Bacteriostatic toilet bowl cleaner compositions
This is a division of application Ser. No. 312,767, filed Dec. 6, 1972, now U.S. Pat. No. 3,897,357. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention relates to novel toilet bowl cleaner compositions. These compositions possess antimicrobial properties at the extremely low dilutions which are normally encountered with a product of this nature. 
     2. Description of the Prior Art 
     Compositions which automatically dispense cleaning agents and cleaning adjuncts into toilet bowls have been in commercial use for many years. However, the inhibition of the growth or multiplication of microbiological organisms in products of the above nature has been difficult to accomplish. This difficulty is due to the fact that most antimicrobial agents are ineffective at the extreme dilutions that automatic bowl cleaners are used. 
     Recently, a new antimicrobial agent, namely, 5 -chloro-2-(2,4-dichlorophenoxy)phenol has been disclosed in U.S. Pat. No. 3,506,720. The assignee of this patent (Ciba-Geigy) has published data (Irgasan DP-300, Publication DC-25) which indicates that the minimum inhibitory concentration of 5-chloro-2-(2,4-dichlorophenoxy)phenol required for specific micro-organisms is 1ppm for S. aureus and P. mirabilis and 3ppm for E. coli. 
     SUMMARY OF THE INVENTION 
     In accordance with this invention it has now been found that the use of 5-chloro-2-(2,4-dichlorophenoxy)phenol as an antimicrobial with isopropanol, an alkoxylated primary fatty alcohol and/or a linear alkyl aryl sulfonate salt combined with known dyes and perfumes produces a cleaning formulation which exhibits bacteriostatic properties against S. aureus, P. mirabilis and E. coli at levels as low as 0.1 per million of the antimicrobial for a solid cleaning formulation and 0.2 parts per million for a liquid cleaning formulation. 
    
    
     DESCRIPTION OF SPECIFIC EMBODIMENTS 
     The novel liquid composition of this invention comprises: 
     
         Ingredient             % By Weight                                        
______________________________________                                    
Isopropanol            10-20                                              
5-chloro-2-(2,4-dichlorophenoxy)phenol                                    
                       0.5-6                                              
Alkoxylated primary fatty alcohol                                         
                       0.1-20                                             
Linear Alkyl Aryl Sulfonate Salt                                          
                       0.5-20                                             
Sodium hydroxide       0-2                                                
Water, Dye, Perfume    Sufficient to                                      
                       make up to 100%                                    
______________________________________                                    
 
    
     The preferred formula for an effective liquid cleaning and bacteriostatic composition is as follows: 
     
         Ingredient             % By Weight                                        
______________________________________                                    
Isopropanol            14-16                                              
5-chloro-2-(2,4-dichlorophenoxy)phenol                                    
                       1.1-1.6                                            
Alkoxylated primary fatty alcohol                                         
                        4-17                                              
Linear Alkyl Aryl Sulfonate Salt                                          
                       0.5-10                                             
Water, Dye, Perfume    Sufficient to                                      
                       make up to 100%                                    
______________________________________                                    
 
    
     The novel solid composition of this invention comprises: 
     
         Ingredients            % By Weight                                        
______________________________________                                    
5-chloro-2-(2,4-dichlorophenoxy)phenol                                    
                       1-3                                                
(97% minimum activity)                                                    
Alkoxylated primary fatty alcohol                                         
                       0.1-10                                             
Ethoxylated alcohol adduct                                                
                       20-90                                              
Polyethylene glycol    0.1-10                                             
Sodium sulfate, Perfume, Dye                                              
                       Sufficient to                                      
                       make up to 100%                                    
______________________________________                                    
 
    
     The preferred formula for an effective solid cleaning and bacteriostatic composition is as follows: 
     
         Ingredients            % By Weight                                        
______________________________________                                    
5-chloro-2-(2,4-dichlorophenoxy)phenol                                    
                       1-3                                                
(97% minimum activity)                                                    
Alkoxylated primary fatty alcohol                                         
                       2-8                                                
Ethoxylated alcohol adduct                                                
                       25-35                                              
Polyethylene glycol    2-8                                                
Sodium sulfate, Perfume, Dye                                              
                       Sufficient to                                      
                       make up to 100%                                    
______________________________________                                    
 
    
     Examples of alkoxylated primary alcohols that are useful in this invention are those alkoxylated primary alcohols wherein the alkyl chain length is primarily C 12  -C 18 . 
     Examples of linear alkyl aryl sulfonate salts that are useful in this invention are the salts of an alkyl aryl sulfonate wherein the alkyl carbon chain length is C 1  -C 15 . The novel composition in its solid form contains an ethoxylated alcohol adduct whose primary alcohol chain length is about C 16  -C 20 . In addition to the cleaning and bacteriostatic properties that the novel formulations of this invention possess, they also have the ability to reduce the surface tension of water. 
     As will be illustrated in the following examples, the liquid compositions of this invention have the ability to exhibit bacteriostatic properties at use levels as low as 0.2 parts per million of the anti-microbial. The solid compositions exhibit bacteriostatic properties at use levels as low as 0.1 parts per million of the anti-microbial. The examples will also indicate the anti-microbial agents known in the prior art are either ineffective or are not readily or efficiently compounded or solubilized. 
     The following examples illustrate the above described invention. The bacteria employed as the test organisms are representative of both gram negative and gram positive bacteria. The test procedure employed is the Agar Plate Test and the Agar Cup Plate Test as described in U.S.D.A. circular No. 198, 1931. The results are reported as zones of inhibition and measured in millimeters. 
     EXAMPLE 1 
     
         Ingredient             % By Weight                                        
______________________________________                                    
Isopropanol (99%)      15.00                                              
5-chloro-2-(2,4-dichlorophenoxy)phenol                                    
                       1.50                                               
(97% minimum activity)                                                    
50% ethylene oxide&gt;adduct                                                 
                       12.00                                              
10% propylene oxide&gt;adduct                                                
of a linear alcohol whose                                                 
carbon chain length is C.sub.12 --C.sub.15                                
Sodium Xylene Sulfonate (40%)                                             
                       2.50                                               
Water, Dye, Perfume    Sufficient to make                                 
                       up to 100%                                         
Average Zone of Inhibition (mm) Dilution 1:23,000                         
              S. aureus  E. coli  P.mirabilis                             
Agar Cup Plate Test                                                       
              10         5        3                                       
Agar Plate Test                                                           
               5         2        1                                       
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     A preferred alternate formulation is represented by Example 2. 
     EXAMPLE 2 
     
         Ingredient              % By Weight                                       
______________________________________                                    
Isopropanol (99%)       15.00                                             
5-chloro-2-(2,4-dichlorophenoxy)phenol                                    
                        1.50                                              
(97% minimum activity)                                                    
Triethanolaminedodecylbenzensulfonate (40%)                               
                        15.00                                             
Water, Dye, Perfume     Sufficient to make                                
                        up to 100%                                        
Average Zone of Inhibition (mm) Dilution 1:23,000                         
              S. aureus  E. coli  P. mirabilis                            
Agar Cup Plate Test                                                       
              7          3        3                                       
Agar Plate Test                                                           
              6          3        3                                       
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     EXAMPLE 3 
     
         Ingredient              % By Weight                                       
______________________________________                                    
Isopropanol (99%)       15.00                                             
5-chloro-2-(2,4-dichlorophenoxy)phenol                                    
                        1.50                                              
(97% minimum activity)                                                    
Triethanolaminedodecylbenzensulfonate (40%)                               
                        11.25                                             
50% ethylene oxide&gt;adduct                                                 
                        4.50                                              
10% propylene oxide&gt;adduct                                                
of a linear alcohol whose                                                 
carbon chain length is C.sub.12 --C.sub.15                                
Water, Dye, Perfume     Sufficient to                                     
                        make up to 100%                                   
Average Zone of Inhibition (mm) Dilution 1:23,000                         
              S. aureus  E. coli  P. mirabilis                            
Agar Cup Plate Test                                                       
              7          15       2.5                                     
______________________________________                                    
 
    
     EXAMPLE 4 
     
         Ingredient              % By Weight                                       
______________________________________                                    
Isopropanol (99%)       4.50                                              
n-Alkyl (60% C.sub.14, 30% C.sub.16, 5% C.sub.12 and                      
8% C.sub.18) Dimethyl Benzyl Ammonium Chloride                            
                        5.00                                              
n-Alkyl (68% C.sub.12, 32% C.sub.14) Dimethyl                             
Ethylbenzyl Ammonium Chloride                                             
                        5.00                                              
50% ethylene oxide&gt; adduct                                                
                        4.00                                              
10% propylene oxide&gt;adduct                                                
of a linear alcohol whose                                                 
carbon chain length is C.sub.12 --C.sub.15                                
Water, Dye, Perfume     Sufficient to                                     
                        make up to 100%                                   
Average Zone of Inhibition (mm) Dilution 1:23,000                         
                  S. aureus    E. coli                                    
Agar Cup Plate Test                                                       
                  2.5          0                                          
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     The above is an example of the use of another antimicrobial agent employed at a much higher level than those in the previous examples which was ineffective against E. coli. 
     EXAMPLE 5 
     
         Ingredient              % By Weight                                       
______________________________________                                    
4&#39;,5 Dibromosalicylanilide and                                            
3,4&#39;5, Tribromosalicylanilide (1:1                                        
                        6.00                                              
mixture)                                                                  
Polyethylene Glycol (molecular weight                                     
about 200)              50.00                                             
Octyl phenoxypoly (ethyleneoxy) Ethanol                                   
                        30.00                                             
Water                   Sufficient to                                     
                        make up to 100%                                   
Average Zone of Inhibition (mm) Dilution 1:20,000                         
                  S. aureus    E. coli                                    
Agar Cup Plate Test                                                       
                  16           11                                         
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     The above is an example of the use of a different antimicrobial agent which requires high levels of solubilizers and which was used at higher levels itself to achieve bacteriological activity. 
     EXAMPLE 6 
     
         Ingredient              % By Weight                                       
______________________________________                                    
3,4&#39;5 Tribromosalicylanilide                                              
                        6.00                                              
Polyethylene Glycol (molecular weight                                     
                        60.00                                             
about 200)                                                                
Octyl phenoxypoly (ethyleneoxy) ethanol                                   
                        30.00                                             
Water                   4.00                                              
Average Zone of Inhibition (mm) Dilution 1:20,000                         
                  S. aureus    E. coli                                    
Agar Cup Plate Test                                                       
                  10           4                                          
                               (Partial)                                  
______________________________________                                    
 
    
     This example illustrates another antimicrobial agent which requires high levels of solubilizers and which results in only a partial zone of inhibition at the high level employed. 
     EXAMPLE 7 
     
         Ingredient              % By Weight                                       
______________________________________                                    
Alkyl pyridinium 5-chloro-2-mercapto-                                     
                        12.00                                             
benzothiazole (96%)                                                       
N-methyl-2-pyrrolidone  60.00                                             
Octyl phenoxy poly (ethyleneoxy) ethanol                                  
                        10.00                                             
Water                   18.00                                             
Average Zone of Inhibition (mm) Dilution 1:20,000                         
                  S. aureus    E. coli                                    
Agar Cup Plate Test                                                       
                  7            0                                          
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     This example illustrates yet another antimicrobial agent which though used at a higher level does not result in a zone of inhibition on E. coli 
     EXAMPLE 8 
     This example illustrates the use of the solid formulation of this invention as a toilet bowl cleaner. The use dilution for microbiological activity with this composition is 0.30 parts per million of the formulation per 23,000 parts of water. 
     
         Component               % By Weight                                       
______________________________________                                    
100 moles of ethylene oxide adduct of                                     
                        31.00                                             
a primary alcohol whose carbon length                                     
is C.sub.16 --C.sub.20                                                    
Polyethylene Glycol (molecular                                            
weight about 6,000)     5.00                                              
50% ethylene oxide&gt; adduct                                                
                        5.00                                              
10% propylene oxide&gt;adduct                                                
of a linear alcohol whose                                                 
carbon chain length is C.sub.12 --C.sub.15                                
5-chloro-2-(2,4-dichlorophenoxy)phenol                                    
                        1.25                                              
(97% minimum activity)                                                    
Sodium Sulfate          55.25                                             
Perfume, Dye            Sufficient to                                     
                        make up to 100%                                   
Average Zone of Inhibition (mm)                                           
              S. aureus  E. coli  P. mirabilis                            
Agar Cup Plate Test                                                       
              4.5        2        2.5                                     
______________________________________                                    
 
    
     EXAMPLE 9 
     This Example illustrates the use of 5 -chloro-2-(2,4-dichlorophenoxy)phenol in the following liquid formulation where it is present at 0.50% by weight in a use dilution of 1:23,000 and 1:40,000. 
     
         ______________________________________                                    
Ingredients            % By Weight                                        
______________________________________                                    
Isopropanol (99%)      15.00                                              
5-chloro-2-(2,4-dichlorophenoxy) phenol                                   
                       0.50                                               
(97% minimum activity)                                                    
50% ethylene oxide&gt; adduct                                                
                       12.00                                              
10% propylene oxide&gt; adduct                                               
of a linear alcohol whose                                                 
carbon chain length is C.sub.12 --C.sub.15                                
Water                  67.75                                              
Sodium Xylene Sulfonate (40%)                                             
                       2.50                                               
Dye                    1.00                                               
Perfume                1.25                                               
Average Zone of Inhibition (mm)                                           
              S. aureus  E. coli  P. mirabilis                            
Agar Cup Plate Test                                                       
              6          2.5      2                                       
(Dilution 1:23,000)                                                       
Agar Cup Plate Test                                                       
              4          1.5      0                                       
(Dilution 1:40,000)                                                       
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     EXAMPLE 10 
     
         Component               % By Weight                                       
______________________________________                                    
Ethoxylated Alcohol Adduct                                                
                        31.00                                             
Polyethylene Glycol (mol. wt. about 6000)                                 
                        5.00                                              
Oxyethylated Alcohol Surfactant                                           
                        5.00                                              
4&#39;, 5 Dibromosalicylanilide, 3, 4&#39;5                                       
Tribromosalicylanilide (1:1 mixture)                                      
                        2.50                                              
Sodium Sulfate          54.00                                             
Perfume, Dye            Sufficient to                                     
                        make up to 100%                                   
Average Zone of Inhibition (mm)                                           
              S. aureus  E. coli  P. mirabilis                            
Agar Cup Plate Test                                                       
              2.5        0        0                                       
______________________________________                                    
 
    
     This example illustrates the use of an antimicrobial agent which does not exhibit activity in the composition. 
     EXAMPLE 11 
     
         Component               % By Weight                                       
______________________________________                                    
Ethoxylated Alcohol Adduct                                                
                        31.00                                             
Polyethylene Glycol (mol. wt about 6000)                                  
                        5.00                                              
Oxyethylated Alcohol Surfactant                                           
                        5.00                                              
3,4&#39;,5 Tribromosalicylanilide                                             
                        2.50                                              
Sodium Sulfate          54.00                                             
Perfume, Dye            Sufficient to                                     
                        make up to 100%                                   
Average Zone of Inhibition (mm)                                           
              S. aureus  E. coli  P. mirabilis                            
Agar Cup Plate Test                                                       
              0          0        0                                       
______________________________________                                    
 
    
     This example illustrates a total lack of activity of an antimicrobial in the composition. 
     EXAMPLE 12 
     The following data represents the ability of the preferred compositions of this invention to help retard stain buildup on a ceramic surface immersed in a solution containing an iron salt. Results are reported as units of stain pickup on white ceramic tiles. Less than 1 unit difference is visible to the naked eye. 
     
         ______________________________________                                    
                           Surface                                        
              Average Units                                               
                           Tension                                        
              Iron Stain Pickup                                           
                           Dynes/CM                                       
______________________________________                                    
Composition (Example 1)                                                   
                4.1            41.4                                       
Water           5.8            72                                         
Composition (Example 8)                                                   
                2.5            33                                         
Water           6.1            72                                         
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