Enhancement of paper dry strength by anionic and cationic guar combination
This application is a continuation of application Ser. No. 08/202,417, filed Feb. 28, 1994, now U.S. Pat. No. 5,502,091 and a CIP of 07/812,534, filed Dec. 23,1991now U.S. Pat. No. 5,338,407. 
    
    
     This invention relates to a process for making paper to enhance the dry strength of the paper produced without reducing its softness, that comprises adding to a pulp furnish a combination of cationic and anionic polymers. 
     BACKGROUND OF THE INVENTION 
     One of the major problems that tissue and towel manufacturers face is the unacceptable reduction of dry strength in paper products such as tissue and toweling in which a high degree of softness as well as dry strength is essential, resulting from the use of an increasing percentage of recycled or secondary pulp, chemithermomechanical pulp (CTMP) (CTMP) and groundwood, and the consequent reduction in average fiber length. Softness is a very important property in paper used for making high quality tissues and toweling, and procedure modifications or additives that achieve a compensating increase in paper strength normally decrease paper softness or increase stiffness. There is therefore a need for an effective additive that will enhance paper strength without adversely affecting the softness off the paper. 
     The tissue and towel manufacturers get the softness of their products evaluated by the perception of a human panel. Because it is a very subjective test, correlation of any single laboratory test evaluation with the perception test results may sometimes be difficult. However, extensive research efforts by workers in this area have shown that the results of a bending stiffness test by itself or in combination with tensile stiffness data correlate very reasonably with human perception evaluation. 
     European published Pat. No. 0 362 770 A2 (Application No. 89118245.3) discloses a mixture of cationic and anionic polymers as a strengthening additive for papermaking processes, essentially for unbleached pulps containing black liquor. The mixture comprises a water-soluble, linear, cationic polymer having a reduced specific viscosity greater than 2dl/g and a charge density of 0.2 to 4 meq/g, and a water-soluble, anionic polymer having a charge density of less than 5 meq/g that is reactable in the presence of water with cationic polymer to form a polyelectrolyte complex. Combinations of cationic guar (for example, guar &#34;derivatized&#34; with glycidyltrimethylammonium chloride) and cationic acrylamide copolymers, with anionic polymers in addition to those already contained in the black liquor (including sodium carboxymethyl guar) are disclosed. The preferred anionic polymer content is constituted by those polymers naturally present in unbleached pulps made by either chemical or mechanical pulping. 
     U.S. Pat. No. 3,058,873 discloses a combination of polyamide-epichlorohydrin resins with cellulose ethers or cationic starches for improving paper wet strength, specifically the use of CMC CT, a crude technical grade of carboxymethyl cellulose (CMC), and a polyamide-epichlorohydrin resin to improve wet strength in paper. 
     Published Japanese patent application JP 53106803 A, for which no counterpart exists, discloses paper production having improved wet strength and transparency by forming sheet from cellulosic material, carboxyalkyl cellulose and polyamide-epichlorohydrin resin, drying and treating with acid. Specifically, the method comprises (1) preparing a sheet from a mixture of (a) cellulosic material and (b) partially substituted carboxy-(lower alkyl)-cellulose of which the degrees of substitution (D.S.) is 0.10-0.50, followed by coating the resulting sheet with (c) polyamide-epichlorohydrin resin (or preparing a sheet from a mixture of (a) +(b) +(c), (2) drying the sheet, and (3) treating the dried sheet with a diluted acid solution. The partially lower-alkyl-carboxylated cellulose (typically CMC of D.S. 0.10-0.50) is firmly fixed on the cellulosic pulp when the polyamide-epichlorohydrin resin is present. 
     It would be desirable to provide a process for making paper from a bleached pulp furnish that uses a combination of cationic and anionic polymers to enhance the dry strength of the paper more efficiently than the known processes. 
     SUMMARY OF THE INVENTION 
     According to the invention, a process for making paper to enhance the dry strength of the paper produced without reducing its softness comprises adding to a bleached pulp furnish, separately or together, (1) an anionic polymer selected from the group consisting of carboxymethyl guar, carboxymethyl bean gum, carboxymethyl hydroxyethyl guar (such as the carboxymethyl guar available under the name Galaxy 707D from Aqualon and the name Jaguar 8707 from Hi-Tek), and a carboxymethyl hydroxypropyl guar (such as the carboxymethyl guar available under the name Jaguar 8600 from Hi-Tek), and (2) a cationic polymer selected from the group consisting of a cationic guar, a cationic acrylamide copolymer, a cationic bean gum, and a cationic wet strength resin that is an amine polymer-epichlorohydrin resin, such as polyamide-epichlorohydrin (PAE) resin, a polyalkylenepolyamine-epichlorohydrin (PAPAE) resin, or an amine polymer-epichlorohydrin (APE) resin, preferably the reaction product of a dibasic acid, more preferable adipic acid, with a polyalkylenepolyamine, more preferably a polyethylenepolyamine, in which amine polymer-epichlorohydrin resin amine groups have been alkylated and crosslinked with epichlorohydrin to produce a polyamide-epichlorohydrin resin that has azetidinium or epoxide functionality. 
     A polyamide-epichlorohydrin resin may more specifically be described as a poly(aminoamide)-epichlorohydrin resin, and is sometimes called a polyamide-polyamine-epichlorohydrin resin. If the cationic additive is a wet strength resin the benefits of the invention are achieved and the wet strength of the paper is additionally increased. 
     In a bleached pulp furnish, the combination of additives according to the invention is significantly more effective as a dry-strength additive than the same mounts of each of the cationic guar or the anionic guar, while maintaining substantially the same degree of softness (as measured by bending stiffness) as found in paper lacking a conventional dry-strength additive. A combination of an anionic guar and a cationic acrylamide copolymer is similarly more effective than the acrylamide copolymer alone as a dry strength additive at the same level of addition. These advantages are only achieved if bleached pulp is used in the process according to the invention. 
     Preferably, the wet strength resin is added to the anionic/cationic guar combination according to the invention. A combination of an anionic guar, a cationic guar (or acrylamide copolymer) and the wet strength resin is more effective than a combination of a cationic guar (or acrylamide copolymer) and the wet strength resin, all the other conditions being the same. It is at least as effective as a combination of an anionic guar and the wet strength resin. 
     When clear solutions of the individual components of the mixtures according to the invention are added together, aggregates of fine colloidal particles (which are usually called coacervates), apparently bound together by some physical or chemical force, are formed. This combination provides dry strength enhancement for paper that is higher than the strength enhancement provided by the same mount of either the cationic guar or the anionic guar, demonstrating a synergistic effect from the aggregates of fine colloidal particles that is substantially identical to the results obtained by adding the same anionic and cationic compounds individually to the pulp system. The cationic additive may also be a wet strength resin, when added with the anionic compound either individually to the pulp system or as coacervates. In either case, the presence of the anionic compound very significantly enhances the efficiency of a wet strength resin, and the use of the coacervates has the advantage of convenience. 
     The invention also comprises a composition for modifying a paper pulp slurry to enhance the dry strength of the paper produced without substantially reducing its softness comprising (1) an anionic polymeric component selected from the group of polymers consisting of carboxymethyl guar, carboxymethyl bean gum, carboxymethyl hydroxyethyl guar, and a carboxymethyl hydroxypropyl guar, and (2) a cationic polymeric component selected from the group of polymers consisting of a cationic guar, a cationic acrylamide copolymer, a cationic bean gum, a cationic wet strength resin, and both a cationic wet strength resin and at least one of the other of said cationic polymers, the wet strength resin being an amine polymer-epichlorohydrin resin selected from the group consisting of a polyamide-epichlorohydrin (PALE) resin, a polyalkylenepolyamine-epichlorohydrin (PAPAE) resin, and an amine polymer-epichlorohydrin (APE) resin, in which amine polymer-epichlorohydrin resin amine groups have been alkylated with epichlorohydrin to produce a polyamine-epichlorohydrin resin that has azetidinium or epoxide functionality. 
     Preferably in the said composition, the anionic polymeric component is a carboxymethyl guar and the cationic polymeric component is a cationic guar and a cationic wet strength that is produced by reacting a saturated aliphatic dicarboxylic acid containing three to ten carbon atoms with a polyalkylenepolyamine, containing from two to four ethylene groups, two primary amine groups, and one to three secondary amine groups (such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine), to form a poly(aminoamide) having secondary amine groups that are alkylated with epichlorohydrin to form a PAE resin. Most preferably, the wet strength resin is Kymene 557H (available from Hercules Incorporated), in which adipic acid is reacted with diethylenetriamine to form a poly(aminoamide) that is alkylated and crosslinked with epichlorohydrin to form a PAE resin. The invention also comprises a paper product containing the said composition according to the invention, and a process for making the composition comprising adding adding a mixture of the anionic guar and the cationic guar, preferably as an aqueous suspension, to a paper pulp slurry and then adding the wet strength resin later to form the composition in the slurry. 
     Under the normal wet end conditions of papermaking, the combination of additives according to the invention enhances paper strength through ionic bonds. That enhancement is an important feature for toweling, toilet tissue, or any other fine paper in which softness and dry strength or a combination of dry and wet strength, without compromising softness, are valued properties. 
     A cationic guar molecule with no anionic guar will have all its ionic groups available bond with the cellulose-fiber ionic groups of opposite charge. Thus, a cationic guar by itself is expected to offer a higher number of ionic bonds. When an anionic and a cationic guar are mixed together either in the presence of pulp or by themselves, an interaction takes place between them and this results in a lower number of ionic sites in the combination to bond with cellulose fibers. (A similar effect occurs when a wet strength resin, such as Kymene 557H, is in the additive system). Hence, the higher effectiveness of a combination as a dry strength is unexpected, particularly since it is not present if used with unbleached pulp containing black liquor. 
     According to the results obtained with various guar additives, this synergistic effect of an anionic and a cationic guar additive is independent of the chain-length of the compound as well as molecular weight as measured by solution viscosity. It is also independent of the charge density of the additives. However, the degree of effectiveness of the combinations depends on the molecular weight. There is evidence that the relatively higher molecular weight guars produce relatively-higher paper strength. 
     DETAILED DESCRIPTION OF THE INVENTION 
     Guar is a natural copolymer consisting of galactose and mannose, usually in the ratio of 1 to 2, in a linear chain of β-d-mamopyransyl with λ-D-galactopyranosyl units as side branches. An anionic guar is obtained by reacting a natural guar with caustic and subsequently with monochloroacetate. The resultant product is a carboxymethyl guar (CMG). Similarly, carboxymethylhydroxypropyl guar (CMHPG) is prepared by reacting natural guar with caustic and subsequently with monochloroacetate and propylene oxide. Examples of CMG are Galaxy 70713 D, (Aqualon), Jaguar 8707 (Hi-Tek) and those of CMHPG are WG-18 (Aqualon), Jaguar 8600 (Hi-Tek). Carboxymethyl hydroxyethyl guars are other examples of anionic guar additives. 
     A cationic guar is obtainable by reacting natural guar with caustic and subsequently with quaternary ammonium chloride, and is available from Dow as Dow Quart 188; such a cationic guar is available under the name Gendrive 162. 
     The structure of natural guar gum is as follows: ##STR1## 
     Polyacrylamide is prepared by polymerization of acrylamide with N,N&#39;-methylene bisacrylamide. A cationic polyacrylamide is usually prepared by making reacting polyacrylamide with acryloxytrimethyl ammonium chloride (ATMAC), methylacryloxytrimethyl ammonium chloride (MTMAC) or diallyldimethyl ammonium chloride (DADMAC). The anionic acrylamide compounds are usually copolymers of acrylamides and sodium acrylates. 
     The preferred wet strength resins are produced by reacting a saturated aliphatic dicarboxylic acid containing three to ten carbon atoms, preferable adipic acid, with a polyalkylenepolyamine, containing from two to four ethylene groups, two primary amine groups, and one to three secondary amine groups, such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine, to form a poly(aminoamide) having secondary amine groups that are alkylated with epichlorohydrin to form tertiary aminochlorohydrin groups. These groups self-alkylate to form hydroxyazetidinium groups which are considered responsible for wet strength in paper. They are cationic in character. If tertiary amines are present in the aminopolyamide or polyamine backbones, quaternary epoxide groups are produced. The actual procedure for synthesizing these wet strength resins differ from product to product, but the objective to generate aminopolyamide-epichlorohydrin functionality remains the same. 
     Kymene® wet strength resins are most preferred. Some examples of wet strength resins available from Hercules Incorporated are Kymene 557H, Kymene 450, and Kymene 2064 (an APE resin based on methyldiallylamine monomer that is polymerized to an amine polymer precursor), as well as low absorbable organic halide (AOX) versions such as Kymene 557LX. Most preferred is Kymene 557H, in which adipic acid is reacted with diethylenetriamine (DETA) to form a poly(aminoamide) that is alkylated and crosslinked with epichlorohydrin to form a PAE resin, namely, adipic acid-DETA poly(aminoamide) epichlorohydrin. 
     The specific amount and the type of the additives will depend on, among other the type of pulp characteristics. The ratios of the anionic and the cationic additives may range from 1/20 to 10/1, preferably from 2/1 to 1/2, and most preferably about 1/1. The combination according to the invention is effective when added to the pulp stock in the amount of 0.05 to 5 percent, depending on the type of pulp. The preferable level of addition is 0.1 to 2% based on the dry weight of pulp. 
     Since the additive combinations of the invention consist of two or more components, they can be added to the furnish in different ways that may affect the rate of production in the plant and the properties of the final product. The usual procedure is to add these additives individually in the wet end system in a predetermined sequence to achieve what experiment shows to be the most desirable product. Preferably, however, these additives are introduced into the wet end system by combining the anionic and cationic additives beforehand and adding the resulting coacervates. 
     In the following examples, handsheets were prepared from pulp which was refined in a Valley beater to 500±5 cc Canadian Standard Freeness. The 22.50% consistency pulp slurry was diluted to 266% solids with normal tap water in a proportioner where the combination of additives according to the invention were added to the pulp while stirring. An aliquot of this pulp slurry was further diluted to about 0.023% consistency in a Deckle box for molding handsheets. Both refining and papermaking were made at pH 7.5 to 8.0. Thus, the papermaking process consists of three main steps. They are (a) formation of an aqueous slurry of cellulose fibers, (b) addition of dry strength additives and (c) formation of sheet and drying to a desired moisture content (preferably 3 to 6 percent). 
     The step (b) may be carried out by adding the anionic component to the pulp first, followed by the cationic component, and the wet strength resin if used. Blends of anionic and cationic components may also be added to the pulp directly in the papermaking system, Whether individually or blended together, the additives are mixed into the wet end of the paper machine, preferably under shear. 
     Tensile strength, modulus, and elongation were measured in an Instron, according to a standard procedure, Tappi 494, as a guide. Drying was to a moisture content of 3 to 6 percent. By the same testing procedure, the tensile energy per unit volume that the fibers have assimilated up to the point of rupture was also determined. This is referred to as tensile energy absorption (TEA). The results of bending stiffness presented here have been measured in a Handle O&#39;Meter (Thwing-Albert Instrument Co.). 
     The same testing procedure measures the combined effect of sheet stiffness, surface friction, and thickness that affect the subjective perception of softness of paper products. (Holger Hollmark, TAPPI Journal, p 97, February 1983; Handbook of Physical and Mechanical Testing of Paper and Paperboard, Ed. Richard E. Mark, Ch. 11, p 511, 1983). 
    
    
     EXAMPLE 1 
     This Example is a laboratory evaluation of strength properties and bending stiffness on handsheets prepared with 70/30 Northern Softwood/CTMP furnish. The results are shown in Table 1. The anionic additives were first added to the pulp followed by the cationic additive. The control used in this case is a handsheet prepared with the same pulp with no additive. Galaxy 707D is a carboxymethyl guar (DS 0.08), and Gendrive 162 is a quaternary ammonium chloride treated guar (DS 0.075). Jaguar 8600, available commercially as Hi-Tek, and WG-18, are hydroxypropylcarboxymethyl guars. Guar AQU-3129 and High DS cationic guar (404-48-3) are available from Aqualon, a Hercules Incorporated unit. WC-100 and Hercofloc 1129 sodium acrylate-acrylamidecopolymer and sodium polyacrylate homopolymer, respectively. Reten® is a polyamide-epichlorohydrin polymeric material used as a retention. The &#34;Jaguar&#34; products are available from High-Tek Co. 
     
                                           TABLE 1                                 
__________________________________________________________________________
                                                    Bending               
                                      Enhancement, % Control              
                                                    Stiffness             
Anionic        Cationic               Tensile       % of                  
Additive  Percent                                                         
               Additive          Percent                                  
                                      Strength                            
                                           TEA                            
                                              Elongation                  
                                                    Control               
__________________________________________________________________________
None      --   Gendrive 162      1.0  6.5  -- --    --                    
Galaxy 707D                                                               
          0.5  Reten ® 200   0.4  8.3  -- --    --                    
Galaxy L07D guar                                                          
          0.5  Gendrive 162      0.5  33.9 -- --     94                   
None      --   Jaguar CP-13      1.00 6.6  13.9                           
                                              10.0  --                    
Jaguar 8600                                                               
          0.5  Jaguar CP-13      0.50 16.0 23.9                           
                                              13.0  106                   
None      --   High MW Cationic Guar (0083-40-3)                          
                                 1.00 4.0  12.7                           
                                              3.1   104                   
K0341A 2 (WG-18)                                                          
          0.5  0083-40-3         0.5  12.0 23.1                           
                                              13.0  105                   
None      --   Percol 743        1.00 2.5  3.5                            
                                              2.8   101                   
WC-100    0.5  Percol 743        0.50 14.0 6.9                            
                                              22.0  113                   
Hercofloc 1129                                                            
          0.5  Reten 157         0.50 15.4 3.2                            
                                              8.9   101                   
None      --   404-48-3          1.0  3.7                                 
AQU-D3129 0.5  404-48-3          0.5  14.3                                
Jaguar 8707                                                               
          0.5  Jaguar CP-13      0.5  21.3 48.0                           
                                              19.4                        
__________________________________________________________________________
 
    
     EXAMPLE 2 
     Results on laboratory evaluation of strength properties, tensile stiffness and bending stiffness on handsheets prepared as in Example 1 are presented in Table 2. Pulp system employed in Set No. 1 is 50/50 recycled/northern softwood bleached kraft pulp. In Set No. 2, the pulp is 100 percent bleached kraft. The process to prepare the guars is similar to what has been explained in Example 1, except that the anionic guar was a carboxymethyl guar (available from Aqualon under the designation AQU-D3129) having a DS of 0.15 and the cationic guar (available from Aqualon under the designation 404-48-3) was a quaternary-modified guar, having a DS of 0.10. 
     
                                           TABLE 2                                 
__________________________________________________________________________
                                  Tensile                                 
                                       Bending                            
                    Enhancement, % of Control                             
                                  Stiffness                               
                                       Stiffness                          
    Anionic  Cationic                                                     
                    Tensile  Elonga-                                      
                                  % of % of                               
None                                                                      
    Guar   % Guar % Strength                                              
                         TEA tion control                                 
                                       Control                            
__________________________________________________________________________
1   AQU-D3129                                                             
           0.5                                                            
             404-48-3                                                     
                  0.5                                                     
                    21.5 37.77                                            
                             13.3 108  95                                 
2   AQU-D3129                                                             
           0.5                                                            
             404-48-3                                                     
                  0.5                                                     
                    15.2 31.22                                            
                             16.1 99   99                                 
__________________________________________________________________________
 
    
     EXAMPLE 3 
     Laboratory evaluation results of strength properties and bending stiffness on handsheets prepared with 70/30 northern softwood/CTMP (Nos. 1 and 2) and recycled pulps (Nos.3 to 5) are shown in Table 3. The anionic additive is added to the pulp prior to adding the cationic additive. The guar additives Galaxy 707D and Gendrive 162 are the same as those used in Example 1. Kymene® 557H is the reaction product of an polyamide and epichlorohydrin conventionally used as a wet strength resin in paper and available from Hercules Incorporated. KN9-56CMG is a carboxymethyl guar. The combinations show minimal adverse effects on paper softness caused by the presence of the wet strength agent, as indicated by the stiffness data. 
     
                                           TABLE 3                                 
__________________________________________________________________________
                                               Bending                    
                          Enhancement, % of Control                       
                                               Stiffness                  
  Anionic     Cationic    Kymene 557H                                     
                                  Dry          % of                       
No                                                                        
  Additive                                                                
         Percent                                                          
              Additive                                                    
                     Percent                                              
                          Percent Tensile                                 
                                      Elongation                          
                                            TEA                           
                                               Control                    
__________________________________________________________________________
1 None   --   None   --   1.0     10.8                                    
                                      10.0  --  95                        
2 KN9-56CMG                                                               
         0.15 Gendrive 162                                                
                     0.15 0.75    18.3                                    
                                      13.9     108                        
3 None   --   None   --   1.0     11.9                                    
                                      22.2  20.6                          
                                               --                         
4 None   --   Gendrive 162                                                
                     0.5  0.5     19.6                                    
                                      25.9  34.4                          
                                               --                         
5 Galaxy 707D                                                             
         0.25 Gendrive 162                                                
                     0.25 0.5     34.5                                    
                                      33.2  77.6                          
                                               104                        
__________________________________________________________________________
 
    
     COMPARATIVE EXAMPLE 4 
     Results of the evaluation of strength on handsheets prepared with unbleached kraft containing about 2 percent black liquor are shown in Table 4. The results show that a combination of an anionic and a cationic guar additive is not more effective than the cationic guar additive alone when added at the same total level. The guar additives, Galaxy 707D and Gendrive 162, are the same as used in Example 1. 
     
                                           TABLE 4                                 
__________________________________________________________________________
                        Enhancement, % of Control                         
Anionic     Cationic    Tensile                                           
Additive                                                                  
       Percent                                                            
            Additive                                                      
                   Percent                                                
                        Strength                                          
                             TEA                                          
                                Elongation                                
__________________________________________________________________________
Galaxy 707D                                                               
       0.50 Gendrive 162                                                  
                   0.5  14.2 21.1                                         
                                12.5                                      
None   --   Gendrive 162                                                  
                   1.0  16.9 25.3                                         
                                12.5                                      
__________________________________________________________________________
 
    
     COMPARATIVE EXAMPLE 5 
     Results of strength properties evaluation on handsheets prepared with partially unbleached kraft incorporated externally with 0.9% black liquor are presented in Table 5. The results show that a combination of an anionic and a cationic guar, when added to this unbleached kraft-black liquor system, is in fact less effective than the cationic guar alone at the same total addition level. The guar additives are the same as those used in Example 1. 
     
                                           TABLE 5                                 
__________________________________________________________________________
                        Tensile                                           
Anionic     Cationic    Strength                                          
                             TEA   Elongation                             
Additive                                                                  
       Percent                                                            
            Additive                                                      
                   Percent                                                
                        (PSI)                                             
                             (ft. lb/ft.sup.2)                            
                                   (%)                                    
__________________________________________________________________________
Control                                                                   
       --   --     --   5877 5.29  2.2                                    
Galaxy 707D                                                               
       0.5  Gendrive 162                                                  
                   0.5  7644 7.58  2.6                                    
None   --   Gendrive 162                                                  
                   1.0  8684 10.62 3.0                                    
__________________________________________________________________________
 
    
     EXAMPLE 6 
     This series of tests examines the strength properties and bending stiffness of paper prepared in a small-scale pilot plant version of a conventional paper machine, located at Kalamazoo, Mich. and referred to herein as the Laboratory Former. The pulps used in the numbered tests were: Nos. 1 and 2, 50/50 NSW/NHW kraft; Nos. 3, 4, 7 and 8, 70/30 long fiber/sawdust; and Nos. 1 and 2, 70/30 virgin fiber/broke. In each case, a combination of an anionic and a cationic additive (guar or acrylamide copolymer) was incorporated in the pulp followed by the same amount of wet strength resin Kymene 557H. The anionic components used were all carboxymethyl guars. Among the cationic additives, Percol 743 is a polyacrylamide copolymer, the rest are guars. These results, recorded after 2 weeks natural curing and presented in Table 6, represent the enhancements of properties over what are obtained with 1 percent Kymene 557H alone. They demonstrate the fact that these combinations of an anionic and a cationic component provide synergistic effects on wet strength as well as dry strength of paper. These effects are significantly greater when one of the components is a conventional wet strength resin, such as Kymene 557H. 
     
                                           TABLE 6                                 
__________________________________________________________________________
                                Enhancement over Bending                  
                           Total                                          
                                Control Containing                        
                                                 Stiffness                
                      Kymene                                              
                           Additive                                       
                                1% Kymene 557H   % of 1%                  
  Anionic   Cationic  557H Level                                          
                                Dry          Wet Kymene                   
No                                                                        
  Additive                                                                
         %  Additive                                                      
                   %  %    %    Tensile                                   
                                    Elongation                            
                                          TEA                             
                                             Tensile                      
                                                 Control                  
__________________________________________________________________________
1 WG-18  0.30                                                             
            Percol 743                                                    
                   0.20                                                   
                      0.50 1.00 20.3                                      
                                    19.5  42.5                            
                                             17.8                         
                                                 99                       
2 Galaxy 707D                                                             
         0.30                                                             
            Gendrive 162                                                  
                   0.20                                                   
                      0.50 1.00 18.0                                      
                                    24.2  45.3                            
                                             10.7                         
                                                 9.6                      
3 0087-08-2                                                               
         0.30                                                             
            Gendrive 162                                                  
                   0.20                                                   
                      0.50 1.00 26.2                                      
                                    28.2  62.2                            
                                             31.9                         
                                                 109                      
4 0087-08-2                                                               
         0.30                                                             
            Percol 743                                                    
                   0.20                                                   
                      0.50 1.00 26.3                                      
                                    32.2  63.1                            
                                             40.5                         
                                                 99                       
5 0087-08-2                                                               
         0.30                                                             
            Percol 743                                                    
                   0.20                                                   
                      0.50 1.00 20.5                                      
                                    26.8  57.1                            
                                             17.5                         
                                                 99                       
6 WG-18  0.30                                                             
            0083-40-3                                                     
                   0.20                                                   
                      0.50 1.00 15.4                                      
                                    18.5  36.8                            
                                             11.3                         
                                                 107                      
7 D-3129 0.30                                                             
            Percol 743                                                    
                   0.20                                                   
                      0.50 1.00 25.0                                      
                                    22.0  52.0                            
                                             36.8                         
                                                 104                      
8 WG-18  0.30                                                             
            0083-40-3                                                     
                   0.20                                                   
                      0.50 1.00 19.3                                      
                                    27.3  62.0                            
                                             29.2                         
                                                 98                       
__________________________________________________________________________
 
    
     EXAMPLE 7 
     This series of tests examines the strength properties and bending stiffness on handsheets prepared in the Laboratory Former. The pulps used in the numbered tests were: Nos. 1 to 6, 55/30/15 northern softwood/CTMP/recycled pulp, and No. 7, 50/50 northern softwood/hardwood furnish. The results in No 8 were produced from handsheets using 70/30 northern softwood/CTMP pulp. All the cationic additives were modified polyacrylamides. Percol 743 is a copolymer of acrylamide and 10 mole % MTMAC (Methylacryloxytrimethyl ammonium chloride), Reten 157 contains 10 mole % ATMAC (acryloxytrimethyl ammonium chloride) and Hercofloc 1154 contains 6 mole % DADMAC (dialcryloxydimethyl ammonium chloride). All the anionic additives are guar products available from Aqualon. The results are recorded in Table 7. 
     
                                           TABLE 7                                 
__________________________________________________________________________
POLYACRYLAMIDE COPOLYMER - GUAR COMBINATIONS                              
                                            Bending                       
                              Enhancement, % of Control                   
                                            Stiffness                     
  Anionic        Cationic     Tensile       % of                          
No                                                                        
  Additive  Percent                                                       
                 Additive                                                 
                         Percent                                          
                              Strength                                    
                                   Elongation                             
                                         TEA                              
                                            Control                       
__________________________________________________________________________
1 None      --   Percol 743                                               
                         1.00 6.4  15.0  22.6                             
                                            --                            
2 K0341 A2 WG-18)                                                         
            0.50 Percol 743                                               
                         0.50 17.8 12.9  36.3                             
                                            --                            
3 None      --   Reten 157                                                
                         1.0  5.3  11.7  14.6                             
                                            --                            
4 AQU-D3129 0.50 Reten 157                                                
                         0.5  12.7 19.5  35.3                             
                                            --                            
5 None      --   Hercofloc 1154                                           
                         1.0  11.7 10.0  21.1                             
                                            --                            
6 AQU-D3129 0.50 Hercofloc 1154                                           
                         0.50 16.9 22.8  44.2                             
                                            --                            
7 AQU-D3129 0.50 Percol 743                                               
                         0.50 37.5 45.5  101                              
                                            106                           
8 Galaxy 707D                                                             
            0.50 Hercofloc 1154                                           
                         0.50 16.3 8.0   26.4                             
                                             92                           
__________________________________________________________________________
 
    
     EXAMPLE 8 
     This series of tests examines the strength properties and bending stiffness of paper prepared in the Kalamazoo Laboratory Former with 70/30 northern softwood/CTMP furnish. The anionic component was added first followed by the cationic component, and the wet strength resin (Kymene 557H) was added last. The results, recorded in Table 8, show that the combination of a wet strength resin and an anionic and a cationic guar, and even the combination of a an anionic guar and a wet strength resin enhances not only the dry strength but also the wet strength very significantly over the corresponding properties obtained by the same amount of the wet strength resin alone. The bending stiffness of the paper samples not adversely affected by the presence of these additive combinations. The additives AQU-D 3129, Galaxy 707D and 0.1 DSCMG are anionic carboxymethyl guars. 404-48-3, 404-48-1 and Gendrive 162 are Aqualon cationic guars of which the first two are developmental. The respective controls used were made with the same furnish, but with no additive. 
     
                                           TABLE 8                                 
__________________________________________________________________________
                           Total                                          
                                Enhancement, % of Control                 
                                                 Bending                  
                      Kymene                                              
                           Additive          Wet Stiffness                
  Anionic   Cationic  557H Level                                          
                                Dry          Tensile                      
                                                 % of                     
No                                                                        
  Additive                                                                
         %  Additive                                                      
                   %  %    %    Tensile                                   
                                    Elonation                             
                                          TEA                             
                                             (P/I)                        
                                                 Control                  
__________________________________________________________________________
1 None   -- None   -- 1.00 1.00  9.1                                      
                                    3.4   13.0                            
                                             5.65                         
                                                 113                      
2 None   -- None   -- 1.50 1.50 --  9.9   15.5                            
                                             5.85                         
                                                 130                      
3 None   -- None   -- 2.00 2.00 11.9                                      
                                    13.0  37.0                            
                                             5.93                         
                                                 --                       
4 AQU-D3129                                                               
         0.13                                                             
            404-48-3                                                      
                   0.13                                                   
                      1.00 1.26 17.5                                      
                                    24.0  52.3                            
                                             6.44                         
                                                 88                       
5 Galaxy 707D                                                             
         0.25                                                             
            404-48-1                                                      
                   0.25                                                   
                      1.00 1.50 16.3                                      
                                    20.0  37.0                            
                                             6.58                         
                                                 91                       
6 0.1 DSCMG                                                               
         0.19                                                             
            404-48-1                                                      
                   0.19                                                   
                      1.50 1.88 28.2                                      
                                    4.3   29.8                            
                                             7.14                         
                                                 --                       
7 0.1 DSCMG                                                               
         0.50                                                             
            Gendrive 162                                                  
                   0.50                                                   
                      1.00 2.00 33.4                                      
                                    8.9   38.9                            
                                             7.15                         
                                                 89                       
8 0.1 DSCMG                                                               
         1.00                                                             
            None   -- 1.00 2.00 32.6                                      
                                    9.8   30.9                            
                                             7.67                         
                                                 --                       
__________________________________________________________________________
 
    
     EXAMPLE 9 
     This series of tests examines the strength properties and bending stiffness of handsheets prepared from the following pulps: Nos. 1 to 4, 50/50 softwood/hardwood kraft (SWK/HWK); (Nos. 5 and 6), 70/30 northern softwood kraft/CTMP (NSK/CTMP). AQU-D3129 and Galaxy 707D are anionic carboxymethyl guars previously referred to, and Gendrive 162 is a cationic guar previously referred to, while 404-48-3 is a developmental cationic guar. The results, which are recorded in Table 9, show that the paper properties obtained by adding to the pulp coacervates formed by premixing the anionic and cationic components are about the same as those obtained by adding the additives individually to the pulp. They were significantly more convenient to use. 
     
                                           TABLE 9                                 
__________________________________________________________________________
                                 Enhancement over Control                 
                                 Containing    Bending                    
                                 1% Kymene 557H                           
                                               Stiffness                  
  Anionic  Cationic Modes of Addition                                     
                                 Tensile       % of                       
No                                                                        
  Additive                                                                
         % Additive                                                       
                  % to Pulp System                                        
                                 Strength                                 
                                      Elongation                          
                                            TEA                           
                                               Control                    
__________________________________________________________________________
1 AQU-D3129                                                               
         0.5                                                              
           404-48-3                                                       
                  0.5                                                     
                    Added individually in pulp                            
                                 12.2 12.5  11.6                          
                                               102                        
2 AQU-D3129                                                               
         0.5                                                              
           404-48-3                                                       
                  0.5                                                     
                    Premixed to form                                      
                                 12.8 8.3   21.7                          
                                               107                        
                    coacervate before adding                              
                    to pulp                                               
3 AQU-D3129                                                               
         1.0                                                              
           404-48-3                                                       
                  1.0                                                     
                    Added individually                                    
                                 28.5 25.0  45.0                          
                                               108                        
4 AQU-D3129                                                               
         1.0                                                              
           404-48-3                                                       
                  1.0                                                     
                    Premixed to form                                      
                                 25.6 29.2  49.8                          
                                               110                        
                    coacervate                                            
5 Galaxy 707D                                                             
         0.5                                                              
           Gendrive 162                                                   
                  0.5                                                     
                    Added individually to pulp                            
                                 17.8 6.5   28.5                          
                                               91                         
6 Galaxy 707D                                                             
         0.5                                                              
           Gendrive 162                                                   
                  0.5                                                     
                    Premixed to form                                      
                                 17.4 9.7   29.3                          
                                               95                         
                    coacervate before adding                              
                    to pulp                                               
__________________________________________________________________________
 
    
     EXAMPLE 10 
     Dry strength properties and bending stiffness of paper prepared in the Kalamazoo Laboratory Former (KLF) with 55/30/15 NSK/CTMP/secondary furnish are presented in Table 10. The dam recorded in K-17803 and K-17822 represent enhancement of dry strength properties over what was obtained with the control with no additive. The anionic additive employed are CMG (AQU-D3129, Galaxy 707D) and CMHPG (WG-18) while the cationic components are cationic guars (Jaguar CP-13-HiTek, and 0083-40-3) and acrylamide copolymer (Percol 743). The results show that in most cases, at the same level of addition, dry strength with a combination of an anionic and a cationic guar (or a cationic polyacrylamide) is significantly higher than what is obtained with a combination of an anionic guar and the wet strength resin Kymene 557H, with less adverse effect of paper softness, as indicated by the bending stiffness results. 
     
                                           TABLE 10                                
__________________________________________________________________________
                                               Bending                    
                        Kymene                                            
                             Total                                        
                                  Enhancement, Stiffness                  
Anionic     Cationic    557H Additive                                     
                                  % of Control % of                       
Additive                                                                  
       Percent                                                            
            Additive                                                      
                   Percent                                                
                        Percent                                           
                             Level %                                      
                                  Tensile                                 
                                      TEA                                 
                                         Elongation                       
                                               Control                    
__________________________________________________________________________
AQU-D3129                                                                 
       0.50 Jaguar CP-13                                                  
                   0.50 None 1.00 43.3                                    
                                      76.0                                
                                         29.0  87                         
WG-18  0.50 Percol 743                                                    
                   0.50 None 1.00 32.9                                    
                                      63.2                                
                                         27.8  89                         
WG-18  0.50 0083-40-3                                                     
                   0.50 None 1.00 26.9                                    
                                      47.0                                
                                         19.5  108                        
AQU-D3129                                                                 
       0.50 None   --   0.50 1.00 23.5                                    
                                      54.2                                
                                         23.9  112                        
WG-18  0.50 None   --   0.50 1.00 9.3 28.0                                
                                         18.0  110                        
Galaxy 707D                                                               
       0.50 None   --   0.50 1.00 25.7                                    
                                      57.0                                
                                         23.9  118                        
__________________________________________________________________________
 
    
     EXAMPLE 11 
     Dry strength properties and bending stiffness of paper prepared in the KLF using 70/30 NSK/CTMP furnish are recorded in Table 11. The data demonstrated enhancement of dry strength properties over what was obtained with the control containing no additive. The anionic additives are CMG and cationic components are either cationic guar or Kymene 157H, a wet strength resin. The results show that in most cases, at the same level of addition, a combination of an anionic and a cationic guar provides significantly higher dry strength than what is obtained with the combination of an anionic guar and Kymene, with less adverse effect on paper softness. 
     
                                           TABLE 11                                
__________________________________________________________________________
                                             Bending                      
                      Kymene                                              
                           Total                                          
                                Enhancement, Stiffness                    
Anionic     Cationic  557H Additive                                       
                                % of Control % of                         
Additive                                                                  
       Percent                                                            
            Additive                                                      
                 Percent                                                  
                      Percent                                             
                           Level %                                        
                                Tensile                                   
                                    TEA                                   
                                       Elongation                         
                                             Control                      
__________________________________________________________________________
AQU-D3129                                                                 
       0.50 404-48-1                                                      
                 0.50 None 1.00 34.8                                      
                                    53.7                                  
                                       25.7  95                           
AQU-D3129                                                                 
       0.60 404-48-3                                                      
                 0.40 None 1.00 25.6                                      
                                    45.9                                  
                                       21.0  92                           
AQU-D3129                                                                 
       0.50 404-48-3                                                      
                 0.50 None 1.00 25.9                                      
                                    96.6                                  
                                       51.2  96                           
AQU-D3129                                                                 
       0.50 None --    0.50                                               
                           1.00 18.4                                      
                                    26.7                                  
                                       9.8   110                          
Galaxy 707D                                                               
       0.50 None --   1.0  1.50 26.5                                      
                                    51.5                                  
                                       22.8  116                          
0.1 DS CMG                                                                
       1.0  None --   1.0  2.00 22.5                                      
                                    30.9                                  
                                       9.2   --                           
__________________________________________________________________________
 
    
     COMPARATIVE EXAMPLE 12 
     Strength properties and bending stiffness of paper prepared at the Kalamazoo Laboratory Former with 70/30 NSW/CTMP are presented in Table 12. The results demonstrate enhancement of dry strength properties over what was obtained with the control with no additive while the wet strength tensile is the enhancement over what was obtained with 0.5% Kymene® alone. To demonstrate the advantages achieved by the combinations of anionic and cationic components according to the invention over the prior art combinations described in U.S. Pat. No. 3,058,873, the anionic additives used according to the invention were CMG and CMHPG, while CMC-6CTL is a technical grade carboxymethyl cellulose such that disclosed in the Patent. Gendrive 162 is a cationic guar and Reten® 157 is an acrylamide copolymer. A sharp drop in dry strength accompanied by an increase in bending stiffness was noted whe the carboxymethyl cellulose was used. 
     
                                           TABLE 12                                
__________________________________________________________________________
                            Kymene             Wet Strength               
                                                        Bending           
Run                                                                       
   Anionic      Cationic    557H Enhancement, % of Control                
                                               Enhancement                
                                                        Stiffness         
No.                                                                       
   Additive                                                               
           Percent                                                        
                Additive                                                  
                       Percent                                            
                            Percent                                       
                                 Tensile                                  
                                     TEA Elongation                       
                                               % 0.5 Kymene               
                                                        % of              
__________________________________________________________________________
                                                        Control           
1  Galaxy 707D                                                            
           0.30 Gendrive 162                                              
                       0.20 0.50 31.0                                     
                                     102 33.6  24.5     --                
2  Galaxy 707D                                                            
           0.50 None   --   0.50 27.6                                     
                                     68  30.6  27.0     --                
3  WG-18   0.20 Reten 157                                                 
                       0.30 0.50 30.8                                     
                                     76  --    --       96                
4  WG-18   0.50 None   --   0.50 22.4                                     
                                     60  37.3  25.7     94                
 5*                                                                       
   CMC-6CTL                                                               
           0.50 None   --   0.50 13.5                                     
                                     21  13.1  12.0     99                
__________________________________________________________________________
 *See US Patnet 3,058,873 described above.                                
 
    
     TESTS OF ADDITIVES FOR EXAMPLES 
     Results of viscosity and relative specific viscosity (RSV) for 0.25% aqueous solutions of the guar additives are shown in Table 13. The results indicate the range of relative molecular weights of typical additives employed in the examples. Since these data do not lead to the absolute molecular weights of the additives, no comparison can be made with similar data for materials of different molecular shapes. Charge densities of typical additives employed in the examples are shown in Table 14. 
     
                       TABLE 13                                                    
______________________________________                                    
Additives       Viscosity (CP)                                            
                            RSV (dl/g)                                    
______________________________________                                    
Guar Gendrive 162                                                         
                31.1        121.5                                         
Guar Galaxy 707D                                                          
                9.0         32.4                                          
Guar Jaguar CP-13                                                         
                66.5        223.8                                         
______________________________________                                    
 
    
     
                       TABLE 14                                                    
______________________________________                                    
             Charge Density                                               
                         Viscosity (cp)                                   
Product      (meq/g)     2% Solution                                      
______________________________________                                    
AQU-D3129    -1.34       2,300                                            
404-48-3     0.86        4,200                                            
Jaguar 8707  -0.012      12,000                                           
Jaguar LP-13 0.23        23,000                                           
______________________________________