wherein the amount of the film-forming polymer is greater than the amount of the ladder-like non-covalent crosslinker or the amount of the carcass-like non-covalent crosslinker.    
     
     
         2 . The composition of  claim 1 , which comprises about 20-95 wt % of the film-forming polymer.  
     
     
         3 . The composition of  claim 1 , which comprises about 0.5-40 wt % of the ladder-like crosslinker.  
     
     
         4 . The composition of  claim 1 , which comprises about 0.5-60 wt % of the carcass-like crosslinker.  
     
     
         5 . The composition of  claim 1 , wherein the water-swellable water-insoluble polymer is selected from cellulose derivatives, and acrylate-based polymers and copolymers.  
     
     
         6 . The composition of  claim 5 , wherein the cellulose derivative is a cellulose ester polymer containing unesterified cellulose monomer units, cellulose acetate monomer units, and either cellulose butyrate monomer units or cellulose propionate monomer units.  
     
     
         7 . The composition of  claim 5 , wherein the cellulose derivative is a polymer containing hydroxyalkyl cellulose monomer units or carboxyalkyl cellulose monomer units.  
     
     
         8 . The composition of  claim 5 , wherein the acrylate-based polymer or copolymer is selected from polymers and copolymers of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.  
     
     
         9 . The composition of  claim 1 , wherein the water-soluble polymer is selected from water-soluble cellulose derived polymers, homopolymer and copolymers of vinyl alcohols, homopolymer and copolymers of vinyl phenols, homopolymer and copolymers of ethylene oxides, homopolymer and copolymers of maleic acid, collagen, gelatin, alginates, starches, and naturally occurring polysaccharides.  
     
     
         10 . The composition of  claim 9 , wherein the water-soluble cellulose derived polymer is selected from hydroxypropylcellulose, hydroxyethylcellulose, methylcellulose, hydroxypropyl methylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, hydratecellulose, and hydroxypropylmethylcellulose.  
     
     
         11 . The composition of  claim 9 , wherein the naturally occurring polysaccharide is selected from agars, alginates, derivatives of alginic acid, carrageenans, chitin, chitosan, glucomannan, gellan gum, gelatin, gum guar, gum Arabic, gum ghatti, gum karaya, gum tragacanth, locust bean gum, pectins, pullulan, starches and starch derivatives, tamarind gum, and xanthans.  
     
     
         12 . The composition of  claim 1 , wherein the ladder-like non-covalent crosslinker is selected from hydrophilic polymers, water-swellable water-insoluble polymers, water-soluble polymers, copolymers of hydrophilic and hydrophobic monomers, and combinations thereof.  
     
     
         13 . The composition of  claim 12 , wherein the hydrophilic polymer is selected from poly(dialkyl aminoalkyl acrylates), poly(dialkyl aminoalkyl methacrylates), polyamines, polyvinyl amines, poly(alkylene imines), polyacrylic acids, polymethacrylic acids, polymaleic acids, polysulfonic acids, poly(N-vinyl lactams), polyalkylene oxides, polyvinyl alcohols, polyvinyl phenols, poly(hydroxyalkyl acrylates), poly(hydroxyalkyl methacrylates), poly(N-vinyl acrylamides), poly(N-alkylacrylamides), polar derivatives of cellulose containing hydroxyl and carboxyl groups, alginic acid, chitosan, gelatin, combinations and copolymers thereof.  
     
     
         14 . The composition of  claim 12 , wherein the water-swellable water-insoluble polymer is selected from cellulose derivatives, acrylate-based polymers and copolymers, and combinations thereof.  
     
     
         15 . The composition of  claim 14 , wherein the cellulose derivative is a cellulose ester polymer containing unesterified cellulose monomer units, cellulose acetate monomer units, and either cellulose butyrate monomer units or cellulose propionate monomer units.  
     
     
         16 . The composition of  claim 14 , wherein the cellulose derivative is a polymer containing hydroxyalkyl cellulose monomer units or carboxyalkyl cellulose monomer units.  
     
     
         17 . The composition of  claim 14 , wherein the acrylate-based polymer or copolymer is selected from polymers and copolymers of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.  
     
     
         18 . The composition of  claim 12 , wherein the water-soluble polymer is selected from water-soluble cellulose derived polymers, homopolymer and copolymers of vinyl alcohols, homopolymer and copolymers of vinyl phenols, homopolymer and copolymers of ethylene oxides, homopolymer and copolymers of maleic acid, collagen, gelatin, alginates, starches, naturally occurring polysaccharides, and combinations thereof.  
     
     
         19 . The composition of  claim 1 , wherein the carcass-like non-covalent crosslinker is selected from monomeric and oligomeric alkylene glycols comprising about 1-20 alkylene oxide units in their chains, polyalcohols, alkane diols, carbonic diacids, ether alcohols, poly(alkylene glycol diacids), and combinations thereof.  
     
     
         20 . The composition of  claim 1 , further comprising at least one active agent.  
     
     
         21 . The composition of  claim 1 , further comprising at least one additive selected from absorbent fillers, preservatives, pH regulators, plasticizers, softeners, thickeners, antioxidants, pigments, dyes, conductive species, refractive particles, stabilizers, toughening agents, tackifiers or adhesive agents, detackifiers, flavorants and sweeteners, antioxidants, and permeation enhancers.  
     
     
         22 . The composition of  claim 1 , wherein the film-forming polymer is an acrylate polymer, the ladder-like crosslinker is a poly(N-vinyl lactam), and the carcass-like crosslinker is an oligomeric alkylene glycol comprising about 1-20 alkylene oxide units in its chain.  
     
     
         23 . The composition of  claim 1 , further comprising a second ladder-like non-covalent crosslinker that contains complementary reactive functional groups in the repeating units of the backbone, and is capable of forming a ladder-like interpolymer complex with the film-forming polymer or the first ladder-like non-covalent crosslinker; and 
 wherein the carcass-like non-covalent crosslinker is capable of forming a carcass-like complex with at least one of the film-forming polymer, the first ladder-like non-covalent crosslinker or the second ladder-like non-covalent crosslinker.    
     
     
         24 . The composition of  claim 23 , wherein the second ladder-like non-covalent crosslinker is capable of forming a ladder-like interpolymer complex with the first ladder-like non-covalent crosslinker and the carcass-like non-covalent crosslinker is capable of forming a carcass-like complex with the second ladder-like non-covalent crosslinker.  
     
     
         25 . The composition of  claim 24 , wherein the film-forming polymer and the first ladder-like crosslinker are acrylate polymers, the second ladder-like crosslinker is a poly(N-vinyl lactam), and the carcass-like crosslinker is an oligomeric alkylene glycol comprising about 1-20 alkylene oxide units in its chain.  
     
     
         26 . A method of selecting polymer components for use in an adhesive composition, comprising: 
 (a) selecting a film-forming polymer;    (b) selecting a ladder-like non-covalent crosslinker that contains complementary reactive functional groups in the repeating units of the backbone, and is capable of forming a ladder-like interpolymer complex with the film-forming polymer selected; and    (c) selecting a carcass-like non-covalent crosslinker that contains complementary reactive functional groups at its ends, and is capable of forming a carcass-like complex with at least one of the film-forming polymer selected or the ladder-like non-covalent crosslinker selected; and wherein the amount of the film-forming polymer is greater than the amount of the ladder-like non-covalent crosslinker or the amount of the carcass-like non-covalent crosslinker.    
     
     
         27 . The method of  claim 26 , wherein the amount of the film-forming polymer is about 20-95 wt % of the composition, the amount of the ladder-like crosslinker is about 0.5-40 wt % of the composition, and the amount of the carcass-like crosslinker is about 0.5-60 wt % of the composition.  
     
     
         28 . The method of  claim 26 , wherein the film-forming polymer is selected from hydrophilic polymers, water-swellable water-insoluble polymers, water-soluble polymers, and copolymers of hydrophilic and hydrophobic monomers.  
     
     
         29 . The method of  claim 28 , wherein the hydrophilic polymer is selected from poly(dialkyl aminoalkyl acrylates), poly(dialkyl aminoalkyl methacrylates), polyamines, polyvinyl amines, poly(alkylene imines), polyacrylic acids, polymethacrylic acids, polymaleic acids, polysulfonic acids, poly(N-vinyl lactams), polyalkylene oxides, polyvinyl alcohols, polyvinyl phenols, poly(hydroxyalkyl acrylates), poly(hydroxyalkyl methacrylates), poly(N-vinyl acrylamides), poly(N-alkylacrylamides), polar derivatives of cellulose containing hydroxyl and carboxyl groups, alginic acid, chitosan, gelatin, and copolymers thereof.  
     
     
         30 . The method of  claim 28 , wherein the water-swellable water-insoluble polymer is selected from cellulose derivatives, and acrylate-based polymers and copolymers.  
     
     
         31 . The method of  claim 30 , wherein the cellulose derivative is a cellulose ester polymer containing unesterified cellulose monomer units, cellulose acetate monomer units, and either cellulose butyrate monomer units or cellulose propionate monomer units.  
     
     
         32 . The method of  claim 30 , wherein the cellulose derivative is a polymer containing hydroxyalkyl cellulose monomer units or carboxyalkyl cellulose monomer units.  
     
     
         33 . The method of  claim 30 , wherein the acrylate-based polymer or copolymer is selected from polymers and copolymers of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.  
     
     
         34 . The method of  claim 28 , wherein the water-soluble polymer is selected from water-soluble cellulose derived polymers, homopolymer and copolymers of vinyl alcohols, homopolymer and copolymers of vinyl phenols, homopolymer and copolymers of ethylene oxides, homopolymer and copolymers of maleic acid, collagen, gelatin, alginates, starches, and naturally occurring polysaccharides.  
     
     
         35 . The method of  claim 26 , wherein the ladder-like non-covalent crosslinker is selected from hydrophilic polymers, water-swellable water-insoluble polymers, water-soluble polymers, copolymers of hydrophilic and hydrophobic monomers, and combinations thereof.  
     
     
         36 . The method of  claim 34 , wherein the hydrophilic polymer is selected from poly(dialkyl aminoalkyl acrylates), poly(dialkyl aminoalkyl methacrylates), polyamines, polyvinyl amines, poly(alkylene imines), polyacrylic acids, polymethacrylic acids, polymaleic acids, polysulfonic acids, poly(N-vinyl lactams), polyalkylene oxides, polyvinyl alcohols, polyvinyl phenols, poly(hydroxyalkyl acrylates), poly(hydroxyalkyl methacrylates), poly(N-vinyl acrylamides), poly(N-alkylacrylamides), polar derivatives of cellulose containing hydroxyl and carboxyl groups, alginic acid, chitosan, gelatin, combinations and copolymers thereof.  
     
     
         37 . The method of  claim 35 , wherein the water-swellable water-insoluble polymer is selected from cellulose derivatives, acrylate-based polymers and copolymers, and combinations thereof.  
     
     
         38 . The method of  claim 37 , wherein the cellulose derivative is a cellulose ester polymer containing unesterified cellulose monomer units, cellulose acetate monomer units, and either cellulose butyrate monomer units or cellulose propionate monomer units.  
     
     
         39 . The method of  claim 37 , wherein the cellulose derivative is a polymer containing hydroxyalkyl cellulose monomer units or carboxyalkyl cellulose monomer units.  
     
     
         40 . The method of  claim 37 , wherein the acrylate-based polymer or copolymer is selected from polymers and copolymers of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.  
     
     
         41 . The method of  claim 35 , wherein the water-soluble polymer is selected from water-soluble cellulose derived polymers, homopolymer and copolymers of vinyl alcohols, homopolymer and copolymers of vinyl phenols, homopolymer and copolymers of ethylene oxides, homopolymer and copolymers of maleic acid, collagen, gelatin, alginates, starches, naturally occurring polysaccharides, and combinations thereof.  
     
     
         42 . The method of  claim 35 , which further comprises selecting one or more additional ladder-like non-covalent crosslinkers.  
     
     
         43 . The method of  claim 26 , wherein the carcass-like non-covalent crosslinker is selected from monomeric and oligomeric alkylene glycols comprising about 1-20 alkylene oxide units in their chains, polyalcohols, alkane diols, carbonic diacids, ether alcohols, poly(alkylene glycol diacids), and combinations thereof.  
     
     
         44 . The method of  claim 43 , which further comprises selecting one or more additional carcass-like non-covalent crosslinkers.  
     
     
         45 . A method of manufacturing an adhesive composition, comprising: 
 (a) 
 (i) selecting a film-forming polymer;  
 (ii) selecting a ladder-like non-covalent crosslinker that contains complementary reactive functional groups in the repeating units of the backbone, and is capable of forming a ladder-like interpolymer complex with the film-forming polymer selected; and  
 (iii) selecting a carcass-like non-covalent crosslinker that contains complementary reactive functional groups at its ends, and is capable of forming a carcass-like complex with at least one of the film-forming polymer selected or the ladder-like non-covalent crosslinker selected; and wherein the amount of the film-forming polymer is greater than the amount of the ladder-like non-covalent crosslinker or the amount of the carcass-like non-covalent crosslinker;  
   (b) mixing the film-forming polymer, ladder-like non-covalent crosslinker and carcass-like non-covalent crosslinker; and    (c) forming an adhesive composition by melt extrusion or solution casting.