Patent Publication Number: US-4147650-A

Title: Slurried detergent and method

Description:
This is a continuation of application Ser. No. 660,588 filed Feb. 23, 1976 now abandoned. 
    
    
     This invention relates to a new improved slurry for use in warewashing machines as well as to a method for using same. The present slurry detergent may be formulated typically with alkali metal hydroxides and/or silicates, condensed phosphates, sodium hypochlorite and sodium polyacrylate, or the like. 
     It has been known in formulating machine dishwashing compositions to use various combinations of inorganic builder salts such as polyphosphates, metasilicates, and carbonates combined with caustic materials such as sodium hydroxide. When sodium orthosilicate is used as a builder salt, there is no need to add the caustic material since the orthosilicate functions as alkaline builder while supplying an alkaline value. 
     Granular and liquid mechanical warewashing, e.g., dishwashing, products are well known to the art. These products also have well known inherent deficiencies. For example, granular products are subject to caking in the package or in the dispensers from which they are fed into the washmachine. Bulk aids or &#34;fillers&#34; are included which serve no direct purpose in mechanical warewashing. 
     On the other hand, liquid mechanical warewashing products are limited in the amount of active ingredients, which can be dissolved in water and still provide a stable detergent system. 
     It has now been found that by incorporating optimum properties of both liquid and granular detergents into a single product it is possible to prepare a novel blend in slurry form. The slurry eliminates caking of detergent and resulting problems in maintaining concentration in the washmachine. It further provides improved performance over liquid products which are limited in their strength by the solubility of its ingredients. The present slurry allows use of more complex phosphates and alkaline ingredients since in a slurry no true solution need be formed. Rather, a mass of semi-fluid ingredients of relatively homogeneous nature is the only prerequisite. 
     Generally, the present mechanical warewashing product in slurried form contains caustic soda or potash which may be replaced completely or in part with sodium metasilicate or other alkali as a source of alkalinity, sodium tripolyphosphate, sodium hypochlorite and sodium polyacrylate. Sodium polacrylate acts synergistically with the sodium tripolyphosphate to form a homogeneous suspension in slurry form, thereby facilitating uniform and complete dispensing. 
     The various components used to formulate the slurry detergent composition may be combined by uniformly mixing the various additions until a substantially uniform slurry is obtained. Ordinary liquid mixing equipment having preferably high speed, high shear mixing blades are especiallay useful for slurry formation. 
     Although not necessarily required in the composition of the present invention, it is recognized that additional components may be added such as filler materials, antiseptic materials, sanitizing material, and the like provided these materials do not deleteriously affect formation of the composition when added to a suitable solvent such as water. 
     Embodiments of this invention are both useful and convenient to disperse as detergents, for example, that are used in cleaning and/or sanitizing food contact surfaces, such as kitchen ware, food processing and bottling equipment and environments and metal cleaning. 
     An advantage of making the present slurried product is that ordinary liquids require complete solution of the ingredients. Ordinary granular products require the use of costly fillers versus the water used in liquids. Furthermore, the optimum product uses sodium hypochlorite which is inexpensive and has not yet been successfully blended into an ordinary granular product. 
     Optionally, the present invention may be formulated most generally of chlorine and a water softening system. 
     Alkaline builders found useful herein include alkali metal hydroxides and/or silicates, or the like. In order to form a proper slurry, no more than 40% weight of either of these ingredients, taken separately or in combined total amount, may be used in the total mix. Usage of greater amounts of alkaline builders tends to lead to formation of solid mass. A minimum amount of alkaline builder forming the present composition is 2.5% by weight of the slurry ingredients, dry basis. 
     A source of chlorine may be sodium hypochlorite which is preferred due to its low cost and good stability. Dichloro-isocyanurate anhydrous, dihydrate or monohydrate may be used as well as chlorinated TSP or Halane, a marked product by BASF-Wyandotte for dichloro-dimethyl hydantoin without destroying the present concept. Chlorine may be eliminated and still the present slurry may be a useful detergent product. 
     The level of chlorine used has little effect on the formation of a slurry when employed at levels below 5% chlorine, on a dry basis by weight. Thus, the chlorine source may be in amounts of 0 to 5% by weight dry basis. 
     The water conditioning system may be formed of sodium tripolyphosphate or tetrasodium pyrophosphate or other complex phosphates such as sodium hexametaphosphate or other builder salts, and sodium polyacrylate or sodium polymethacrylate, as well as other polyelectrolytes as desired. Aside from water conditioning, these materials serve as binder for the slurry, forming a matrix which forms the homogeneous mass. As long as no more than 30% by weight of sodium tripolyphosphate and 5.0% by dry weight of sodium polyacrylate is used, satisfactory slurry is formed. If more is used, the mass becomes too viscous or may solidify in the mixer and prevent transfer to the shipping container. A minimum amount of water conditioner is 5% by weight tripolyphosphate and 1% by weight polyacrylate, dry weight basis. 
     Generally, the water conditioning system may be a water-soluble polyelectrolyte polymer having a molecular weight of from 1,000 to 15,000,000 and having repeated groups with the formula: ##STR1## wherein R is either hydrogen or a methyl radical, and R&#39; is selected from the group consisting of amide radical, carboxyl radical and salts thereof. 
     Preferably the water soluble organic polymer of the present invention is an alkali metal salt of the polyacrylate component having a molecular weight in the range of about 1,000 to about 15,000,000 and having repeated groups with the formula: ##STR2## wherein R is a hydrogen radical and R&#39; is a carboxyl group or an alkali metal salt thereof. The water soluble organic polymer is included in an amount from about 1,0 to about 20 parts by weight and preferably in an amount from about 1 to about 10 parts by weight on an anhydrous basis. 
     A number of additional specific examples of the water conditioning system are disclosed in U.S. Pat. No. 3,623,991, the effective parts of which are incorporated herein by reference. 
     Dispensing of the slurry product is effected by means of the system taught by Farison in U.S. Pat. No. 3,200,835 since it is not a true liquid. 
     The following formulations generally define the present the relative amounts of ingredients useful in practice of the present invention: 
     
                       TABLE I                                                     
______________________________________                                    
                    Wet Basis                                             
Ingredients         Range     Preferred                                   
______________________________________                                    
Water               15-85%    30-50%                                      
Liquid sodium or potassium                                                
hydroxide (50%)     5-40%     10-30%                                      
Sodium metasilicate anhydrous                                             
                    0-20%     0-10%                                       
Potassium silicate (20%)                                                  
1:2.50 ratio        0-20%     0-10%                                       
Sodium hypochlorite (15%)                                                 
                    0-34%     0-20%                                       
Sodium tripolyphosphate                                                   
                    5-30%     15-25%                                      
Sodium polyacrylate (20%)                                                 
Avg. molecular wt (85,000-95,000)                                         
                    5-20%     5-15%                                       
______________________________________                                    
 
    
     
                       TABLE II                                                    
______________________________________                                    
                    Dry Basis                                             
Ingredients         Range     Preferred                                   
______________________________________                                    
Water               40-85%    50-70%                                      
Sodium or potassium hydroxide                                             
                    2.5-20%   5-15%                                       
Sodium metasilicate anhydrous                                             
                    0-20%     0-10%                                       
Potassium silicate (20%)                                                  
1:2.50 ratio        0-8%      0-4%                                        
Sodium hypochlorite 0-5.0%    0-3.0%                                      
Sodium tripolyphosphate                                                   
                    5-30%     15-25%                                      
Sodium polyacrylate                                                       
Avg. molecular wt (85,000-95,000)                                         
                    1.0-5.0%  1.0-2.0%                                    
______________________________________                                    
 
    
     It is generally found that after application of the present slurry detergent and removal thereof from a surface, the surface is effectively sanitized and substantially cleaned. 
    
    
     In order to further illustrate the present invention, the following examples are given wherein all parts are by weight unless otherwise indicated: 
     
                                           TABLE III                               
__________________________________________________________________________
EXAMPLES                                                                  
               EXAMPLE                                                    
INGREDIENT     1   2   3   4   5   6   7   8   9   10  11  12             
__________________________________________________________________________
               %   %   %   %   %   %   %   %   %   %   %   %              
Water          35.0                                                       
                   45.0                                                   
                       46.2                                               
                           56.2                                           
                               20.0                                       
                                   30.0                                   
                                       35.0                               
                                           45.0                           
                                               46.2                       
                                                   56.2                   
                                                       20.0               
                                                           30.0           
Sodium Hydroxide (50%)                                                    
               20.0                                                       
                   20.0                                                   
                       20.0                                               
                           20.0                                           
                               20.0                                       
                                   20.0                                   
                                       --  --  --  --  --  --             
Sodium Metasilicate                                                       
Anhydrous      --  --  --  --  --  --  10.0                               
                                           10.0                           
                                               10.0                       
                                                   10.0                   
                                                       10.0               
                                                           10.0           
Potassium Silicate                                                        
20% SiO.sub.2 1:2.50 ratio                                                
               --  --  --  --  --  --  10.0                               
                                           10.0                           
                                               10.0                       
                                                   10.0                   
                                                       10.0               
                                                           10.0           
Sodium Tripolyphosphate                                                   
               20.0                                                       
                   20.0                                                   
                       20.0                                               
                           20.0                                           
                               20.0                                       
                                   20.0                                   
                                       20.0                               
                                           20.0                           
                                               20.0                       
                                                   20.0                   
                                                       20.0               
                                                           20.0           
Sodium Hypochlorite                                                       
(15%)          15.0                                                       
                   15.0                                                   
                       --  --  --  --  15.0                               
                                           15.0                           
                                               --  --  --  --             
Sodium Dichloro-                                                          
isocyanurate dihydrate                                                    
               --  --   3.8                                               
                            3.8                                           
                               --  --  --  --   3.8                       
                                                    3.8                   
                                                       --  --             
Chlorinated TSP                                                           
               --  --  --  --  30.0                                       
                                   30.0                                   
                                       --  --  --  --  30.0               
                                                           30.            
Sodium Polyacrylate                                                       
Avg. Mol. Wt.                                                             
85,000-95,000  10.0                                                       
                   --  10.0                                               
                           --  10.0                                       
                                   --  10.0                               
                                           --  10.0                       
                                                   --  10.0               
                                                           --             
Initial Available                                                         
Chlorine       1.24%                                                      
                   1.33%                                                  
                       1.13%                                              
                           1.20%                                          
                               1.11%                                      
                                   1.20%                                  
                                       1.32%                              
                                           1.32%                          
                                               1.13%                      
                                                   1.17%                  
                                                       .53%               
                                                           .60%           
Available Chlorine                                                        
after 24 hours at 120° F.                                          
               1.15%                                                      
                   1.27%                                                  
                       .53%                                               
                           .60%                                           
                               .71%                                       
                                   .79%                                   
                                       1.20%                              
                                           1.28%                          
                                               .53%                       
                                                   .61%                   
                                                       .01%               
                                                           .02%           
Available Chlorine                                                        
after 96 hours at 120° F.                                          
               .92%                                                       
                   1.06%                                                  
                       .07%                                               
                           .10%                                           
                               .31%                                       
                                   .32%                                   
                                       .92%                               
                                           1.09%                          
                                               .07%                       
                                                   .09%                   
                                                       .00%               
                                                           .00%           
__________________________________________________________________________
 
    
     In order to show polyphosphate and sodium polyacrylate: 
     The formulations of Examples 1 and 2 were tested by making dilutions of 0.1%, 0.2% and 0.3% in synthetic hard water of 5, 10, 15 and 20 grains and in Cincinnati tap water of 9.5 grains. These solutions were heated to 160°F. and then allowed to stand twenty-four hours to exhibit the synergistic effect of sodium tripolyphosphate and sodium polyacrylate. Sodium polyacrylate &#34;extends&#34; the water softening capacity of sodium tripolyphosphate beyond its theoretical value. 
     The formulation of Example 2 has a theoretical water softening capacity of 8-9 grains per gallon at a 0.3% concentration. Threshholding normally adds several grains of hard water tolerance to the system. Thus, the formulation of Example 2 exhibits no floc at 10 grains of hardness, but a trace of floc at 15 grains. The formulation of Example 1 exhibits some turbidity, but no floc through 20 grains of hardness. 
     In slurry products containing available chlorine, other suitable polyelectrolytes, such as polymethacrylate, which are chlorine compatible may be beneficially employed. The choice of polyelectrolyte is much less restrictive in slurries not containing available chlorine. 
     Results of using the formulation of Example 1: 
     
                                           TABLE IV                                
__________________________________________________________________________
       WATER HARDNESS                                                     
           91/2                                                           
DILUTIONS                                                                 
       5 GR.                                                              
           GR. TAP                                                        
                10 GR.                                                    
                      15 GR. 20 GR. TIME SPAN                             
__________________________________________________________________________
.1%    Clear                                                              
           Clear                                                          
                5/8&#34; floc                                                 
                      7/8&#34; floc                                           
                             7/8&#34; floc                                    
                                    Initial                               
       Clear                                                              
           Clear                                                          
                14 mm floc                                                
                      18 mm floc                                          
                             19 mm floc                                   
                                    24 hrs.                               
.2%    Clear                                                              
           Clear                                                          
                Clear Moderate                                            
                             21 mm floc                                   
                                    Initial                               
                      Turbidity                                           
       Clear                                                              
           Clear                                                          
                Clear Trace of floc                                       
                             21 mm floc                                   
                                    24 hrs.                               
.3%    Clear                                                              
           Clear                                                          
                Clear Slight Highly turbid                                
                                    Initial                               
                      Turbidity                                           
       Clear                                                              
           Clear                                                          
                Clear Slight Turbid but                                   
                                    24 hrs.                               
                      Turbidity                                           
                             no floc                                      
__________________________________________________________________________
 
    
     Results using the formulation of Example 2: 
     
                                           TABLE V                                 
__________________________________________________________________________
       WATER HARDNESS                                                     
           91/2                                                           
DILUTIONS                                                                 
       5 GR.                                                              
           GR. TAP                                                        
                10 GR.                                                    
                      15 GR. 20 GR.                                       
                                   TIME SPAN                              
__________________________________________________________________________
.1%    Slight                                                             
           Slight                                                         
                14 mm floc                                                
                      20 mm floc                                          
                             15 mm floc                                   
                                   Initial                                
       Cloud                                                              
           Cloud                                                          
       Slight                                                             
           Cloudy                                                         
                14 mm floc                                                
                      17 mm floc                                          
                             15 mm floc                                   
                                   24 hrs.                                
       Cloud                                                              
.2%    Clear                                                              
           Clear                                                          
                Cloudy                                                    
                      14 mm floc                                          
                             25 mm floc                                   
                                   Initial                                
       Clear                                                              
           Clear                                                          
                Cloudy                                                    
                      14 mm floc                                          
                             25 mm floc                                   
                                   24 hrs.                                
.3%    Clear                                                              
           Clear                                                          
                Clear Trace of floc                                       
                             10 mm floc                                   
                                   Initial                                
       Clear                                                              
           Clear                                                          
                Clear Very cloudy                                         
                             10 mm floc                                   
                                   24 hrs.                                
__________________________________________________________________________
 
    
     The same builder system of STPP and polyacrylate exhibits a water conditioning &#34;synergism&#34; or &#34;extension&#34; Formulations of Examples 3 and 4 exhibit the same phenomenon using as a source of chlorine, sodium dichloro iso-cyanurate dihydrate. 
     Results using the formulation of Example 3: 
     
                                           TABLE VI                                
__________________________________________________________________________
       WATER HARDNESS                                                     
           91/2                                                           
DILUTIONS                                                                 
       5 GR.                                                              
           GR. TAP                                                        
                10 GR.                                                    
                      15 GR. 20 GR.                                       
                                   TIME SPAN                              
__________________________________________________________________________
.1%    Clear                                                              
           Cloudy                                                         
                18 mm floc                                                
                      16 mm floc                                          
                             10 mm floc                                   
                                   Initial                                
       Clear                                                              
           Cloudy                                                         
                18 mm floc                                                
                      16 mm floc                                          
                             15 mm floc                                   
                                   24 hrs.                                
.2%    Clear                                                              
           Clear                                                          
                Cloudy                                                    
                      Cloudy 21 mm floc                                   
                                   Initial                                
       Clear                                                              
           Clear                                                          
                Cloudy                                                    
                      Heavy cloud                                         
                             21 mm floc                                   
                                   24 hrs.                                
.3%    Clear                                                              
           Clear                                                          
                Clear Cloudy Cloudy                                       
                                   Initial                                
       Clear                                                              
           Clear                                                          
                Clear Cloudy,                                             
                             Cloudy                                       
                                   24 hrs.                                
                      no ppt No floc                                      
__________________________________________________________________________
 
    
     Results using the formualation of Example 4: 
     
                                           TABLE VII                               
__________________________________________________________________________
       WATER HARDNESS                                                     
           91/2                                                           
DILUTIONS                                                                 
       5 GR.                                                              
           GR. TAP                                                        
                10 GR.                                                    
                      15 GR. 20 GR.                                       
                                   TIME SPAN                              
__________________________________________________________________________
.1%    Slight                                                             
           Slight                                                         
                16 mm floc                                                
                      21 mm floc                                          
                             20 mm floc                                   
                                   Initial                                
       Cloud                                                              
           Cloud                                                          
       Slight                                                             
           Cloudy                                                         
                16 mm floc                                                
                      21 mm floc                                          
                             20 mm floc                                   
                                   24 hrs.                                
       Cloud                                                              
.2%    Clear                                                              
           Clear                                                          
                Cloudy                                                    
                      18 mm floc                                          
                             25 mm floc                                   
                                   Initial                                
       Clear                                                              
           Clear                                                          
                Cloudy                                                    
                      18 mm floc                                          
                             25 mm floc                                   
                                   24 hrs.                                
.3%    Clear                                                              
           Clear                                                          
                Clear 7 mm floc                                           
                             15 mm floc                                   
                                   Initial                                
       Clear                                                              
           Clear                                                          
                Clear 7 mm floc                                           
                             15 mm floc                                   
                                   24 hrs.                                
__________________________________________________________________________
 
    
     The same base as in Tables IV and V with chlorinated TSP as the chlorine source exhibits the same phenomenon in which the inclusion of sodium polyacrylate extends the water softening properties of the tripolyphosphate. 
     Results using the formulation of Example 5: 
     
                                           TABLE VIII                              
__________________________________________________________________________
       WATER HARDNESS                                                     
           91/2                                                           
DILUTIONS                                                                 
       5 GR.                                                              
           GR. TAP                                                        
                10 GR.                                                    
                    15 GR.                                                
                        20 GR.                                            
                              TIME SPAN                                   
__________________________________________________________________________
.1%    Clear                                                              
           Clear                                                          
                Cloudy                                                    
                    Cloudy                                                
                        45 mm floc                                        
                              Initial                                     
       Clear                                                              
           Clear                                                          
                Cloudy                                                    
                    Cloudy                                                
                        45 mm floc                                        
                              24 hrs.                                     
.2%    Clear                                                              
           Clear                                                          
                Slight                                                    
                    Cloudy                                                
                        Cloudy                                            
                              Initial                                     
                Cloud                                                     
       Clear                                                              
           Clear                                                          
                Slight                                                    
                    Cloudy                                                
                        Cloudy                                            
                              24 hrs.                                     
                Cloud                                                     
.3%    Clear                                                              
           Clear                                                          
                Slight                                                    
                    Cloudy                                                
                        Cloudy                                            
                              Initial                                     
                Cloud                                                     
       Clear                                                              
           Clear                                                          
                Slight                                                    
                    Cloudy                                                
                        Cloudy                                            
                              24 hrs.                                     
                Cloud                                                     
__________________________________________________________________________
 
    
     Results using the formulation of Example 6: 
     
                                           TABLE IX                                
__________________________________________________________________________
       WATER HARDNESS                                                     
           91/2                                                           
DILUTIONS                                                                 
       5 GR.                                                              
           GR. TAP                                                        
                10 GR.                                                    
                      15 GR.                                              
                            20 GR.                                        
                                  TIME SPAN                               
__________________________________________________________________________
.1%    Cloudy                                                             
           Cloudy                                                         
                15 mm floc                                                
                      25 mm floc                                          
                            45 mm floc                                    
                                  Initial                                 
       Cloudy                                                             
           Cloudy                                                         
                15 mm floc                                                
                      25 mm floc                                          
                            45 mm floc                                    
                                  24 hrs.                                 
.2%    Clear                                                              
           Cloudy                                                         
                7 mm floc                                                 
                      25 mm floc                                          
                            40 mm floc                                    
                                  Initial                                 
       Clear                                                              
           Cloudy                                                         
                7 mm floc                                                 
                      25 mm floc                                          
                            40 mm floc                                    
                                  24 hrs.                                 
.3%    Clear                                                              
           Clear                                                          
                Trace floc                                                
                      14 mm floc                                          
                            21 mm floc                                    
                                  Initial                                 
       Clear                                                              
           Clear                                                          
                Trace floc                                                
                      14 mm floc                                          
                            21 mm floc                                    
                                  24 hrs.                                 
__________________________________________________________________________
 
    
     The formulations of Examples 7 and 8 are compared versions the same builder stock, but using a blend of sodium metasilicate anhydrous and socium silicate 20%, 1:2.5 ratio to yield an aluminum safe product with a sodium hypochlorite chlorine source. Once more, the extender effect of polyacrylate on tripoly is noted. 
     Results using the formulation of Example 7: 
     
                                           TABLE X                                 
__________________________________________________________________________
       WATER HARDNESS                                                     
           91/2                                                           
DILUTIONS                                                                 
       5 GR.                                                              
           GR. TAP                                                        
                10 GR.                                                    
                      15 GR.  20 GR. TIME SPAN                            
__________________________________________________________________________
.1%    Slight                                                             
           Clear                                                          
                Light floc                                                
                      Moderate floc                                       
                              19 mm floc                                  
                                     Initial                              
       Cloud                                                              
       Clear                                                              
           Clear                                                          
                14 mm floc                                                
                      17 mm floc                                          
                              19 mm floc                                  
                                     24 hrs.                              
.2%    Clear                                                              
           Clear                                                          
                Cloudy                                                    
                      Cloudy  21 mm floc                                  
                                     Initial                              
       Clear                                                              
           Clear                                                          
                Cloudy                                                    
                      Trace of floc                                       
                              21 mm floc                                  
                                     24 hrs.                              
.3%    Clear                                                              
           Clear                                                          
                Clear Slight cloud                                        
                              Cloudy Initial                              
       Clear                                                              
           Clear                                                          
                Clear Cloudy  Trace of floc                               
                                     24 hrs.                              
__________________________________________________________________________
 
    
     Results using the formulation of Example 8: 
     
                                           TABLE XI                                
__________________________________________________________________________
       WATER HARDNESS                                                     
           91/2                                                           
DILUTIONS                                                                 
       5 GR.                                                              
           GR. TAP                                                        
                10 GR.                                                    
                      15 GR. 20 GR.                                       
                                   TIME SPAN                              
__________________________________________________________________________
.1%    Slight                                                             
           Clear                                                          
                Moderate                                                  
                      18 mm floc                                          
                             18 mm floc                                   
                                   Initial                                
       Cloud    Floc                                                      
       Slight                                                             
           Slight                                                         
                14 mm floc                                                
                      18 mm floc                                          
                             18 mm floc                                   
                                   24 hrs.                                
       Cloud                                                              
           Cloud                                                          
.2%    Clear                                                              
           Clear                                                          
                Cloudy                                                    
                      17 mm floc                                          
                             25 mm floc                                   
                                   Initial                                
       Clear                                                              
           Clear                                                          
                Cloudy                                                    
                      17 mm floc                                          
                             25 mm floc                                   
                                   24 hrs.                                
.3%    Clear                                                              
           Clear                                                          
                Clear Cloudy 17 mm floc                                   
                                   Initial                                
       Clear                                                              
           Clear                                                          
                Clear Trace of floc                                       
                             17 mm floc                                   
                                   24 hrs.                                
__________________________________________________________________________
 
    
     Products based on Examples 9 and 10 and using a silicate alkali source and a dichloro isocyanurate dihydrate chlorine source exhibits an extender effect. 
     Results using the formulation of Example 9: 
     
                                           TABLE XII                               
__________________________________________________________________________
       WATER HARDNESS                                                     
           91/2                                                           
DILUTIONS                                                                 
       5 GR.                                                              
           GR. TAP                                                        
                10 GR. 15 GR. 20 GR.                                      
                                    TIME SPAN                             
__________________________________________________________________________
.1%    Clear                                                              
           Clear                                                          
                12 mm floc                                                
                       18 mm floc                                         
                              17 mm floc                                  
                                    Initial                               
       Slight                                                             
           Slight                                                         
                12 mm floc                                                
                       18 mm floc                                         
                              17 mm floc                                  
                                    24 hrs.                               
       Cloud                                                              
           Cloud                                                          
.2%    Clear                                                              
           Clear                                                          
                2 mm floc                                                 
                       4 mm floc                                          
                              25 mm floc                                  
                                    Initial                               
       Clear                                                              
           Clear                                                          
                Trace of floc                                             
                       Trace of floc                                      
                              25 mm floc                                  
                                    24 hrs.                               
.3%    Clear                                                              
           Clear                                                          
                Clear  Clear  Slight floc                                 
                                    Initial                               
       Clear                                                              
           Clear                                                          
                Clear  Clear  Slight floc                                 
                                    24 hrs.                               
__________________________________________________________________________
 
    
     Results using the formulation of Example 10: 
     
                                           TABLE XIII                              
__________________________________________________________________________
       WATER HARDNESS                                                     
           91/2                                                           
DILUTIONS                                                                 
       5 GR.                                                              
           GR. TAP                                                        
                10 GR. 15 GR.                                             
                             20 GR.                                       
                                   TIME SPAN                              
__________________________________________________________________________
.1%    Slight                                                             
           Cloudy                                                         
                14 mm floc                                                
                       20 mm floc                                         
                             25 mm floc                                   
                                   Initial                                
       Cloud                                                              
       Slight                                                             
           Cloudy                                                         
                14 mm floc                                                
                       20 mm floc                                         
                             25 mm floc                                   
                                   24 hrs.                                
       Cloud                                                              
           Slight                                                         
.2%    Clear                                                              
           Cloud                                                          
                10 mm floc                                                
                       15 mm floc                                         
                             20 mm floc                                   
                                   Initial                                
       Clear                                                              
           Clear                                                          
                10 mm floc                                                
                       15 mm floc                                         
                             20 mm floc                                   
                                   24 hrs.                                
.3%    Clear                                                              
           Clear                                                          
                Trace of floc                                             
                       7 mm floc                                          
                             9 mm floc                                    
                                   Initial                                
       Clear                                                              
           Clear                                                          
                Trace of floc                                             
                       7 mm floc                                          
                             9 mm floc                                    
                                   24 hrs.                                
__________________________________________________________________________
 
    
     Products based on Examples 11 and 12 and using a silicate blend as the alkali source and chlorinated TSP as the chlorine source exhibits the extender effect. 
     Results using the formulation of Example 11: 
     
                                           TABLE XIV                               
__________________________________________________________________________
       WATER HARDNESS                                                     
           91/2                                                           
DILUTIONS                                                                 
       5 GR.                                                              
           GR. TAP                                                        
                10 GR.                                                    
                     15 GR.                                               
                          20 GR. TIME SPAN                                
__________________________________________________________________________
.1%    Clear                                                              
           Clear                                                          
                Cloudy                                                    
                     Cloudy                                               
                          45 mm floc                                      
                                 Initial                                  
       Clear                                                              
           Clear                                                          
                Cloudy                                                    
                     Cloudy                                               
                          45 mm floc                                      
                                 24 hrs.                                  
.2%    Clear                                                              
           Clear                                                          
                Slight                                                    
                     Cloudy                                               
                          20 mm floc                                      
                                 Initial                                  
                Cloud                                                     
       Clear                                                              
           Clear                                                          
                Slight                                                    
                     Cloudy                                               
                          20 mm floc                                      
                                 24 hrs.                                  
                Cloud                                                     
.3%    Clear                                                              
           Clear                                                          
                Slight                                                    
                     Cloudy                                               
                          Very cloudy                                     
                                 Initial                                  
                Cloud                                                     
       Clear                                                              
           Clear                                                          
                Slight                                                    
                     Cloudy                                               
                          Very cloudy                                     
                                 24 hrs.                                  
                Cloud                                                     
__________________________________________________________________________
 
    
     Results using the formulation of Example 12: 
     
                                           TABLE XV                                
__________________________________________________________________________
       WATER HARDNESS                                                     
           91/2                                                           
DILUTIONS                                                                 
       5 GR.                                                              
           GR. TAP                                                        
                10 GR.                                                    
                      15 GR.                                              
                            20 GR.                                        
                                  TIME SPAN                               
__________________________________________________________________________
.1%    Cloudy                                                             
           Cloudy                                                         
                15 mm floc                                                
                      25 mm floc                                          
                            45 mm floc                                    
                                  Initial                                 
       Cloudy                                                             
           Cloudy                                                         
                15 mm floc                                                
                      25 mm floc                                          
                            45 mm floc                                    
                                  24 hrs.                                 
.2%    Clear                                                              
           Cloudy                                                         
                7 mm floc                                                 
                      25 mm floc                                          
                            40 mm floc                                    
                                  Initial                                 
       Clear                                                              
           Cloudy                                                         
                7 mm floc                                                 
                      25 mm floc                                          
                            40 mm floc                                    
                                  24 hrs.                                 
.3%    Clear                                                              
           Clear                                                          
                2 mm floc                                                 
                      18 mm floc                                          
                            25 mm floc                                    
                                  Initial                                 
       Clear                                                              
           Clear                                                          
                2 mm floc                                                 
                      18 mm floc                                          
                            25 mm floc                                    
                                  24 hrs.                                 
__________________________________________________________________________
 
    
     It is understood that the foregoing detailed description is given merely by way of illustration and that many variations may be made therein without departing from this invention.