Polyurethane-polyacrylate hybrid systems for packaging inks and coatings

Abstract

Described herein are compositions suitable for use as binder components for inclusion in printing inks and coatings, such as those used in the gravure and flexographic printing process and which are printed on substrates such as polyolefin (e.g., polyethylene, polypropylene) and poly(ethylene terephthalate) (PET). The compositions are non-aqueous dispersions in which an one or more ethylenically unsaturated acrylates or (meth)acrylates is polymerized with a polyurethane, polyurethane-urea or polyurea in a non-aqueous polymerization medium, such as esters, ketones, and mixtures thereof, forming polymeric hybrid resins in the polymerization medium, which are solvent-dispersible hybrid resins of polyurethane-polyacrylate, polyurethane-urea-polyacrylate, and polyurea-polyacrylate. Films of hybrid resins are also disclosed. These materials exhibit improved film adhesion and are suitable for flexographic and gravure printing inks, especially for printing applications where adhesive lamination bond strengths are required, especially plastic films packaging applications.

1 - 29 . (canceled) 
     
     
         30 . A multilayer structure comprising:
 a substrate, optionally having a primer layer applied thereto;   a plurality of ink layers;   optionally, an overprint varnish layer,   
       wherein one or more of the ink layers, optional primer layer, and optional overprint varnish layer comprise a non-aqueous dispersion comprising:
 a non-aqueous medium consisting of one or more solvents selected from the group consisting of alcohols, esters and ketones, and 
 one or more polymeric hybrid resins selected from polyurethane-polyacrylate, polyurethane-urea-polyacrylate, and polyurea-polyacrylate, dispersed in the non-aqueous medium, 
 
       wherein the hybrid resins are produced in the non-aqueous medium in a polymerization reaction between one or more ethylenically unsaturated acrylates and one or more of a polyurethane, a polyurethane-urea, and a polyurea polymer soluble in the medium,
 and 
 
       wherein the non-aqueous dispersion contains no aromatic hydrocarbon solvents. 
     
     
         31 . The multilayer structure of  claim 30 , further comprising a curing component, and wherein the multilayer structure is cured by actinic radiation. 
     
     
         32 . The multilayer structure of  claim 30 , further comprising a second substrate positioned over the plurality of ink layers. 
     
     
         33 . A multilayer laminated structure comprising:
 a substrate;   a top laminate layer; and   intermediate layers between the substrate and top laminate layer, comprising:
 an optional primer layer applied to the substrate; 
 a plurality of ink layers; and 
 an optional overprint varnish layer; 
   
       wherein one or more of intermediate layers comprise a non-aqueous dispersion comprising:
 a non-aqueous medium consisting of one or more solvents selected from the group consisting of alcohols, esters and ketones, and 
 one or more polymeric hybrid resins selected from polyurethane-polyacrylate, polyurethane-urea-polyacrylate, and polyurea-polyacrylate, dispersed in the non-aqueous medium, 
 
       wherein the hybrid resins are produced in the non-aqueous medium in a polymerization reaction between one or more ethylenically unsaturated acrylates and one or more of a polyurethane, a polyurethane-urea, and a polyurea polymer soluble in the medium,
 and 
 
       wherein the non-aqueous dispersion contains no aromatic hydrocarbon solvents. 
     
     
         34 . The multilayer laminated structure of  claim 33 , wherein the top laminate layer comprises a layer of molten resin extruded onto the intermediate layers; and/or wherein the multilayer laminated structure further comprises an adhesive layer applied over the intermediate layers; and wherein the top laminate layer comprises a plastic film applied over the adhesive layer. 
     
     
         35 . The multilayer laminated structure of  claim 33 , further comprising a curing component, and wherein the multilayer laminated structure is cured by actinic radiation. 
     
     
         36 . The multilayer laminated structure of  claim 33 , further comprising a second substrate positioned between the overprint varnish and the plurality of ink layers. 
     
     
         37 . A polymeric film comprising a hybrid polymer produced by polymerizing one or more ethylenically unsaturated acrylates with a polymer selected from a polyurethane, a polyurethane-urea, and a polyurea. 
     
     
         38 . A polymeric film of  claim 37 , wherein the film is derived from a non-aqueous dispersion comprising:
 a non-aqueous medium consisting of one or more solvents selected from the group consisting of alcohols, esters and ketones, and   one or more polymeric hybrid resins selected from polyurethane-polyacrylate, polyurethane-urea-polyacrylate, and polyurea-polyacrylate, dispersed in the non-aqueous medium,   wherein the hybrid resins are produced in the non-aqueous medium in a polymerization reaction between one or more ethylenically unsaturated acrylates and one or more of a polyurethane, a polyurethane-urea, and a polyurea polymer soluble in the medium, and   wherein the non-aqueous dispersion contains no aromatic hydrocarbon solvents;   by separating the medium from the hybrid resins, whereby a film comprised of the hybrid resins is produced.   
     
     
         39 . An ink-, coating-, primer-, or overprint varnish-composition, comprising the film of  claim 37 . 
     
     
         40 . An ink-, coating-, primer-, or overprint varnish-composition, comprising the film of  claim 38 . 
     
     
         41 . The multilayer laminated structure of  claim 30 , wherein the substrate, plurality of ink layers; and/or overprint varnish layer, comprises a polymeric film comprising a hybrid polymer produced by polymerizing one or more ethylenically unsaturated acrylates with a polymer selected from a polyurethane, a polyurethane-urea, and a polyurea. 
     
     
         42 . The multilayer laminated structure of  claim 41 , wherein the polymeric film is derived from a non-aqueous dispersion comprising:
 a non-aqueous medium consisting of one or more solvents selected from the group consisting of alcohols, esters and ketones, and   one or more polymeric hybrid resins selected from polyurethane-polyacrylate, polyurethane-urea-polyacrylate, and polyurea-polyacrylate, dispersed in the non-aqueous medium,   wherein the hybrid resins are produced in the non-aqueous medium in a polymerization reaction between one or more ethylenically unsaturated acrylates and one or more of a polyurethane, a polyurethane-urea, and a polyurea polymer soluble in the medium, and   wherein the non-aqueous dispersion contains no aromatic hydrocarbon solvents;   
       by separating the medium from the hybrid resins, whereby a film comprised of the hybrid resins is produced. 
     
     
         43 . The multilayer laminated structure of  claim 33 , wherein the substrate, top laminate layer; and/or intermediate layers between the substrate and top laminate layer comprises a polymeric film comprising a hybrid polymer produced by polymerizing one or more ethylenically unsaturated acrylates with a polymer selected from a polyurethane, a polyurethane-urea, and a polyurea. 
     
     
         44 . The multilayer laminated structure of  claim 43 , wherein the polymeric film is derived from a non-aqueous dispersion comprising:
 a non-aqueous medium consisting of one or more solvents selected from the group consisting of alcohols, esters and ketones, and   one or more polymeric hybrid resins selected from polyurethane-polyacrylate, polyurethane-urea-polyacrylate, and polyurea-polyacrylate, dispersed in the non-aqueous medium,   wherein the hybrid resins are produced in the non-aqueous medium in a polymerization reaction between one or more ethylenically unsaturated acrylates and one or more of a polyurethane, a polyurethane-urea, and a polyurea polymer soluble in the medium, and   wherein the non-aqueous dispersion contains no aromatic hydrocarbon solvents;   
       by separating the medium from the hybrid resins, whereby a film comprised of the hybrid resins is produced. 
     
     
         45 . The multilayer laminated structure of  claim 34 , comprising a polymeric film comprising a hybrid polymer produced by polymerizing one or more ethylenically unsaturated acrylates with a polymer selected from a polyurethane, a polyurethane-urea, and a polyurea. 
     
     
         46 . The multilayer laminated structure of  claim 45 , wherein the polymeric film is derived from a non-aqueous dispersion comprising:
 a non-aqueous medium consisting of one or more solvents selected from the group consisting of alcohols, esters and ketones, and   one or more polymeric hybrid resins selected from polyurethane-polyacrylate, polyurethane-urea-polyacrylate, and polyurea-polyacrylate, dispersed in the non-aqueous medium,   wherein the hybrid resins are produced in the non-aqueous medium in a polymerization reaction between one or more ethylenically unsaturated acrylates and one or more of a polyurethane, a polyurethane-urea, and a polyurea polymer soluble in the medium, and   wherein the non-aqueous dispersion contains no aromatic hydrocarbon solvents;   
       by separating the medium from the hybrid resins, whereby a film comprised of the hybrid resins is produced.