Easily cleanable polymer laminates

Abstract

A substrate having an adherent and stain resistant layer having durability and flexibility, said layer comprising the reaction product of a reactive polyester having free carboxylic acid and/or hydroxyl groups, a hydroxyl terminated polymer including repeat units from an oxetane having pendant —CH 2 —O—(CH 2 ) n —Rf groups (said Rf groups generally being a fluorinated alkyl group) and an amino resin curative. The substrate may be printed or embossed or both. The coated substrate has both stain resistant properties and dry erase properties with dry erase markers. The coated substrate can be used as prepared or applied to other substrates.

What is claimed:  
     
         1 . A laminate comprising 
 1) a substrate    2) a stain resistant and adherent layer on said substrate, comprising the cross-linked reaction product of at least; 
 a) at least one amino resin cross-linking agent and either  
 b1) reactive polyester resin and  
 b2) a hydroxyl terminated polymer including repeat units from an oxetane having a pendant —CH 2 —O—(CH 2 ) n —Rf group or  
 c) a reactive polyester resin including therein at least one repeat unit derived from copolymerizing into said polyester a hydroxyl terminated polymer including repeat units from an oxetane having a pendant —CH 2 —O—(CH 2 ) n —Rf group, or combinations of a), b), or c), 
 wherein said Rf group, independently, being a linear or branched alkyl group of 1 to 20 carbon atoms and a minimum of 25 percent of the hydrogen atoms of said alkyl group being replaced by F, or said Rf group, independently, being a oxaperflourinated or perfluorinated polyether having from 4 to 60 carbon atoms, and n being from 1 to 3 and optionally, up to 20 wt %, based on the weight of said hydroxyl terminated polymer, of a cyclic tetramer from the polymerization of an oxetane monomer having a pendant —CH 2 —O—(CH 2 ) n —Rf group wherein Rf is described above.  
 
   
     
     
         2 . A laminate according to    claim 1    wherein a surface of said substrate has been printed at least one time.  
     
     
         3 . A laminate according to    claim 1   , wherein a surface of said substrate has been embossed.  
     
     
         4 . A laminate according to    claim 1   , wherein a surface of said substrate has been both printed and embossed.  
     
     
         5 . A laminate according to    claim 1   , wherein the surface of said substrate includes a layer of plasticized vinyl chloride polymer.  
     
     
         6 . A laminate according to    claim 1   , wherein said substrate comprises a cellulosic product, fibers, synthetic polymers, metal or ceramic.  
     
     
         7 . A laminate according to    claim 1   , wherein said Rf group is independently a linear or branched perfluorinated alkyl group of 1 to 20 carbon atoms.  
     
     
         8 . A laminate according to    claim 7   , wherein said hydroxyl terminated polymer includes repeat units from oxetanes and repeat units from tetrahydrofuran.  
     
     
         9 . A laminate according to    claim 7   , wherein said second layer has the characteristic of being easily cleaned of undesired markings without using liquids.  
     
     
         10 . The method which comprises; 
 1) applying to a substrate a layer of a catalyzed mixture of at least    a) one amino resin cross-linking agent and either    b1) a reactive polyester resin and    b2) a hydroxyl terminated polymer including repeat units from an oxetane having a pendant —CH 2 —O—(CH 2 ) n —Rf group or    c) a reactive polyester resin including at least one repeat unit derived from copolymerizing into said polyester a hydroxyl terminated polymer including repeat units from an oxetane having a pendant —CH 2 —O—(CH 2 ) n —Rf group, or combinations of a), b), and c)    2) subsequently heating said mixture to at least about 150° F. for a period of time sufficient to cure and cross-link said layer,    thereby providing a crosslinked layer,    wherein said Rf group, independently is a linear or branched alkyl group of 1 to 20 carbon atoms with a minimum of 25 percent of the hydrogens of said alkyl groups being replaced by F or said Rf group independently being an oxaperfluorinated or perfluorinated polyether having from 4 to 60 carbon atoms, and n being from 1 to 3.    
     
     
         11 . A method according to    claim 10   , wherein said Rf of said repeat units is individually on said repeat units a perfluorinated alkyl having from 1 to 20 carbon atoms.  
     
     
         12 . A method according to    claim 10   , where prior to applying said layer to said substrate, said substrate is printed at least one time.  
     
     
         13 . A method according to    claim 10   , wherein said substrate comprises a cellulosic product, fibers, synthetic polymer, metal or ceramic.  
     
     
         14 . A method according to    claim 10   , where prior to applying said layer to said substrate, said substrate is printed and embossed.  
     
     
         15 . A method according to    claim 10   , wherein said substrate includes a layer of plasticized vinyl chloride polymer.  
     
     
         16 . A method according to    claim 15   , wherein said vinyl chloride polymer is coated onto a fabric or backing.  
     
     
         17 . A method according to    claim 15   , of forming a wallcovering.  
     
     
         18 . A method according to    claim 11    of forming a dry erase surface.  
     
     
         19 . A composition, comprising; 
 a) at least one amino resin cross-linking agent and either    b1) reactive polyester resin and    b2) a hydroxyl terminated polymer including repeat units from an oxetane having a pendant —CH 2 —O—(CH 2 ) n —Rf group, or    c) a reactive polyester resin including therein at least one repeat unit derived from copolymerizing into said polyester a hydroxyl terminated polymer including repeat units from an oxetane having a pendant —CH 2 —O—(CH 2 ) n —Rf group or combinations of a), b), and c), 
 wherein said pendant —CH 2 —O—(CH 2 ) n —Rf group, independently, on different repeat units is a linear or branched alkyl group of 1 to 20 carbon atoms, a minimum of 25 percent of the hydrogen atoms of said alkyl group being replaced by F or said Rf group independently, being an oxaperfluorinated or perfluorinated polyether having from 4 to 60 carbon atoms, and n is from 1 to 3.  
   
     
     
         20 . A composition according to    claim 19   , wherein Rf is said linear or branched alkyl group.  
     
     
         21 . A composition according to    claim 19   , wherein said Rf is a linear or branched alkyl group of 3 to 10 carbon atoms.  
     
     
         22 . A composition according to    claim 19   , wherein at least said amino resin and said polyester including repeat units from said hydroxyl terminated polymer are reacted together to form a reaction product.  
     
     
         23 . A composition according to    claim 21   , wherein at least said polyester, said hydroxyl terminated polymer, and said amino resin are reacted together to form a reaction product.  
     
     
         24 . In an article including a substrate having a protective coating thereon, the improvement wherein the protective coating comprises 
 a) at least one amino resin cross-linking agent and either    b1) reactive polyester resin and    b2) a hydroxyl terminated polymer including repeat units from an oxetane having a pendant —CH 2 —O—(CH 2 ) n —Rf group or    c) a reactive polyester resin including therein at least one repeat unit derived from copolymerizing into said polymester a hydroxyl terminated polymer including repeat units from an oxetane having a pendant —CH 2 —O—(CH 2 ) n —Rf group, or combinations of a), b), and c), 
 wherein said pendant —CH 2 —O—(CH 2 ) n RF group independently on different repeat units is a linear or branched alkyl group of 1 to 20 carbon atoms and a minimum of 25 percent of the hydrogen atoms of said alkyl group being replaced by F or said Rf, independently, being an oxaperfluorinated or perfluorinated polyether having from 4 to 60 carbon atoms, and in being from 1 to 3.  
   
     
     
         25 . In an article according to    claim 24    wherein said a) and c) are reacted to form a crosslinked composition.  
     
     
         26 . In an article according to    claim 25   , wherein the substrate is a cellulosic sheet.