Patent Publication Number: US-4259411-A

Title: Electroconductive coating formulations

Description:
This application is a continuation-in-part of copending U.S. Ser. No. 960,793, filed Nov. 15, 1978, and now abandoned. 
    
    
     This invention relates to an improved electroconductive paper. 
     More particularly, this invention relates to an improved electroconductive paper that has improved solvent holdout and conductive properties with lower degrees of tackiness, particularly in high relative humidity environments. 
     In the coating art, as presently practiced for electroconductive papers, barrier coatings usually consist of only starch, commonly chemically modified types of starch, or a combination of starch and a resin, such as styrene-maleic anhydride copolymer. The barrier coated sheet is subsequently overcoated with a coating that has electroconductive properties and is then referred to in the trade as conductive base stock. Using the preceding manufacturing process, frequenct problems occur with the base stock in obtaining the required degree of solvent holdout, conductivity and low tackiness. Particularly, at high relative humidities, tackiness of the conductivized paper causes numerous production problems on the coating machine and calender stacks, resulting in reel blocking and processing difficulties. 
     Our unique barrier coating for electroconductive paper, when used in combination with a suitable conductive polymer formulation, will provide a finished conductive base stock that has improved solvent holdout and conductivity, and a low degree of tackiness at high relative humidities. 
     These and other objects of this invention are accomplished by applying the special barrier coating of this invention to the paper raw stock. The barrier coating consists essentially of from about 5 to about 50 percent by weight of a copolymer of ethylene and vinyl acetate, a styrene-butadiene latex, sodium alginate or a fluorocarbon; and from about 50 to about 95 percent by weight of a modified starch. This coating may be applied to the paper raw stock by conventional coating techniques in amounts ranging from about 0.8 to about 3.5 g/m 2 . The conductive coating contains from about 10 to about 90 percent by weight, preferably about 70 to about 90 percent by weight, of an electroconductive polymer and from about 10 to about 90 percent by weight of a combination of pigments and/or binders. This coating may also be applied to one or both sides of the barrier-coated paper by conventional coating techniques, such as blade, air knife or reverse roll methods in amounts ranging from about 0.8 to about 6.0 g/m 2  per side of the paper. 
     The preferred copolymer of ethylene and vinyl acetate is an aqueous latex product marketed by Air Products and Chemicals, Inc., as Airflex 110 and the preferred modified starch is a hydroxyethylated, acetylated, oxidized or cationic starch. 
     The nature of the electroconductive polymer component of the improved coating formulations of this invention is not critical. Any of a variety of electroconductive polymers, both cationic and anionic, may be employed provided that the conductive polymer selected is capable of imparting adequate surface resistivity to the base raw stock. As cationic electroconductive polymers, there may be employed any water-soluble cationic polymer containing quaternary ammonium functional groups. Included in such cationic polymers are those of the formula: ##STR1## wherein: R stands for hydrogen or lower alkyl; 
     R 1  represents a member of the class composed of ##STR2## R 2  stands for 
     
         --A--N.sup.⊕ --(R.sub.3).sub.3 
    
     wherein, in turn, A represents a lower alkylene, an hydroxy-lower alkylene or lower- alkyl-substituted lower alkylene group, and R 3  stands for a lower alkyl group. These polymers include those wherein the quaternary ammonium functional group is carried as a pendant group to the principal polymer chain, such as, for example, polyvinyl benzyl trimethyl ammonium chloride, poly- [alpha-(methylene trimethyl ammonium chloride)ethylene oxide] and poly(methacryloyloxyethyl trimethyl ammonium chloride). Also useful are those polymers wherein the quaternary ammonium functional group is incorporated in a cyclic structure which comprises a portion of the polymer backbone, such as, for example, polymers containing repeating units of the formula: ##STR3## where R is an alkyl group of 1 to 18 carbon atoms and R 1  is R or β-propionamido and A is an anion. A preferred polymer of this class is poly-(dimethyldiallylammonium chloride); and those wherein the quaternary ammonium functional group forms a part of the polymer chain, such cationic polymers being commonly designated as &#34;ionenes&#34;. 
     Included in this group, for example, are ionene polymers prepared from halo alkyl dialkyl amine monomer units, such as 3-ionene(poly-(dimethyl propyl)ammonium chloride), prepared by the polymerization of 3-chloropropyl dimethyl amine, and ionene polymers prepared from di-tertiaryamines and dihalides, such as 3,4-ionene which is prepared from 1,3-bis-dimethylamino propane and 1,4-dichlorobutene. Other ionene polymers, of course, which are prepared similarly, may be employed as the electroconductive component of the coating formulations of this invention. 
     In addition to the cationic electroconductive polymers mentioned above, water-soluble cationic phosphonium and sulfonium polymers also may be employed as the electroconductive component in the coating formulations of this invention. Included among these are polymers, such as, for example, poly-(2-acryloxyethyldimethyl sulfonium chloride) and poly-(glycidyltributyl phosphonium chloride) and the like. 
     It should be noted that the typical cationic and anionic polymers mentioned above may contain one or more other mer units. For example, copolymers such as the copolymer of dimethyl diallyl ammonium chloride and diacetone acrylamide or the reaction product of dimethyl diallyl ammonium chloride and the copolymer of styrene and maleic anhydride also can be used as the electroconductive component of the coating formulations of this invention. The ratio of mer units in such copolymers will be determined by the quantity of cationic or anionic necessary to impart the desired surface resistivity to the base sheet. 
     Although any of the electroconductive polymers noted above, or other electroconductive polymers capable of imparting the necessary degree of surface resistivity to the base sheet, may be employed as the electroconductive component in the improved coating formulations of this invention, the preferred electroconductive polymers are the cationic polymers and copolymers and especially cationic quaternary ammonium polymers and copolymers. Of these, the most preferred polymers are poly-(dimethyldiallylammonium chloride), copolymers of dimethyl diallyl ammonium chloride and diacetone acrylamide containing from 70 to 98% diallyl monomer, polyvinylbenzyl trimethyl ammonium chloride, polymethacryloyloxyethyl trimethyl ammonium chloride, polymethacryloyloxytrimethylammonium methosulfate, polyepiclorohydrin 80 to 100% quaternized with trimethylamine, copolymers of acrylamide and methacryloyloxyethyl trimethyl ammonium chloride containing from 90 to 99.5% methacryloyloxyethyl monomer units, poly-methacryloyloxyethyl dimethyl hydroxyethyl ammonium chloride) and poly-(dimethylpropylammonium chloride). 
     As noted above, the binders employed in the improved coating formulations of this invention can be of great variety and do not constitute a critical aspect of the instant invention. Any of the water-soluble, film-forming polymers conventionally employed for this purpose may be used in the coating formulations of this invention. Suitable binders will include, for example, polyvinylalcohols, polyvinyl acetates, styrenebutadiene latices, polyethylene-polyvinyl acetate copolymers, unmodified starches, acetylated starches, hydroxyethylated starches, enzyme converted starches, oxidized starches, proteins, caseins, and the like or mixtures thereof. Similarly, any of the variety of pigments conventionally employed in coating formulations may be employed in the improved coating formulations of this invention including commercially available calcium carbonates, kaolin clays, titanium dioxides, aluminas or combinations of these materials. 
     The electroconductive coating fromulation utilized in this invention may also contain certain mono- and bis-(1H,1H,2H,2H-perfluoroalkyl)-phosphate esters, when incorporated into electroconductive coating formulations in the quantities specified below, are effective in imparting to such formulations improved solvent holdout properties. In general, useful perfluoroalkyl phosphate esters will have the formula, 
     
         (C.sub.m F.sub.2m+1 C.sub.n H.sub.2n O).sub.y PO(OM).sub.3-y 
    
     wherein m is an integer between 4 and 10, n is an integer between 1 and 11, y is 1 or 2 and M is a water-solubilizing cation, such as, for example, an alkali metal (Li, K, Na and the like), ammonium or substituted ammonium including methylamine, dimethylamine, diethylamine, monoethanolamine, diethanolamine, triethanolamine or morpholine and the like. Preferred salts generally are the diethanolamine salts. Desirably, C m  and C n  taken together, constitute a straight chain of at least 8 carbon atoms. Such perfluoroalkyl phosphate esters are well-known materials and are available commercially or readily prepared by methods fully described in the art. Particularly preferred is the perfluoroalkyl phosphate ester manufactured by E. I. de Pont de Nemours Company, Inc., Wilmington, Delaware, under the Trademark, ZONYL RP, which contains diethanolamine salts of mono- and bis-(1H,1H,2H,2H-perfluoroalkyl) phosphates where the alkyl group is even numbered in the range C 8  -C 18  and the salts have a fluorine content of 52.4% to 54.4% as determined on a solids basis or ammonium bis(N-ethyl-2-perfluoroalkylsulfonamido ethyl) phosphates, containing not more than 15% ammonium mono(N-ethyl-2-perfluoroalkylsulfonamido ethyl) phosphates, where the alkyl group is more than 95% C 8  and the salts have a fluorine content of 50.2% to 52.8% as determined on a solids basis. Materials of this type are sold by 3 M Co., Inc., under the Trademark SCOTCHBAN. 
    
    
     In order to illustrate the advantages derived from the present invention, the barrier coating and conductive coating formulations were applied to raw stock by drawdowns with the appropriate wire-wound rod and also ran a Keegan Pilot Coater. The coated sheets were conditioned overnight at 20% and 50% relative humidity (RH) and 72° F. after which they were weighed to obtain coatweight and evaluated for conductivity by using a Keithley 610B Electrometer to measure surface resistivity. Solvent holdout was determined by measuring dyed toluene penetration after 10 seconds contact time. Tackiness of the paper was determined by hand feel. The results of these tests are set forth in the following tables. 
     
                                           TABLE I                                 
__________________________________________________________________________
                   Total Coat Weight (g/m.sup.2)                          
Coating Composition    Conduc-  % Toluene Penetration                     
Barrier  Conductive                                                       
                   Barrier                                                
                       tive Total                                         
                                Top   Back                                
__________________________________________________________________________
90% Starch                                                                
         90% PCL-7513                                                     
10% Scripset                                                              
         10% CaCO.sub.3                                                   
                   2.3 4.6  6.9 20-30 40                                  
100%     100%                                                             
90% Starch                                                                
         80% PCL-7513                                                     
                   2.2 4.5  6.7 20-30 40                                  
10% Scripset                                                              
         20% CaCO.sub.3                                                   
                   2.2 4.8  7.0 40    50                                  
100%     100%                                                             
90% Starch                                                                
         70% PCL-7513                                                     
                   2.1 4.2  6.3 20    95                                  
10% Scripset                                                              
         30% CaCO.sub.3                                                   
100%     100%                                                             
90% Starch                                                                
         70% CP-261                                                       
                   2.2 4.3  6.5 10    50                                  
10% Scripset                                                              
         30% CaCO.sub.3                                                   
100%     100%                                                             
90% Starch                                                                
         80% PCL-7513                                                     
                   2.2 4.2  6.4 10    70                                  
10% Scripset                                                              
         20% Clay  2.2 4.9  7.1 10    60                                  
100%     100%      2.3 4.3  6.6 10    60                                  
                   2.0 4.7  6.7  6    15                                  
                   2.0 5.9  7.9  6    40                                  
                   2.1 4.5  6.6  6    15                                  
90% Starch                                                                
         80% CP-261                                                       
                   2.2 4.5  6.7 30    50                                  
10% Scripset                                                              
         20% Clay                                                         
100%     100%                                                             
90% Starch                                                                
         30% CP-261                                                       
                   2.2 3.8  6.0 30    50                                  
10% Scripset                                                              
         25% Airflex 110                                                  
100%     45% Clay                                                         
         100%                                                             
90% Starch                                                                
         80% ECR-77                                                       
                   2.0 4.1  6.1 50    70                                  
10% Scripset                                                              
         20% Clay                                                         
100%     100%                                                             
85% Starch                                                                
         90% PCL-7513                                                     
                   2.2 4.8  7.0 30    40                                  
15% Scripset                                                              
         10% CaCO.sub.3                                                   
100%     100%                                                             
85% Starch                                                                
         80% PCL-7513                                                     
                   2.0 4.6  6.6 15    40                                  
15% Scripset                                                              
         20% Clay  2.1 4.1  6.2 20    85                                  
100%     100%                                                             
85% Starch                                                                
         70% CP-261                                                       
                   2.3 4.2  6.5 20    50                                  
15% Scripset                                                              
         30% CaCO.sub.3                                                   
100%     100%                                                             
80% Starch                                                                
         90% PCL-7513                                                     
                   2.1 4.3  6.4 20    70                                  
20% Scripset                                                              
         10% CaCO.sub.3                                                   
100%     100%                                                             
80% Starch                                                                
         80% PCL-7513                                                     
                   2.0 4.3  6.3 30    70                                  
20% Scripset                                                              
         20% CaCO.sub.3                                                   
100%     100%                                                             
80% Starch                                                                
         80% PCL-7513                                                     
                   2.1 4.1  6.2 20    90                                  
20% Scripset                                                              
         20% Clay  2.2 4.3  6.5 40    50                                  
100%     100%      2.2 4.1  6.3 40    90                                  
                   2.2 4.7  6.9  6    50                                  
80% Starch                                                                
         70% CP-261                                                       
                   2.1 4.2  6.3 20    70                                  
20% Scripset                                                              
         30% CaCO.sub.3                                                   
100%     100%                                                             
80% Starch                                                                
         40% CP-261                                                       
                   2.2 3.7  5.9 40    80                                  
20% Scripset                                                              
         25% Airflex 110                                                  
                   2.0 5.5  7.5 15    50                                  
100%     35% Clay  2.0 4.0  6.0 40    90                                  
         100%                                                             
80% Starch                                                                
         30% CP-261                                                       
                   2.0 4.0  6.0 90    90                                  
20% Scripset                                                              
         25% Airflex 110                                                  
                   2.0 5.2  7.2 70    90                                  
100%     45% Clay  2.0 5.6  7.6 40    80                                  
         100%                                                             
80% Starch                                                                
         80% PCL-7513                                                     
                   2.3 5.0  7.3 10    20                                  
20% Airflex                                                               
         20% Clay                                                         
100%     100%                                                             
80% Starch                                                                
         80% CP-261                                                       
                   2.5 4.9  7.4 50    70                                  
20% Airflex                                                               
         20% Clay                                                         
100%     100%                                                             
80% Starch                                                                
         80% ECR-77                                                       
                   2.3 4.2  6.5 10    30                                  
20% Airflex                                                               
         20% Clay                                                         
100%     100%                                                             
80% Starch                                                                
         70% CP-261                                                       
                   2.4 4.0  6.4 60    90                                  
20% Airflex                                                               
         10% Airflex                                                      
100%     20% Clay                                                         
         100%                                                             
100%                                                                      
    Starch                                                                
         80% PCL-7513                                                     
         20% Clay  2.2 4.5  6.7 50    100                                 
         100%                                                             
100%                                                                      
    Starch                                                                
         30% CP-261                                                       
                   2.2 4.3  6.5 70    90                                  
         25% Airflex 110                                                  
         45% Clay                                                         
         100%                                                             
__________________________________________________________________________
 Scripset is a styrene/maleic anhydride latex.                            
 Airflex is a ethylene/vinylacetate latex.                                
 CP261 is a homopolymer of dimethyl diallyl ammonium chloride.            
 PCL7513 is a physical blend of a homopolymer of dimethyl diallyl ammonium
 chloride and a fluorosurfactant.                                         
 ECR77 is a homopolymer of benzyl trimethyl ammonium chloride.            
 
    
     
                                           TABLE II                                
__________________________________________________________________________
                Total Coat                                                
                Weight (g/m.sup.2)                                        
                           Surface Resistivity (ohms/sq.)                 
Coating Composition                                                       
                Bar-                                                      
                   Conduc-                                                
                        To-                                               
                           at 50% R.H.                                    
                                     at 17.5% R.H.                        
Barrier Conductive                                                        
                rier                                                      
                   tive tal                                               
                           Top  Back Top   Back                           
__________________________________________________________________________
90% Starch                                                                
        90% PCL-                                                          
            7513                                                          
                2.3                                                       
                   4.6  6.9                                               
                           2.8 × 10.sup.7                           
                                1.9 × 10.sup.7                      
                                     4.1 × 10.sup.8                 
                                           3.8 × 10.sup.8           
10% Scrip-                                                                
        10% CaCO.sub.3                                                    
    set                                                                   
100%    100%                                                              
90% Starch                                                                
        80% PCL-                                                          
            7513                                                          
                2.2                                                       
                   4.5  6.7                                               
                           3.0 × 10.sup.7                           
                                1.5 × 10.sup.7                      
                                     4.9 × 10.sup.8                 
                                           3.1 × 10.sup.8           
10% Scrip-                                                                
        20% CaCO.sub.3                                                    
    set                                                                   
100%    100%                                                              
90% Starch                                                                
        70% PCL-                                                          
            7513                                                          
                2.1                                                       
                   4.2  6.3                                               
                           3.0 × 10.sup.7                           
                                1.9 × 10.sup.7                      
                                     4.5 × 10.sup.8                 
                                           3.3 × 10.sup.8           
10% Scrip-                                                                
        30% CaCO.sub.3                                                    
    set                                                                   
100%    100%                                                              
90% Starch                                                                
        70% CP-261                                                        
                2.2                                                       
                   4.3  6.5                                               
                           2.1 × 10.sup.7                           
                                1.7 × 10.sup.7                      
                                     4.5 × 10.sup.8                 
                                           3.0 × 10.sup.8           
10% Scrip-                                                                
        30% CaCO.sub.3                                                    
    set                                                                   
100%    100%                                                              
90% Starch                                                                
        80% PCL-                                                          
                2.2                                                       
                   4.2  6.4                                               
                           3.1 × 10.sup.7                           
                                2.2 × 10.sup.7                      
                                     4.1 × 10.sup.8                 
                                           3.3 × 10.sup.8           
            7513                                                          
                2.2                                                       
                   4.9  7.1                                               
                           4.5 × 10.sup.7                           
                                1.7 × 10.sup.7                      
                                     4.5 × 10.sup.8                 
                                           3.1 × 10.sup.8           
10% Scrip-                                                                
        20% Clay                                                          
                2.3                                                       
                   4.3  6.6                                               
                           3.1 × 10.sup.7                           
                                1.8 × 10.sup.7                      
                                     4.5 × 10.sup.8                 
                                           3.6 × 10.sup.8           
    set         2.0                                                       
                   4.7  6.7                                               
                           6.4 × 10.sup.6                           
                                9.4 × 10.sup.6                      
                                     4.9 × 10.sup.8                 
                                           4.5 × 10.sup.8           
100%    100%    2.0                                                       
                   5.9  7.9                                               
                           5.6 × 10.sup.7                           
                                1.1 × 10.sup.7                      
                                     4.5 × 10.sup.8                 
                                           3.1 × 10.sup.8           
                2.1                                                       
                   4.5  6.6                                               
                           2.0 × 10.sup.7                           
                                1.4 × 10.sup.7                      
                                     1.0 × 10.sup.9                 
                                           6.1 × 10.sup.8           
90% Starch                                                                
        80% CP-261                                                        
                2.2                                                       
                   4.5  6.7                                               
                           3.8 × 10.sup.7                           
                                2.0 × 10.sup.7                      
                                     6.6 × 10.sup.8                 
                                           4.1 × 10.sup.8           
10% Scrip-                                                                
        20% Clay                                                          
    set                                                                   
100%    100%                                                              
90% Starch                                                                
        30% CP-261                                                        
                2.2                                                       
                   3.8  6.0                                               
                           7.2 × 10.sup.8                           
                                2.5 × 10.sup.8                      
                                     1.8 × 10.sup.10                
                                           4.1 × 10.sup.9           
10% Scrip-                                                                
        25% Airflex                                                       
    set     110                                                           
        45% Clay                                                          
100%    100%                                                              
90% Starch                                                                
        80% ECR-77                                                        
                2.0                                                       
                   4.1  6.1                                               
                           2.1 × 10.sup.7                           
                                1.7 × 10.sup.7                      
                                     9.8 × 10.sup.8                 
                                           7.6 × 10.sup.8           
10% Scrip-                                                                
        20% Clay                                                          
    set                                                                   
100%    100%                                                              
85% Starch                                                                
        90% PCL-                                                          
                2.2                                                       
                   4.8  7.0                                               
                           1.8 × 10.sup.7                           
                                1.1 × 10.sup.7                      
                                     3.1 × 10.sup.8                 
                                           2.1 × 10.sup.8           
            7513                                                          
15% Scrip-                                                                
        10% CaCO.sub.3                                                    
    set                                                                   
100%    100%                                                              
85% Starch                                                                
        80% PCL-                                                          
                2.0                                                       
                   4.6  6.6                                               
                           2.3 × 10.sup.7                           
                                3.0 × 10.sup.7                      
                                     4.9 × 10.sup.8                 
                                           4.5 × 10.sup.8           
            7513                                                          
                2.1                                                       
                   4.1  6.2                                               
                           1.3 × 10.sup.7                           
                                1.9 × 10.sup.7                      
                                     4.1 × 10.sup.8                 
                                           3.0 ×  10.sup.8          
15% Scrip-                                                                
        20% Clay                                                          
    set                                                                   
100%    100%                                                              
85% Starch                                                                
        70% CP-261                                                        
                2.3                                                       
                   4.2  6.5                                               
                           3.3 × 10.sup.7                           
                                1.9 × 10.sup.7                      
                                     4.1 × 10.sup.8                 
                                           3.3 × 10.sup.8           
15% Scrip-                                                                
        30% CaCO.sub.3                                                    
    set                                                                   
100%    100%                                                              
80% Starch                                                                
        90% PCL-                                                          
                2.1                                                       
                   4.3  6.4                                               
                           1.4 × 10.sup.7                           
                                1.4 × 10.sup.7                      
                                     3.3 × 10.sup.8                 
                                           3.0 × 10.sup.8           
            7513                                                          
20% Scrip-                                                                
        10% CaCO.sub.3                                                    
    set                                                                   
100%    100%                                                              
80% Starch                                                                
        80% PCL-                                                          
                2.0                                                       
                   4.3  6.3                                               
                           1.8 × 10.sup.7                           
                                3.0 × 10.sup.7                      
                                     3.3 × 10.sup.8                 
                                           1.2 × 10.sup.8           
            7513                                                          
20% Scrip-                                                                
        20% CaCO.sub.3                                                    
    set                                                                   
100%    100%                                                              
80% Starch                                                                
        80% PCL-                                                          
                2.1                                                       
                   4.1  6.2                                               
                           2.8 × 10.sup.7                           
                                2.8 × 10.sup.7                      
                                     4.1 × 10.sup.8                 
                                           3.8 × 10.sup.8           
            7513                                                          
                2.2                                                       
                   4.3  6.5                                               
                           2.3 × 10.sup.7                           
                                2.1 × 10.sup.7                      
                                     3.6 × 10.sup.8                 
                                           4.1 × 10.sup.8           
20% Scrip-                                                                
        20% Clay                                                          
                2.2                                                       
                   4.1  6.3                                               
                           2.1 × 10.sup.7                           
                                2.5 × 10.sup.7                      
                                     3.6 × 10.sup.8                 
                                           3.8 × 10.sup.8           
    set         2.2                                                       
                   4.7  6.9                                               
                           6.3 × 10.sup.6                           
                                6.3 × 10.sup.6                      
                                     4.5 × 10.sup.8                 
                                           6.4 × 10.sup.8           
100%    100%                                                              
80% Starch                                                                
        70% CP-261                                                        
                2.1                                                       
                   4.2  6.3                                               
                           1.9 × 10                                 
                                1.9 × 10                            
                                     3.8 × 10                       
                                           3.1 × 10                 
20% Scrip-                                                                
        30% CaCO.sub.3                                                    
    set                                                                   
100%    100%                                                              
80% Starch                                                                
        40% CP-261                                                        
                2.2                                                       
                   3.7  5.9                                               
                           1.3 × 10.sup.8                           
                                3.1 × 10.sup.7                      
                                     1.9 × 10.sup.9                 
                                           1.1 × 10.sup.9           
20% Scrip-                                                                
        25% Airflex                                                       
                2.0                                                       
                   5.5  7.5                                               
                           3.1 × 10.sup.7                           
                                2.7 × 10.sup.7                      
                                     9.2 × 10.sup.8                 
                                           9.5 × 10.sup.8           
    set     110 2.0                                                       
                   4.0  6.0                                               
                           1.3 × 10.sup.8                           
                                8.2 × 10.sup.7                      
                                     2.1 × 10.sup.9                 
                                           1.8 × 10.sup.9           
        35% Clay                                                          
100%    100%                                                              
80% Starch                                                                
        30% CP-261                                                        
                2.0                                                       
                   4.0  6.0                                               
                           2.2 × 10.sup.8                           
                                2.5 × 10.sup.8                      
                                     6.5 × 10.sup.9                 
                                           6.7 × 10.sup.9           
20% Scrip-                                                                
        25% Airflex                                                       
                2.0                                                       
                   5.2  7.2                                               
                           1.3 × 10.sup. 8                          
                                1.3 × 10.sup.8                      
                                     4.1 × 10.sup.9                 
                                           4.5 × 10.sup.9           
    set     110 2.0                                                       
                   5.6  7.6                                               
                           3.1 × 10.sup.7                           
                                2.7 × 10.sup.9                      
                                     4.1 × 10.sup.9                 
                                           4.1 × 10.sup.9           
        45% Clay                                                          
100%    100%                                                              
80% Starch                                                                
        80% PCL-                                                          
                2.3                                                       
                   5.0  7.3                                               
                           4.1 × 10.sup.7                           
                                4.5 × 10.sup.7                      
                                     1.9 × 10.sup.9                 
                                           6.6 × 10.sup.8           
            7513                                                          
20% Airflex                                                               
        20% Clay                                                          
100%    100%                                                              
80% Starch                                                                
        80% CP-261                                                        
                2.5                                                       
                   4.9  7.4                                               
                           1.4 × 10.sup.8                           
                                3.0 × 10.sup.7                      
                                     2.7 × 10.sup.9                 
                                           8.3 × 10.sup.8           
20% Airflex                                                               
        20% Clay                                                          
100%    100%                                                              
80% Starch                                                                
        80% ECR-77                                                        
                2.3                                                       
                   4.2  6.5                                               
                           1.2 × 10.sup.8                           
                                7.0 × 10.sup.7                      
                                     1.0 × 10.sup.9                 
                                           8.2 × 10.sup.8           
20% Airflex                                                               
        20% Clay                                                          
100%    100%                                                              
80% Starch                                                                
        70% CP-261                                                        
                2.4                                                       
                   4.0  6.4                                               
                           9.4 × 10.sup.7                           
                                4.5 × 10.sup.7                      
                                     2.4 × 10.sup.9                 
                                           8.9 × 10.sup.8           
20% Airflex                                                               
        10% Airflex                                                       
        20% Clay                                                          
100%    100%                                                              
100%                                                                      
    Starch                                                                
        80% PCL-                                                          
                2.2                                                       
                   4.5  6.7                                               
                           4.5 ×  10.sup.7                          
                                7.2 × 10.sup.7                      
                                     7.3 × 10.sup.9                 
                                           1.0 × 10.sup.9           
            7513                                                          
        20% Clay                                                          
        100%                                                              
100%                                                                      
    Starch                                                                
        30% CP-261                                                        
                2.2                                                       
                   4.3  6.5                                               
                           5.8 × 10.sup.8                           
                                4.1 × 10.sup.8                      
                                     9.1 × 10.sup.9                 
                                           8.2 × 10.sup.9           
        25% Airflex                                                       
            110                                                           
        45% Clay                                                          
        100%                                                              
__________________________________________________________________________
 Scripset is a styrene/maleic anhydride latex.                            
 Airflex is a ethylene/vinylacetate latex.                                
 CP261 is a homopolymer of dimethyl diallyl ammonium chloride.            
 PCL7513 is a physical blend of a homopolymer of dimethyl diallyl ammonium
 chloride and a fluorosurfactant.                                         
 ECR77 is a homopolymer of benzyl trimethyl ammonium chloride.            
 
    
     
                                           TABLE III                               
__________________________________________________________________________
                        Total Coat Weight (g/m.sup.2)                     
                                    % Toluene                             
Coating Composition     Conduc-  Tack                                     
                                    Penetration                           
Barrier   Conductive                                                      
                    Barrier                                               
                        tive Total                                        
                                 (0-5)                                    
                                    Top                                   
                                       Back                               
__________________________________________________________________________
90% Starch                                                                
          80% PCL-7513                                                    
                    2.4 5.8  8.2 4-5                                      
                                    20-30                                 
                                       20-30                              
10% Scripset 540                                                          
          20% Clay                                                        
100%      100%                                                            
80% Starch                                                                
          70% CP-261                                                      
                    2.4 3.6  6.0 5  30-40                                 
                                       40-60                              
20% Scripset 540                                                          
          10% Airflex                                                     
          20% Clay                                                        
100%      100%                                                            
80% Starch                                                                
          70% CP-261                                                      
                    2.4 5.4  7.8 2-3                                      
                                    40-50                                 
                                       60-70                              
20% Airflex 110                                                           
          10% Airflex                                                     
          20% Clay                                                        
100%      100%                                                            
80% Starch                                                                
          80% ECR-77                                                      
                    2.4 4.1  6.5 1  40- 50                                
                                       60-70                              
 20%                                                                      
    Airflex 110                                                           
          20% Clay                                                        
100%      100%                                                            
80% Starch                                                                
          80% PCL-7513                                                    
                    2.4 5.3  7.7 2   10                                   
                                        10                                
20% Airflex 110                                                           
          20% Clay                                                        
100%      100%                                                            
              Raw Stock                                                   
                    --  --   --  0  100                                   
                                       100                                
__________________________________________________________________________
 Scripset is a styrene/maleic anhydride latex.                            
 Airflex is a ethylene/vinylacetate latex.                                
 CP261 is a homopolymer of dimethyl diallyl ammonium chloride.            
 PCL7513 is a physcial blend of a homopolymer of dimethyl diallyl ammonium
 chloride and a fluorosurfactant.                                         
 ECR77 is a homopolymer of benzyl trimethyl ammonium chloride.            
 
    
     
                                           TABLE IV                                
__________________________________________________________________________
                  Total Coat                                              
                  Weight (g/m.sup.2)                                      
                             Surface Resistivity (ohms/sq.)               
Coating Composition                                                       
                  Bar-                                                    
                     Conduc-                                              
                          To-                                             
                             at 50% R.H. at 17.5% R.H.                    
Barrier Conductive                                                        
                  rier                                                    
                     tive tal                                             
                             Top   Back  Top   Back                       
__________________________________________________________________________
90% Starch                                                                
        80% PCL-                                                          
            7513  2.4                                                     
                     5.8  8.2                                             
                             1.1 × 10.sup.7                         
                                   1.1 × 10.sup.7                   
                                         4.5 × 10.sup.8             
                                               4.5 × 10.sup.8       
10% Scrip-                                                                
        20% Clay                                                          
    set 540                                                               
100%    100%                                                              
80% Starch                                                                
        70% CP-261                                                        
                  2.4                                                     
                     3.6  6.0                                             
                             1.2 × 10.sup.7                         
                                   1.2 × 10.sup.7                   
                                         4.1 × 10.sup.8             
                                               4.1 × 10.sup.8       
20% Scrip-                                                                
        10% Airflex                                                       
    set 540                                                               
        20% Clay                                                          
100%    100%                                                              
80% Starch                                                                
        70% CP-261                                                        
                  2.4                                                     
                     5.4  7.8                                             
                             2.5 × 10.sup.7                         
                                   2.8 × 10.sup.7                   
                                         6.5 × 10.sup.8             
                                               6.7 × 10.sup.8       
20% Airflex                                                               
        10% Airflex                                                       
    110 20% Clay                                                          
100%    100%                                                              
80% Starch                                                                
        80% ECR-77                                                        
                  2.4                                                     
                     4.1  6.5                                             
                             3.3 × 10.sup.7                         
                                   2.8 × 10.sup.7                   
                                         6.7 × 10.sup.8             
                                               7.7 × 10.sup.8       
20% Airflex                                                               
        20% Clay                                                          
    110                                                                   
100%    100%                                                              
80% Starch                                                                
        80% PCL-                                                          
            7513  2.4                                                     
                     5.3  7.7                                             
                             2.1 × 10.sup.7                         
                                   2.3 × 10.sup.7                   
                                         6.7 × 10.sup.8             
                                               6.7 × 10.sup.8       
20% Airflex                                                               
        20% Clay                                                          
    110                                                                   
100%    100%                                                              
            Raw Stock                                                     
                  -- --   -- 1.1 × 10.sup.12                        
                                   1.7 × 10.sup.12                  
                                         4.1 × 10.sup.14            
                                               4.5 × 10.sup.14      
__________________________________________________________________________
 Scripset is a styrene/maleic anhydride latex.                            
 Airflex is a ethylene/vinylacetate latex.                                
 CP261 is a homopolymer of dimethyl diallyl ammonium chloride.            
 PCL7513 is a physical blend of a homopolymer of dimethyl diallyl ammonium
 chloride and a fluorosurfactant.                                         
 ECR77 is a homopolymer of benzyl trimethyl ammonium chloride.            
 
    
     The following tables (Tables V, VI and VII) illustrate the formulation and performance of other representative barrier and conductive coating formulations. 
     
                       TABLE V                                                     
______________________________________                                    
COMPOSITION OF CONDUCTIVE COATING COLORS                                  
AND BARRIER COATING COLORS                                                
                 Wt. %   Wt. &#34;as                                          
                 in Dry  rec&#39;d&#34; in                                        
                                  Dry Wt.                                 
  Component      Coating Color (g)                                        
                                  in Color (g)                            
______________________________________                                    
Barrier Coatings                                                          
Kofilm 80 (25%).sup.1                                                     
                 80      96.0     24.0                                    
Airflex 110 (55%)                                                         
                 20      10.9     6.0                                     
Water             --     193.1     --                                     
                 100     300.0    30.0                                    
Kofilm 80        80      96.0     24.0                                    
Dylex K-55E (50%)                                                         
                 20      12.0     6.0                                     
Water             --     192.0     --                                     
                 100     300.0    30.0                                    
Kofilm 80        90      108.0    27.0                                    
Kelgin XL.sup.2  10      3.0      3.0                                     
Water             --     179.0     --                                     
                 100     300.0    30.0                                    
Kofilm 80        98      117.6    29.4                                    
Zonyl RP (33%)   2       1.8      0.6                                     
Water             --     180.6     --                                     
                 100     300.0    30.0                                    
Conductive Coatings                                                       
PCL-7513 (20%)   70      140.0     28.0                                   
Nuclay (50%).sup.3                                                        
                 30      24.0     12.0                                    
Water             --     36.0      --                                     
                 100     200.0    40.0                                    
Polymer E-949 (40%)                                                       
                 70      70.0     28.0                                    
Nuclay           30      24.0     12.0                                    
Water             --     106.0     --                                     
                 100     200.0    40.0                                    
CP-261 LV (40%)  68.6    68.6     27.4                                    
Scotchban FC-809 (33%)                                                    
                 1.4     1.7      0.6                                     
Nuclay           30.0    24.0     12.0                                    
Water             --     105.7     --                                     
                 100.0   200.0    40.0                                    
CP-261 LV        70      70.0     28.0                                    
Nuclay           30      24.0     12.0                                    
Water             --     106.0     -- - 100 200.0 40.0                    
Dow ECR-77 (34%) 70      82.4     28.0                                    
Nuclay           30      24.0     12.0                                    
Water            --      93.6      --                                     
                 100     200.0    40.0                                    
CP-261 LV        68.6    68.6     27.4                                    
Scotchban FC-809 1.4     1.7      0.6                                     
Albaglos (50%)   30.0    24.0     12.0                                    
Water             --     106.8     --                                     
                 100.0   200.0    40.0                                    
______________________________________                                    
 .sup.1 Kofilm 80 was added as a 25% solution to the                      
 .sup.2 Kelgin XL was dissolved in the available water before mixing with 
 the Kofilm solution.                                                     
 .sup.3 Nuclay was added as a 50% solids slurry to the formulations.      
  Kofilm 80 is an acetylated starch.                                      
 Airflex 110 is an ethylene/vinylacatate latex.                           
 Dylex K55E is a styrene/butadiene latex.                                 
 Kelgin XL is sodium alginate.                                            
 PCL7513 is a physical blend of a homopolymer of dimethyl diallyl ammonium
 chloride and a fluorosurfactant.                                         
 Nuclay is kaolin clay.                                                   
 Polymer E949 is a copolymer of 90% by weight dimethyldiallylammonium     
 chloride and 10% by weight acrylamide.                                   
 Scotchban FC809 is a fluorosurfactant.                                   
 Albaglos is a precipitated calcium carbonate.                            
 
    
     
                       TABLE VI                                                    
______________________________________                                    
SOLVENT HOLDOUT AND SURFACE RESISTIVITY                                   
PROPERTIES OF DRAWDOWNS COATED WITH                                       
VARIOUS CONDUCTIVE COATINGS                                               
ON THE SAME TYPE                                                          
Paper Substrate: raw stock coated with a starch/Scripset                  
barrier coating applied in paper mills                                    
                                  Surface                                 
             Coatweight                                                   
                       % Toluene  Resistivity                             
Conductive Coating                                                        
             on Top    Penetration                                        
                                  at 15% R.H.                             
Composition  Side (g/m.sup.2)                                             
                       on Top Side                                        
                                  (top side)                              
______________________________________                                    
70% PCL-7513 4.2       10-20      1.8 × 10.sup.8                    
30% Clay     4.5       10         1.8 × 10.sup.8                    
             4.9       0          1.5 × 10.sup.8                    
70% E-949    4.2       50         4.1 × 10.sup.8                    
30% Clay     4.4       50         4.5 × 10.sup.8                    
68.6% CP-261LV                                                            
 1.4% Scotchban                                                           
             4.4       20-30      2.0 × 10.sup.8                    
FC-809                                                                    
30.0% Clay   4.8       30         1.6 × 10.sup.8                    
70% CP-261LV 4.2       50-60      1.3 × 10.sup.8                    
30% Clay     4.4       50-60      1.2 × 10.sup.8                    
70% ECR-77   3.9       40         2.5 × 10.sup.8                    
30% Clay     4.1       30-40      2.8 × 10.sup.8                    
68.6% CP-261LV                                                            
 1.4% Scotchban                                                           
             4.4       30-40      1.8 × 10.sup.8                    
FC-809                                                                    
30.0% Calcium Carb-                                                       
             4.7       40         1.7 × 10.sup.8                    
onate                                                                     
______________________________________                                    
 PCL-7513 is a physical blend of a homopolymer of dimethyl diallyl ammoniu
 chloride.                                                                
 E949 is a copolymer of 90% by weight dimethyldiallylammonium chloride and
 10% by weight acrylamide.                                                
 CP261LV is a homopolymer of dimethyldiallyl ammonium chloride.           
 Scotchban FC809 is a fluorosurfactant.                                   
 ECR77 is a homopolymer of benzyl trimethyl ammonium chloride.            
 
    
     
                       TABLE VII                                                   
______________________________________                                    
SOLVENT HOLDOUT AND SURFACE RESISTIVITY                                   
PROPERTIES OF DRAWDOWNS COATED WITH A                                     
PCL-7513 CONDUCTIVE FORMULATION ON                                        
VARIOUS TYPES OF BARRIER                                                  
COATED RAW STOCKS                                                         
Conductive Coating:                                                       
                   70% PCL-7513                                           
                   30% Clay                                               
Barrier Coating.sup.1                                                     
             Conductive                                                   
                       % Toluene  Surface                                 
         Coatweight                                                       
                 Coatweight                                               
                           Penetration                                    
                                    Resistivity                           
Identity (g/m.sup.2)                                                      
                 g/m.sup.2).sup.2                                         
                           on Top Side                                    
                                    at 15% R.H.                           
______________________________________                                    
80%     1.6      2.0       10       6.1 × 10.sup.8                  
Kofilm                                                                    
20%                                                                       
Airflex                                                                   
80%    1.5       2.3       10       4.5 × 10.sup.8                  
Kofilm                                                                    
90%%                                                                      
Dylex                                                                     
90%    1.7       1.9        20-30   5.6 × 10.sup.8                  
Kofilm                                                                    
10%                                                                       
Kelgin                                                                    
98%    1.4       2.0       30       6.4 × 10.sup.8                  
Kofilm                                                                    
 2%                                                                       
Zonyl                                                                     
______________________________________                                    
 .sup.1 Applied to top side only                                          
 .sup.2 Applied to top side only                                          
 Kofilm is an acetylated starch.                                          
 Airflex is an ethylene/vinylacetate latex.                               
 Dylex is a styrene/butadiene latex.                                      
 Kelgin is sodium alginate.