Abstract:
The present invention relates to an automatic dishwashing composition including from about 0.1 to 5 weight, percent cross-linked anionic polyacrylate polymer, from about 0.1 to 40 weight percent alkali metal citrate chelating agent and from about 1 to 40 weight percent alkali metal sulfate, with from about 0.1 to 20 weight percent nonionic surfactant and from about 0.05 to 8.0 weight percent bleaching agent as optional components. The present invention also relates to a method for reducing residues on washed and dried dish surfaces, which includes the use of an automatic dishwashing composition containing the above components,

Description:
FIELD OF THE INVENTION 
       [0001]    The present invention relates to a composition to be used as a detergent, and which may also be applicable to other applications, such as a hard surface cleaner or a carpet cleaner. 
       BACKGROUND OF THE INVENTION 
       [0002]    Automatic dishwashing detergents are well-known in the art. Most of the automatic dishwashing detergents currently available are suitable tier their intended purposes, i.e., effectively cleaning, and leaving previously soiled eating and cooking utensils in a generally spot-free, clean condition. Due to the special design of automatic dishwashers, the detergent should have very high viscosity for users to control proper dosage. Almost all of the liquid automatic dishwashing detergents exist in the form of a gel, which is, in most cases, made of a polymer thickener. 
         [0003]    Polymer thickeners can be in three forms when dissolved in water: nonionic, which bears no charges; anionic, which bears multiple negative charges; and cationic, which bears multiple positive charges. Because tap water naturally contains positive charges of calcium (Ca +2 ) and magnesium (Mg +2 ) from the hardness of water, these positive ions can bind to the negative ions of anionic polymer and form precipitation deposits. This is one of the reasons that residues are formed, left on washed and dried dish surfaces in the form of so-called “water spots” and “filming” when a polyanionic polymer, such as Carbopol® 676, is used as the thickener. 
         [0004]    In order to reduce the residues, it has been believed that a chelating agent should be used. The chelating agents used in automatic dishwashing gels thus far are of two types: inorganic and organic. The inorganic type includes, but is not limited to, phosphates, polyphosphates, carbonates, borates, silicates etc., while the organic type includes, but is not limited to, EDTA (ethylenediaminetetraacetic acid and its salts), NTA (nitrilotriacetic acid and its salts), phosphonates, etc. 
         [0005]    The typical inorganic chelating agents of polyphosphates, phosphates, carbonates, silicates, etc. have the ability to chelate the Ca +2  and Mg +2  by forming water insoluble complexes as shown below: 
         [0000]      CaCl 2  (10 percent, clear solution)+Na 5 P 3 O 10  (5 percent clear solution)=→Ca 2.5  P 3 O 10  (turbid solution)
 
         [0000]      CaCl 2  (10 percent, clear solution)+Na 2 CO 3  (10 percent clear solution)=→CaCO 3  (turbid solution)
 
         [0000]      CaCl 2  (10 percent, clear solution)+Na 2 SiO 3 ) percent clear solution)=→Ca SiO 3  (turbid solution),
 
         [0000]    hence reducing the residues from a polymer, and so have been used widely in auto dishwashing gel. formulations as mentioned in the prior art. 
         [0006]    For instance, U.S. Pat. No. 5,981,457 describes a cross-linked polyacrylate as the thickener and tripolyphosphate as the builder/chelating agent. WO9429428 discloses polymers including cross-linked polyacrylate as the thickener, and carbonate, citrate, EDTA or NTA as the chelating agent (sometimes called a builder or water softener). U.S. Pat. No. 6,911,422 describes the manufacture of a transparent or translucent automatic dishwashing gel, but still contains 10 to 40 percent sodium tripolyphosphate as a chelating agent. 
         [0007]    U.S. Pat. No. 7,459,420 does not mention the application of typical chelating agents, but rather sodium citrate as the water softener. In the formulation described in the reference, the polymer is not anionic, but rather nonionic; the xanthan gum thickener does not have a anionic functional group to bind the Ca +2 /Mg +2 . In other words, the xanthan gum does not precipitate from tap water. 
         [0008]    Different types of electrolytes have different efficacies to prevent or slow down polymer precipitation. It would be desirable if Ca +2  anionic polymer salt precipitation could be avoided, reduced or slowed down for an automatic dishwashing process. Note that the wash waste is rinsed away with fresh water immediately after the wash cycle; the Ca +2  complex with traditional chelating agents of carbonate, silicate, phosphate, or even tripolyphosphate is not water-soluble. These inorganic water-insoluble complexes can be rinsed away during the state of suspension before precipitation. 
       SUMMARY OF THE INVENTION 
       [0009]    The present invention provides an improved composition to prevent anionic polymers from precipitating (depending on type and amount of electrolytes), hence reducing the residues in the form of “water spots” or “films” on washed and dried dish surfaces, when a formulation containing the polymer is diluted with tap water during use conditions, especially at about 120° F. for an automatic dishwashing process. In accordance with the present invention, an electrolyte can prevent or slow down the precipitation of polymeric anionic polymers without the addition of any traditional inorganic or organic chelating agents. The composition of the present invention comprises from about 0.1 to 5 weight percent cross-linked anionic polacrylate polymer, from about 0.1 to 40 weight percent alkali metal citrate chelating agent and from about 1 to 40 weight percent alkali metal sulfate, with from about 0.1 to 20 weight percent nonionic surfactant and from about 0.05 to 8.0 weight percent bleaching agent as optional components. 
         [0010]    The present invention further relates to a method for reducing residues on washed and dried dish surfaces which comprises the use of an automatic dishwashing composition comprising from about 0.1 to 5 weight percent cross-linked anionic polyacrylate polymer, from about 0.1 to 40 weight percent alkali metal citrate chelating agent, and from about 1 to 40 weight percent alkali metal sulfate, with from about 0.1 to 20 weight percent nonionic surfactant and from about 0.05 to 8.0 weight percent bleaching agent as optional components. 
     
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0011]    Particular terms to be used in describing the invention are as follows: An electrolyte is a water soluble salt, either inorganic or organic. When dissolved into water, an electrolyte can dissociate the molecule into positively and negatively charged ions. The negatively charged ion may or may not combine some mono-, di-valent (or higher than di-) metal or earth metal ions to form precipitation from water. 
         [0012]    A chelating or sequestering agent is an organic, water soluble salt or acid. When it dissolves into water, a chelating agent can dissociate the molecule into positively and negatively charged ions. The negatively charged ions may combine divalent (or higher than di-) metal or earth metal ions to form a water soluble complex. Some chelating agents are also electrolytes, such as sodium citrate, potassium nitrilotriacetate (NTA), sodium ethylenediaminetetraacetate (EDTA). 
         [0013]    A water softener is an inorganic water soluble salt, which can remove water hardness of calcium and magnesium ions from water by forming precipitation. Exemplary water softeners are, e.g., phosphate, polyphosphate, carbonate, bicarbonate and silicate. A water softener may also be (chemically) an electrolyte. 
         [0014]    By “low foaming surfactants” it is meant surfactants that do not generate as much foam as regular surfactants, such as sodium dodecyl benzene sulfonate, fatty alcohol ethoxylate, fatty alcohol ethoxylate sulfate. Low foaming surfactants include but are not limited the following structures: 
         [0000]      R(OCH 2 CH 2 ) x (OCH 2 CH 2 CH 2 ) y OH 
         [0000]      R(OCH 2 CH 2 ) x [OCH(CH 3 )CH 2 ] y OH 
         [0015]    An antifoaming agent is an additive which reduces the surface tension of a solution or emulsion, thus inhibiting or modifying the formation of a foam. Commonly used antifoaming agents are insoluble oils, dimethyl polysiloxanes and other silicones, certain alcohols, stearates, fatty acid calcium salt and glycols. The additive is used to prevent formation of foam or is added to break a foam already formed, 
         [0016]    A polycarboxylic polymer includes but is not limited to the following structure, including cross-linked and non-cross-linked versions: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0017]    In accordance with the present invention, when an electrolyte where, for example Na 2 SO 4 , is added into a formulation with an anionic polymer, for example M polyacrylate (where M may be Na, K, NH 4  etc), and 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    the formulation is diluted into tap water at 120° F for an automatic dish washing process, there are equilibriums established between different complexes, as shown by equation (1), (2), (3), (4) and (5). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0018]    Note: In equations (2), (3), (4) &amp; relationships between r, s, p, q and n are as follows: 
         [0000]      0≦ r   1,2,3,4,5,6   ≦n ; 1≦ s≦n ; ( r   1   +r   2 +1) s =( r   3   +r   4 +1) s=n  
 
         [0000]      0 ≦p≦ ( n−r   5   −r   6 −2); 1≦ q≦n ; ( p+r   5   +r   6 −2) q=n  
 
         [0019]    Equation (1) indicates that the anionic portion from an electrolyte will combine with the Ca +2 , i.e., there will be less Ca +2  left for the anionic polymer to combine with and then precipitate. 
         [0020]    Equation (2) shows that two polymer molecules combine with s Ca +2  ion to form precipitation. 
         [0021]    Equation (3) indicates that one polymer molecule combines with q Ca +2  ions to form precipitation. 
         [0022]    Equations (4) and (5) demonstrate that Ca +2  in water insoluble or precipitated complexes with the anionic polymer molecule can be replaced fully or partially by Na +  brought in by the electrolyte, and hence the precipitation will disappear or be reduced. 
         [0023]    The present invention will now be described in the following non-limiting examples, as summarized in Table 1, below. 
         [0000]    
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
             
             
               
                 Polyanionic Polymer Precipitation When Formulations Diluted in 120° F. Tap Water 
               
             
          
           
               
                 Ingredient 
                 Example 1 
                 Example 2 
                 Example 3 
                 Example 4 
               
               
                   
               
               
                 Plurafac ® SLF 180 (Low foaming nonionic 
                 20 
                 20 
                 20 
               
               
                 surfactant) 
               
               
                 Carbopol ® 676/Cross-linked anionic 
                 1.5 
                 1.5 
                 1.5 
                 2 
               
               
                 polyacrylate polymer 
               
               
                 Sodium citrate (chelating agent) 
                 2 
                 2 
                 2 
               
               
                 H 2 O 2  (a bleaching agent) 
                 4.5 
                 4.5 
                 5.5 
               
               
                 STPP (chelating agent) 
               
               
                 Sodium sulfate 
                   
                   
                 30 
               
               
                 Deionized water 
                 72 
                 72 
                 41 
                 98 
               
               
                 Total for the formulation 
                 100 percent 
                 100 percent 
                 100 percent 
                 100 percent 
               
               
                 Appearance 
                 gel 
                 gel 
                 gel 
                 gel 
               
               
                 Surface tension of 0.5 percent formulation at 
                 28.5 
                 28.5 
                 29.0 
               
               
                 70° F.: mN/m 
               
               
                 Polymer precipitation of 0.5 percent sample 
                 precipitation 
                 precipitation 
                 clear 
                 precipitation 
               
               
                 in 120° F. tap water 
               
               
                 0.44 grams Na 2 SO 4  added in 200 ml of 
                 precipitation 
                   
                   
                 precipitation 
               
               
                 above solution at 120° F. 
                 disappears 
                   
                   
                 disappears 
               
               
                 0.44 grams NaCl added in 200 ml of above 
                   
                 precipitation 
               
               
                 solution at 120° F. 
                   
                 disappears 
               
               
                   
               
               
                 Ingredient 
                 Example 5 
                 Example 6 
                 Example 7 
                 Example 8 
               
               
                   
               
               
                 Plurafac ® SLF 180 (Low foaming nonionic 
               
               
                 surfactant) 
               
               
                 Carbopol ® 676/Cross-linked anionic 
                 2 
                 2 
                 2 
                 2 
               
               
                 polyacrylate polymer 
               
               
                 Sodium citrate (chelating agent) 
               
               
                 H 2 O 2  (a bleaching agent) 
               
               
                 STPP (chelating agent) 
                   
                 17 
               
               
                 Sodium sulfate 
                   
                   
                 8 
                 30 
               
               
                 Deionized water 
                 98 
                 81 
                 90 
                 68 
               
               
                 Total for the formulation 
                 100 percent 
                 100 percent 
                 100 percent 
                 100 percent 
               
               
                 Appearance 
                 gel 
                 gel 
                 gel 
                 emulsion 
               
               
                 Surface tension of 0.5 percent formulation at 
                   
                   
                   
                 72.0 
               
               
                 70° F.: mN/m 
               
               
                 Polymer precipitation of 0.5 percent sample 
                 precipitation 
                 clear 
                 precipitation 
                 clear 
               
               
                 in 120° F. tap water 
               
               
                 0.44 grams Na 2 SO 4  added in 200 ml of 
               
               
                 above solution at 120° F. 
               
               
                 0.44 grams NaCl added in 200 ml of above 
                 precipitation 
               
               
                 solution at 120° F. 
                 disappears 
               
               
                   
               
             
          
         
       
     
         [0024]    Example 1 contains 2 percent chelating agent of sodium citrate but when diluted to 0.5 percent in 120° F. tap water, the anionic polymer combines with the Ca +2  to precipitate, which can be described by equation (2) &amp; (3). When 0.44 grams of Na 2 SO 4  is added to 200 ml of the 0.5 percent solution with precipitation, the polymer precipitation disappears, which is shown by equations (4) and (5). 
         [0025]    Example 2 shows that when 0.44 grams of NaCl is added into 200 ml of 0.5 percent of solution with precipitation, the precipitation disappears, which is described by equations (4) and (5). 
         [0026]    Example 3 demonstrates that when 30 percent Na 2 SO 4  is directly added into the formulation which is then diluted into 0.5 percent in 120° F. tap water, there is no polymer precipitation observed. The phenomena can be described by equations (1) or (4) and (5). 
         [0027]    Example 4 does not contain any surfactant or chelating agent, but merely the anionic polymer and deionized water, When it is diluted to 0.5 percent with 120° F. tap water the polymer precipitates confirms that it is the anionic polymer complex with Ca that precipitates, as concluded by Examples 1, 2 and 3. This is described by equations (2) and (3). The Ca-polymer complex precipitation in 0.5 percent diluted solution at 120° F. will disappear when 0.44 grains of Na 2 SO 4  in added into 200 ml of the solution, as shown in equations (4) or (5). 
         [0028]    Example 5 indicates that the electrolyte NaCl can have a similar function to prevent the polymer from precipitation in tap water as Na 2 SO 4  does, although CaCl is water soluble and CaSO 4  is not. 
         [0029]    Example 6 shows that STPP (sodium tripolyphosphate) behaves similarly as other electrolytes, such as NaCl and Na 2 SO 4 , to prevent the polymer from precipitating, although STPP is traditionally thought of as a key chelating agent, especially in automatic dishwashing gel detergents, 
         [0030]    Examples 7 and 8 demonstrate that 8 percent Na 2 SO 4  in the formulation is not sufficient to prevent the polymer from precipitation, but 30 percent is enough to do so. Examples 6, 7 and 8 suggest that different electrolytes have different thresholds to prevent the polymer from precipitating, which may depend on the types and amounts of electrolytes themselves, as well as other ingredients in the formulation. 
         [0031]    In a preferred embodiment, the composition of the present invention comprises from about 0.2 to 3 weight percent cross-linked anionic polyacrylate polymer, from about 0.3 to 15 weight percent alkali metal citrate chelating agent and from about 2 to 30 weight percent alkali metal sulfate, with from about 0.2 to 10 weight percent nonionic surfactant and front about 0. 5 to 5 weight percent bleaching agent as optional components. In a particularly preferred embodiment, the composition of the present invention comprises from about 0.5 to 2 weight percent cross-linked anionic polyacrylate polymer, from about 0.5 to 5 weight percent alkali metal citrate chelating agent and from about 5 to 20 weight percent alkali metal sulfate, with front about I to 5 weight percent nonionic surfactant and from about 1 to 3 weight percent bleaching agent as optional components. 
         [0032]    While the present invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of the invention will be obvious to those skilled in the art. The appended claims and the present invention generally should be construed to cover all such obvious forms and modifications which are within the true spirit and scope of the presort invention.