Patent Publication Number: US-7915213-B2

Title: High ash liquid laundry detergents comprising a urea and/or glycerine hygroscopic agent

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     This application claims priority to Provisional Application 60/914,599, filed Apr. 27, 2007. 
    
    
     BACKGROUND OF THE INVENTION 
     Field of the Invention 
     This invention relates to laundry detergent compositions having a high water soluble alkaline carbonate (soda ash) builder content. 
     Laundry detergent compositions comprising a water-soluble alkaline carbonate are well-known in the art. For example, it is conventional to use such a carbonate as a builder in detergent compositions which supplement and enhance the cleaning effect of an active surfactant present in the composition. Such builders improve the cleaning power of the detergent composition, for instance, by the sequestration or precipitation of hardness causing metal ions such as calcium, peptization of soil agglomerates, reduction of the critical micelle concentration, and neutralization of acid soil, as well as by enhancing various properties of the active detergent, such as its stabilization of solid soil suspensions, solubilization of water-insoluble materials, emulsification of soil particles, and foaming and sudsing characteristics. Other mechanisms by which builders improve the cleaning power of detergent compositions are probably present but are less well understood. Builders are important not only for their effect in improving the cleaning ability of active surfactants in detergent compositions, but also because they allow for a reduction in the amount of the surfactant used in the composition, the surfactant being generally much more costly than the builder. 
     Sodium carbonate (Na 2 CO 3 ) and/or potassium carbonate (K 2 CO 3 ) are the most common carbonates included in laundry detergents to impart increased alkalinity to wash loads, thereby improving detergency against many types of soils. In particular, soils having acidic components e.g. sebum and other fatty acid soils, respond especially well to increased alkalinity. 
     While laundry detergents containing a relatively large amount of carbonate builder are generally quite satisfactory in their cleaning ability, the use of such carbonate builders often results in the problem of calcium carbonate precipitation, which may give rise to fabric encrustation due to the deposition of the calcium carbonate on the fiber surfaces of fabrics which in turn causes fabric to have a stiff hand and gives colored fabrics a faded appearance. Thus, any change in available carbonate built laundry detergent compositions which reduces their tendency to cause fabric encrustation is highly desirable. 
     In many applications, it is desirable to include Na 2 CO 3  and K 2 CO 3  in detergent formulations at levels greater than 20%. This is readily achieved in the case of a powdered detergent. However, incorporating such large amounts into an aqueous liquid is much more difficult. In liquid laundry detergent compositions, the incorporation of a large amount of detergent builder poses a significant formulation challenge since the presence of a major quantity of detergent builder inevitably causes the detergent composition to phase separate. Liquid detergent formulations that contain a detergent builder ingredient require careful control of the surfactant to builder ratio so as to prevent salting-out of the surfactant phase. Liquid laundry detergent compositions are also susceptible to instability under extended freeze/thaw and high/low temperature conditions. 
     Additionally, sodium carbonate forms an extensive array of low water soluble hydrates at low temperatures and high, i.e., &gt;15 wt. % levels of the sodium carbonate builder. For example, a system with 20% carbonate builder will form a decahydrate phase below 23° C. At 30% sodium carbonate, the decahydrate will form below 31° C. Therefore, even at room temperature, systems containing greater than 20% carbonate builder are inherently unstable and readily form decahydrate phases. Once the decahydrate forms, redissolution can take an inordinate amount of time. 
     Accordingly, there is still a desire and a need to provide a stable liquid laundry detergent which has a high ash content. 
     SUMMARY OF THE INVENTION 
     In accordance with the present invention, a stable aqueous-based liquid laundry detergent is provided with an ash content of greater than 15 wt. % by incorporating a hygroscopic agent therein in sufficient amounts to prevent excessive insoluble hydrate formation. One or more surfactants including anionic, non-ionic and amphoteric or zwitterionic surfactants can be added. Stability of the liquid composition is further provided by adjusting the ratio of anionic surfactant to zwitterionic surfactant contained in the composition. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The water-soluble alkaline carbonate builder in the detergent composition of this invention may be, for example, an alkali metal carbonate, bicarbonate or sesquicarbonate, preferably sodium or potassium carbonate, bicarbonate or sesquicarbonate, and most preferably sodium carbonate or mixtures of sodium carbonate and potassium carbonate. A combination of more than one of such compounds may be used, e.g., sodium carbonate and sodium bicarbonate. The total alkaline carbonate may be present in an amount, for example, of greater than 15 wt. %, up to about 40 wt. %. Preferably about 20 to about 30 wt. % of sodium carbonate or mixtures of sodium carbonate and potassium carbonate are used. 
     To reduce the formation of water insoluble hydrates of the carbonate builder, the composition of the present invention includes one or more hygroscopic agents. Useful hygroscopic agents include polyols such as glycerin as well as urea. Other compounds known to bind water are useful hygroscopic agents for incorporation into the composition. In general, 5-25 percent by weight of the composition will comprise the hygroscopic agent. 
     The active surfactant component of the detergent composition of this invention may be, for example, one or more of many suitable synthetic detergent active compounds which are commercially available and described in the literature, e.g., in “Surface Active Agents and Detergents,” Volumes 1 and 2 by Schwartz, Perry and Berch. Several detergents and active surfactants are also described in, for example, U.S. Pat. Nos. 3,957,695; 3,865,754; 3,932,316 and 4,009,114. In general, the composition may include a synthetic anionic, nonionic, amphoteric or zwitterionic detergent active compound, or mixtures of two or more of such compounds. 
     More preferably, the laundry detergent compositions of this invention contain at least one anionic, and, most preferably, a mixture of at least one anionic and an amphoteric or zwitterionic surfactant. 
     The contemplated water soluble anionic detergent surfactants are the alkali metal (such as sodium and potassium) salts of the higher linear alkyl benzene sulfonates and the alkali metal salts of sulfated ethoxylated and unethoxylated fatty alcohols, and ethoxylated alkyl phenols. The particular salt will be suitably selected depending upon the particular formulation and the proportions therein. 
     The sodium alkybenzenesulfonate surfactant (LAS), if used in the composition of the present invention, preferably has a straight chain alkyl radical of average length of about 11 to 13 carbon atoms. 
     Specific sulfated surfactants which can be used in the compositions of the present invention include sulfated ethoxylated and unethoxylated fatty alcohols, preferably linear primary or secondary monohydric alcohols with C 10 -C 18 , preferably C 12 -C 16 , and more preferably, C 11 -C 15 , alkyl groups and, if ethoxylated, on average about 1-15, preferably 2-12, and most preferably 2-7 moles of ethylene oxide (EO) per mole of alcohol, and sulfated ethoxylated alkylphenols with C 8 -C 16  alkyl groups, preferably C 8 -C 9  groups, and on average from 4-12 moles of EO per mole of alkyl phenol. 
     The preferred class of anionic surfactants are the sulfated ethoxylated linear alcohols, such as the C 12 -C 16  alcohols ethoxylated with an average of from about 1 to about 12 moles of ethylene oxide per mole of alcohol. 
     Specific non-ionic surfactants which can be used in the composition of the present invention include ethoxylated fatty alcohols, preferably linear primary or secondary monohydric alcohols with C 10 -C 18  and preferably C 12 -C 16 , alkyl groups and on average about 1-15, preferably 1-12 moles of ethylene oxide (EO) per mole of alcohol, and ethoxylated alkylphenols with C 8 -C 16  alkyl groups, preferably C 8 -C 9  alkyl groups, and on average about 4-12 moles of EO per mole of alkyl phenol. 
     The preferred class of nonionic surfactants are the ethoxylated linear alcohols, such as the C 12 -C 16  alcohols ethoxylated with an average of from about 1 to about 12 moles of ethylene oxide per mole of alcohol. 
     Mixtures of the foregoing synthetic detergent types of surfactants, e.g., of anionic and nonionic, or of different specific anionic or nonionic surfactants, may be used to modify the detergency, sudsing characteristics, and other properties of the composition. For example, a mixture of different fatty alcohols of 12 to 16 carbon atoms may be ethoxylated, directly sulfated, or sulfated after ethoxylation, a fatty alcohol may be partially ethoxylated and sulfated, or an ethoxylated fatty acid may be partially sulfated to yield a mixture of different anionic and nonionic surfactants or different specific anionic or nonionic surfactants. 
     Further surfactants which can be used in the laundry detergent formulations according to the invention are amphoteric or zwitterionic surfactants, e.g. alkylbetaines, alkylamidobetaines, alkyliminopropionates, aminoglycinates or amphoteric imidazolineum carboxylates, sulfobetaines, sultaines and amine oxide compounds. 
     Preferred amphoteric surfactants of this formula are monocarboxylates and dicarboxylates. Examples thereof are cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, cocoamphocarboxyglycinate (also referred to as cocoamphodiacetate) and cocoamphoacetate. 
     Further preferred amphoteric surfactants are alkyldimethylbetaines and alkyldipolyethoxybetaines with an alkyl radical having about 8 to about 22 carbon atoms, which may be linear or branched, preferably having 8 to 18 carbon atoms and particularly preferably having about 12 to about 18 carbon atoms. These compounds are marketed, for example, by Clariant GmbH under the trade name Genagen LAB. 
     The total active surfactant in the composition may be in the range, for example, of about 3 to 10 wt. %, preferably about 4 to 6 wt. % based on the weight of the composition. If, as preferred, the active surfactant contains of a combination of anionic and amphoteric surfactants, then the weight ratio of anionic surfactant to amphoteric surfactant should be in the range of about 1/30 to 8/1. A more preferred range would be from about 2/3 to about 3/1. 
     Other agents useful to stabilize the composition and prevent phase separation include thickening agents, gelling agents and dispersing agents. Examples include silica, polyacrylates such as Carbopols, alkyloxylated polycarboxylates, alkoyxylated diamines, e.g. Tetronics from BASF, and alkylpolyglucosides, etc. In general, the stabilizing agents will comprise from about 0.5 to 10 wt. % of the composition. 
     The balance of the detergent composition will comprise water, generally from about 15 to 75 wt. % of the composition. More preferably, the composition will contain at least 45 wt. % up to 75 wt. % water. 
     Example 1 
     The following samples shown in Table 1 were made. 
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                   
                 Wt. % 
                 Wt. % 
                 Wt. % 
                 Wt. % 
                 Wt. % 
                 Wt. % 
                 Wt. % 
                 Wt. % 
               
               
                 Sample 
                 NaLAS 
                 C 12-16 (EO) 7   
                 CAP-betaine 
                 Carbopol 676 
                 Ash 
                 ES8018-O 1   
                 Glycerin 
                 Water 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 1 
                 1.56 
                 0.44 
                 1.5 
                 0.4 
                 30 
                 0 
                 0 
                 q.s. 
               
               
                 2 
                   
                   
                   
                   
                   
                   
                 5 
               
               
                 3 
                   
                   
                   
                   
                   
                   
                 10 
               
               
                 4 
                   
                   
                   
                   
                   
                   
                 15 
               
               
                 5 
                   
                   
                   
                   
                   
                 1.5 
                 0 
               
               
                 6 
                   
                   
                   
                   
                   
                   
                 5 
               
               
                 7 
                   
                   
                   
                   
                   
                   
                 10 
               
               
                 8 
                   
                   
                   
                   
                   
                   
                 15 
               
               
                 9 
                   
                   
                   
                   
                   
                 3.0 
                 0 
               
               
                 10 
                   
                   
                   
                   
                   
                   
                 5 
               
               
                 11 
                   
                   
                   
                   
                   
                   
                 10 
               
               
                 12 
                   
                   
                   
                   
                   
                   
                 15 
               
               
                   
               
               
                   1 ethoxylated polycarboxylate- BASF 
               
            
           
         
       
     
     The samples were prepared and allowed to sit for 24 to 48 hours. Following formulation, a portion of each was additionally frozen and thawed later at 25° C. to observe freeze-thaw recoverability. The results are summarized in Table 2. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 2 
               
               
                   
               
               
                   
                   
                   
                 Appearance 
               
               
                   
                 Appearance before 
                 Appearance 
                 following 
               
               
                 Sample 
                 hand stir 
                 after stir 
                 1X Freeze-thaw 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 1 
                 Granular soil 
                   
                   
               
               
                 2 
                 Hard solid 
               
               
                 3 
                 Flowable, homogeneous 
                 Flowable, 
                 No flow, 
               
               
                   
                   
                 homogeneous 
                 but deformable 
               
               
                 4 
                 Slow flow, homogeneous 
                 Slow flow, 
                 No flow, 
               
               
                   
                   
                 homogeneous 
                 but deformable 
               
               
                 5 
                 Soft granular solid 
               
               
                 6 
                 Hard granular solid 
               
               
                 7 
                 Flowable, homogeneous 
                 Flowable, 
                 Very slow 
               
               
                   
                   
                 homogeneous 
                 flow 
               
               
                 8 
                 Slow flow, homogeneous 
                 Slow flow, 
                 No flow, 
               
               
                   
                   
                 homogeneous 
                 but deformable 
               
               
                 9 
                 Soft granular solid 
               
               
                 10 
                 Soft granular solid 
               
               
                 11 
                 Flowable, homogeneous 
                 Flowable, 
                 Very slow 
               
               
                   
                   
                 homogeneous 
                 flow 
               
               
                 12 
                 No flow, deformable 
                 No flow, 
                 No flow, 
               
               
                   
                   
                 deformable 
                 deformable 
               
               
                   
               
            
           
         
       
     
     Initially it was found that between 5 and 10 wt. % glycerin was required to produce liquid samples. It was further observed that compositions 7 and 11 recovered from the freeze-thaw cycle with some degree of flowability, however, the rate of flow was very slow. It was thought that the level of Carbopol (at 0.4%) may have been too high. Therefore, a series of samples based on samples 3, 4, 7, 8, 11, and 12 above, only with 0.2% Carbopol 676 instead, were prepared. Observations of these samples are recorded below in Table 3 
     
       
         
           
               
               
               
               
             
               
                 TABLE 3 
               
               
                   
               
               
                   
                   
                   
                 Appearance 
               
               
                   
                 Appearance before 
                 Appearance 
                 following 
               
               
                 Sample 
                 hand stir 
                 after stir 
                 Freeze-thaw 
               
               
                   
               
             
            
               
                 3A 
                 Liquid + settled solid 
                 Liquid + 
                 Flowable 
               
               
                   
                   
                 settled solid 
               
               
                 4A 
                 Liquid + settled solid 
                 Liquid + 
                 Flowable 
               
               
                   
                   
                 settled solid 
               
               
                 7A 
                 Some settled material, liquid 
                 Homogenous, 
                 Not flowable 
               
               
                   
                 phase has more dispersed 
                 temporarily 
               
               
                   
                 material than 3, 4 
                 stable 
               
               
                 8A 
                 Soft, non-flowable granular 
                 Soft, 
                 No flow 
               
               
                   
                 paste 
                 non-flowable 
               
               
                   
                   
                 granular paste 
               
               
                 11A 
                 Flowable, homogeneous 
                 Flowable, 
                 Flowable 
               
               
                   
                   
                 homogeneous 
               
               
                 12A 
                 Soft granular paste 
                 Soft granular 
                 No flow 
               
               
                   
                   
                 solid 
               
               
                   
               
            
           
         
       
     
     The decrease in Carbopol level therefore improved the freeze-thaw recoverability of sample 11, but may have decreased the degree of structure for 3, 4, and 7. 
     Example 2 
     Systems were also formulated containing urea. Compositions are shown in Table 4. 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 4 
               
               
                   
                   
               
               
                   
                   
                 Urea formula 1 
                 Urea formula 2 
               
               
                   
                 Component 
                 (Wt. %) 
                 (Wt. %) 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 NaLAS 
                 1.56 
                 1.56 
               
               
                   
                 C 12 - 16 (EO) 7   
                 0.44 
                 0.44 
               
               
                   
                 Cocamidopropyl betaine 
                 1.5 
                 1.5 
               
               
                   
                 Carbopol 676 
                 0.2 
                 0.2 
               
               
                   
                 Soda ash 
                 30 
                 30 
               
               
                   
                 Urea 
                 10 
                 5 
               
               
                   
                 Glycerin 
                   
                 5 
               
               
                   
                 Water 
                 q.s. 
                 q.s. 
               
               
                   
                   
               
            
           
         
       
     
     Both systems were pourable 24 hours later and recovered from 1 freeze-thaw cycle. 
     Example 3 
     Additional samples as shown in Table 5 were formulated. 
     
       
         
           
               
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 5 
               
               
                   
               
               
                   
                 Wt. % 
                 Wt % 
                 Wt. % 
                 Wt % 
                 Wt. % 
                 Wt. % 
                 Wt. % 
                 Wt. % 
                 Wt. % 
               
               
                 Sample 
                 NaLAS 
                 P103 2   
                 C 12-16 (EO) 7   
                 CAP-betaine 
                 Carbopol 676 
                 Ash 
                 ES8018-O 
                 Glycerin 
                 Water 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 5-1 
                 1.28 
                 0.56 
                 0.64 
                 1.89 
                 0.05 
                 30 
                 3.0 
                 10 
                 q.s. 
               
               
                 5-2 
                   
                   
                   
                   
                 0.07 
               
               
                 5-3 
                   
                   
                   
                   
                 0.1 
               
               
                   
               
               
                   2 Pluronic EO-PO surfactant- BASF 
               
            
           
         
       
     
     All formulas were shear-deformable gel-like slurries. 
     Example 4 
     Compositions prepared substituting Pluronic L101 for P103 are shown in Table 6. 
     
       
         
           
               
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 6 
               
               
                   
               
               
                   
                 Wt. % 
                 Wt % 
                 Wt. % 
                 Wt. % 
                 Wt. % 
                 Wt. % 
                 Wt. % 
                 Wt. % 
                 Wt. % 
               
               
                 Sample 
                 NaLAS 
                 L101 
                 C 12-16 (EO) 7   
                 CAP-betaine 
                 Carbopol 676 
                 Ash 
                 ES8018-O 
                 Glycerin 
                 Water 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 6-1 
                 1.66 
                 0.58 
                 0.83 
                 1.30 
                 0.05 
                 30 
                 3.0 
                 10 
                 q.s. 
               
               
                 6-2 
                   
                   
                   
                   
                 0.07 
               
               
                 6-3 
                   
                   
                   
                   
                 0.1 
               
               
                   
               
            
           
         
       
     
     All formulas were shear-deformable gel-like slurries. 
     Example 5 
     Compositions containing a mixture of alkali metal carbonates were prepared as shown in Table 7. 
                             TABLE 7                   Sample 7-1   Sample 7-2       Material   (wt. %)   (wt. %)                                            Biosoft D62LT (Stepan)(55% active   3.01   3.01       Na-dodecylbenzesulfonate)       Pluronic L101 (BASF)(EO-PO-EO   1.05   1.05       block copolymer)       Tetronic 901 (BASF)(Ethylene   0.25   0.25       diamine derivatized with EO-PO-EO       block copolymers)       Alfonic 1216CO7 (Sasol)(C 12 -C 16     0.83   0.83       (EO) 7  ethoxylated alcohol)       Tego ZF (Degussa)(30% active   4.34   4.34       cocamidopropyl betaine)       Carbopol 676 (Noveon)(polyacrylic   0.2   0.4       acid copolymer)       Sokalon ES8018-0 (BASF)(45% acive   6.66   6.66       ethoxylated polyacrylic acid)       Na 2 CO 3     22.5   22.5       K 2 CO 3     7.5   7.5       CaCO 3 (approx. 15 μm particle size)       1.5       Glycerin   10   10       Deionized water   q.s.   q.s.                    
Comments on Processing
 
     It has been found that at least two processing factors are useful to the stability of the system. A series of samples similar to composition 7-1 (only that Na 2 CO 3  was added first) were prepared at different temperatures. Appearances of each are noted in Table 8. 
     
       
         
           
               
               
             
               
                 TABLE 8 
               
               
                   
               
               
                 Processing temperature (° C.) 
                 Sample appearance at 25° C. 
               
               
                   
               
             
            
               
                 25 
                 Creaming and settled solid 
               
               
                 40 
                 Creaming and settled solid 
               
               
                 50 
                 Loose flocculent, slight settling of solid 
               
               
                 55 
                 Uniform, creamy emulsion, little to no 
               
               
                 60 
                 settling over 3 days. After 6 days, more 
               
               
                 65 
                 creaming evident. 
               
               
                   
               
            
           
         
       
     
     A second useful processing factor was found to be the relative orders of K 2 CO 3  and Na 2 CO 3 . It was found that samples based on Example 7-1, where K 2 CO 3  was added first, did not exhibit creaming like similar samples made with the addition of Na 2 CO 3  first. Thus, adding K 2 CO 3  first promoted increased stability in these systems. 
     Example 6 
     The following compositions encompassed varying ratios of Alkyl poly glucoside (APG) and Pluronic L101. Values are in weight % and presented on an as is basis in Table 9. 
                                     TABLE 9               Material   9-1   9-2   9-3   9-4                                                    Steol CS130 (Stepan)   7.38   7.38   7.38   7.38       (26% active Na-laureth-1-       sulfate)       Pluronic L101 (BASF)   0.90   0.80   0.70   0.60       (EO-PO-EO block copolymer       MW = 3800, HLB = 1)       Glucopon 625 (Cognis)   0.30   0.49   0.69   0.89       (50.7% active lauryl       polyglucoside)       Tetronic 901 (BASF)   0.25   0.25   0.25   0.25       (Ethylene diamine derivatized       with EO-PO-EO block       copolymers)       Alfonic 1216CO7 (Sasol)   0.64   0.64   0.64   0.64       (C 12 -C 16  7EO ethoxylated       alcohol)       Alfonic 1216CO3 (Sasol)   0.32   0.32   0.32   0.32       (C 12 -C 16  3EO ethoxylated       alcohol)       Mirataine BET O-30 (Rhodia)   2.09   2.09   2.09   2.09       (30% active oleoamidopropyl       dimethyl betaine)       Carbopol 676 (Noveon)   0.20   0.20   0.20   0.20       (polyacrylic acid copolymer)       Sokalan ES95044 (BASF)   6.00   6.00   6.00   6.00       (50% active ethoxylated       polyacrylic acid)       Na 2 CO 3  (Finely Ground)   25.00   25.00   25.00   25.00       K 2 CO 3     5.00   5.00   5.00   5.00       Glycerin   10.00   10.00   10.00   10.00       Deionized water   q.s.   q.s.   q.s.   q.s.                    
Procedure:
 
     Samples were prepared at quantities of 300 g in a 600 mL beaker. Mixing was done with an overhead mixer, using a 1.5″ radial flow impeller (for example, Lightnin R-100).
     1. Water was added to the beaker and stirred at 350 rpm. The water was then heated to 60° C.   2. During the heating, before the temperature reached 40° C., a mass of K 2 CO 3  equal to 1% of the total formula mass being made was added (e.g. 3.0 g of K 2 CO 3  was added, since the total mass of the sample was 300 g).   3. At 40° C., the Carbopol 676 was added. The mixture was further stirred at 350 rpm while it was heated to 60° C. Stirring continued for about 35 minutes until the Carbopol was dissolved.   4. Glycerin was then added and dissolved.   5. ES95044 was added and dissolved.   6. The balance of the K 2 CO 3  was added and dissolved.   7. The Na 2 CO 3  was added. The mixtures were stirred during the Na 2 CO 3  addition at 500 rpm. The rate was reduced to 400 rpm when all of the Na 2 CO 3  was added. Stirring continued until uniform, with the mixtures appearing as white dispersed systems.   8. The stirring rate was maintained at 400 rpm.   9. The CS130 was then added. The mixtures were stirred until uniform.   10. The BET O-30 was then added. The mixtures were stirred until uniform.   11. The Alfonic 1216-7 was then added. The mixtures were stirred until uniform.   12. The Alfonic 1216-3 was then added. The mixtures were stirred until uniform   13. The Glucopon was then added. The mixtures were stirred until uniform.   14. The Pluronic L101 was then added. The mixtures were stirred until uniform.   15. The Tetronic 901 was then added. The mixtures were stirred until uniform.   16. The mixtures then continued to be stirred at 400 rpm and 60° C. for 20 minutes.   17. The mixtures were then removed from the heat, and the rate was reduced to 300 rpm.   18. The mixtures were allowed to cool to 25° C. over a period of 4 hours, while being stirred at 300 rpm.   19. The mixtures were then stirred overnight at 130 rpm.   20. The mixtures were removed from the mixers, and poured into polystyrene containers.   

     All formulas were uniform, flowable dispersions. 
     Detergency Testing 
     Example 9-3, containing 4.8% total surfactant (actives basis), 25% Na 2 CO 3 , and 5% K 2 CO 3 , was evaluated for detergency against a commercial laundry detergent formula containing 6.9% total surfactant and 3.3% Na 2 CO 3 . Evaluations were performed in a Terg-o-Tometer (Instrument Marketing Services, Inc., Fairfield, N.J.). The device consists of six 1 L buckets with accompanying agitators in order to simulate a washing cycle. 
     Six soils were chosen for evaluation: 
     
       
         
           
               
               
               
             
               
                   
                   
               
               
                   
                 Soil 
                 Fabric 
               
               
                   
                   
               
             
            
               
                   
                 Dust-sebum 
                 Cotton 400 
               
               
                   
                 EMPA 101 (Olive oil-carbon black) 
                 Cotton 400 
               
               
                   
                 Clay 
                 Cotton 400 
               
               
                   
                 Dust-sebum 
                 Polyester-cotton 
               
               
                   
                   
                 7435WRL 
               
               
                   
                 EMPA 101 (Olive oil-carbon black) 
                 Polyester-cotton 
               
               
                   
                   
                 7435WRL 
               
               
                   
                 Clay 
                 Polyester-cotton 
               
               
                   
                   
                 7435WRL 
               
               
                   
                   
               
            
           
         
       
     
     Swatches of each were cut to 2 and ¼ inches square peak to valley with a pinked (zig-zag) cut. 
     Detergents were added to the Terg buckets at a level of 1.3 g. An appropriate level of water was then added in order to make a total of 990 mL. The water had previously been pre-heated to about 88° F. (the target wash temperature). The solutions in the buckets were then allowed to equilibrate with the terg bath to a temperature of 88±1° F. The terg timer was then set at 11 minutes. The terg was started, and 10 mL of 10,000 ppm (calculated as equivalent level of CaCO 3 ) hard water was added to each bucket. The hardness of each bucket was therefore 100 ppm. With approximately 10 minutes remaining in the wash cycle, 2 swatches of each soil were added to each terg bucket (for a total of 14 swatches per bucket). 
     At the conclusion of the wash cycle, the swatches were removed from each bucket, squeezed by hand, and placed on a screen. The buckets were then rinsed. To each bucket was then added 990 ml of fresh deionized water along with 10 mL of 10,000 ppm water. Solutions in each bucket were mixed as before. The temperature in each bucket was then allowed to equilibrate at 88±1° F. The terg timer was set to 5 minutes, started, and swatches were added to each bucket. Following this rinse process, the swatches were removed, squeezed by hand, and placed on sieves. 
     To dry the swatches, a cap was placed on top of the sieve holding the swatches. A heat gun was then used to blow hot air up beneath and through the sieve. Drying of the swatches typically took a couple of minutes. 
     Runs were performed in duplicate with samples assignments randomized between the buckets for each run. 
     Evaluation of Soil Removal 
     Soil removal was evaluated by comparing color assessments on swatches before washing and after washing. Color assessments in the CIE L*a*b* color space were performed on unwashed and washed swatches via a BYK Gardner Color-view spectrophotometer. 
     Summaries of % SR for each detergent are shown in Table 10. Values represent the average of four values. Standard deviations (SD) are also shown. Each of the values were assessed for significance versus the control using a double-sided t-test, with the assumption that the variability between the assessments was unknown, but about equal. Significance was assessed at a level of α=0.05. In Table 10 below, values of % SR from the 9-3 formula not determined to be significantly different from the control are noted as “parity,” while % SR values significantly greater than those of the control are noted as “significantly greater.” 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 10 
               
             
            
               
                   
                   
               
               
                   
                 Control 
                 9-3 
                 Signifi- 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Soil 
                 Fabric 
                 % SR 
                 SD 
                 % SR 
                 SD 
                 cance 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Dust-sebum 
                 Cotton 
                 18.45 
                 1.286 
                 18.73 
                 1.610 
                 Parity 
               
               
                   
                 400 
               
               
                 EMPA 101 
                 Cotton 
                 29.29 
                 2.969 
                 32.20 
                 3.761 
                 Parity 
               
               
                 (Olive oil- 
                 400 
               
               
                 carbon black) 
               
               
                 Clay 
                 Cotton 
                 37.18 
                 3.178 
                 36.95 
                 3.137 
                 Parity 
               
               
                   
                 400 
               
               
                 Dust-sebum 
                 Polyester- 
                 32.17 
                 0.9331 
                 52.50 
                 1.117 
                 Significantly 
               
               
                   
                 cotton 
                   
                   
                   
                   
                 Greater 
               
               
                   
                 7435WRL 
               
               
                 EMPA 104 
                 Polyester- 
                 28.10 
                 2.330 
                 28.76 
                 1.830 
                 Parity 
               
               
                 (Olive oil- 
                 cotton 
               
               
                 carbon black) 
                 7435WRL 
               
               
                 Clay 
                 Polyester- 
                 71.36 
                 1.537 
                 73.26 
                 2.506 
                 Parity 
               
               
                   
                 cotton 
               
               
                   
                 7435WRL 
               
               
                   
               
            
           
         
       
     
     The experimental formula, with a lower total surfactant level than that of the control, performed at a level equal to or significantly greater than that of the control. 
     Example 7 
     The following compositions in Table 11 were made with Pluronic L121 (MW=4400, HLB=1). The compositions differ in the levels of Na 2 CO 3  and K 2 CO 3 . All values are in weight % on an as is basis: 
     
       
         
           
               
               
               
             
               
                 TABLE 11 
               
               
                   
               
               
                 Material 
                 11-1 
                 11-2 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 Steol CS130 (Stepan) 
                 6.16 
                 6.16 
               
               
                 (26% active Na-laureth-1-sulfate) 
               
               
                 Pluronic L121 (BASF) 
                 0.70 
                 0.70 
               
               
                 (EO-PO-EO block copolymer MW = 4400, HLB = 1) 
               
               
                 Glucopon 625 (Cognis) 
                 0.69 
                 0.69 
               
               
                 (50.7% active lauryl polyglucoside) 
               
               
                 Tetronic 901 (BASF) 
                 0.25 
                 0.25 
               
               
                 (Ethylene diamine derivatized with EO-PO-EO 
               
               
                 block copolymers) 
               
               
                 Alfonic 1216CO7 (Sasol) 
                 0.60 
                 0.60 
               
               
                 (C 12 -C 16  7EO ethoxylated alcohol) 
               
               
                 Alfonic 1216CO3 (Sasol) 
                 0.20 
                 0.20 
               
               
                 (C 12 -C 16  3EO ethoxylated alcohol) 
               
               
                 Mirataine BET O-30 (Rhodia) 
                 4.17 
                 4.17 
               
               
                 (30% active oleoamidopropyl dimethyl betaine) 
               
               
                 Carbopol 676 (Noveon) 
                 0.20 
                 0.20 
               
               
                 (polyacrylic acid copolymer) 
               
               
                 Sokalan ES95044 (BASF) 
                 6.00 
                 6.00 
               
               
                 (50% active ethoxylated polyacrylic acid) 
               
               
                 Na 2 CO 3  (Finely Ground) 
                 25.00 
                 22.5 
               
               
                 K 2 CO 3   
                 5.00 
                 7.5 
               
               
                 Glycerin 
                 10.00 
                 10.00 
               
               
                 Deionized water 
                 q.s. 
                 q.s. 
               
               
                   
               
            
           
         
       
     
     Both compositions were uniform, flowable dispersions. 
     Detergency Evaluation 
     The 11-1 and 11-2 formulas were assessed for detergency as described above. Results are shown in Tables 12 and 13. 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 12 
               
             
            
               
                   
                   
               
               
                   
                 Control 
                 11-1 
                 Signifi- 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Soil 
                 Fabric 
                 % SR 
                 SD 
                 % SR 
                 SD 
                 cance 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Dust-sebum 
                 Cotton 
                 16.13 
                 0.8725 
                 19.35 
                 0.2971 
                 Signifi- 
               
               
                   
                 400 
                   
                   
                   
                   
                 cantly 
               
               
                   
                   
                   
                   
                   
                   
                 Greater 
               
               
                 EMPA 101 
                 Cotton 
                 25.23 
                 1.761 
                 29.43 
                 2.126 
                 Signifi- 
               
               
                 (Olive oil- 
                 400 
                   
                   
                   
                   
                 cantly 
               
               
                 carbon black) 
                   
                   
                   
                   
                   
                 Greater 
               
               
                 Clay 
                 Cotton 
                 31.06 
                 1.486 
                 32.91 
                 1.654 
                 Parity 
               
               
                   
                 400 
               
               
                 Dust-sebum 
                 Polyester- 
                 32.56 
                 0.3984 
                 52.31 
                 1.213 
                 Signifi- 
               
               
                   
                 cotton 
                   
                   
                   
                   
                 cantly 
               
               
                   
                 7435WRL 
                   
                   
                   
                   
                 Greater 
               
               
                 EMPA 104 
                 Polyester- 
                 22.97 
                 0.8235 
                 22.34 
                 0.6315 
                 Parity 
               
               
                 (Olive oil- 
                 cotton 
               
               
                 carbon black) 
                 7435WRL 
               
               
                 Clay 
                 Polyester- 
                 71.49 
                 3.482 
                 71.49 
                 2.802 
                 Parity 
               
               
                   
                 cotton 
               
               
                   
                 7435WRL 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 13 
               
             
            
               
                   
                   
               
               
                   
                 Control 
                 11-2 
                 Signifi- 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Soil 
                 Fabric 
                 % SR 
                 SD 
                 % SR 
                 SD 
                 cance 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Dust-sebum 
                 Cotton 
                 16.13 
                 0.8725 
                 17.31 
                 0.8879 
                 Parity 
               
               
                   
                 400 
               
               
                 EMPA 101 
                 Cotton 
                 25.23 
                 1.761 
                 29.74 
                 0.6231 
                 Signifi- 
               
               
                 (Olive oil- 
                 400 
                   
                   
                   
                   
                 cantly 
               
               
                 carbon black) 
                   
                   
                   
                   
                   
                 Greater 
               
               
                 Clay 
                 Cotton 
                 31.06 
                 1.486 
                 32.91 
                 1.654 
                 Parity 
               
               
                   
                 400 
               
               
                 Dust-sebum 
                 Polyester- 
                 32.56 
                 0.3984 
                 49.07 
                 0.9982 
                 Signifi- 
               
               
                   
                 cotton 
                   
                   
                   
                   
                 cantly 
               
               
                   
                 7435WRL 
                   
                   
                   
                   
                 Greater 
               
               
                 EMPA 104 
                 Polyester- 
                 22.97 
                 0.8235 
                 22.78 
                 1.513 
                 Parity 
               
               
                 (Olive oil- 
                 cotton 
               
               
                 carbon black) 
                 7435WRL 
               
               
                 Clay 
                 Polyester- 
                 71.49 
                 3.482 
                 74.40 
                 1.452 
                 Parity 
               
               
                   
                 cotton 
               
               
                   
                 7435WRL 
               
               
                   
               
            
           
         
       
     
     Both formulas (containing 4.96% total surfactant) performed at parity or significantly better than the control having 6.9% surfactant. 
     Example 8 
     The experimental formula 9-1 was tested at dose levels of 2.37 and 1.56 oz., and compared with a standard 3.125 oz. dose of a typical commercial laundry detergent. The effective surfactant levels at each dose are compared in Table 14. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 14 
               
               
                   
               
               
                   
                 Dose in 71 L 
                 Dose in 71 L 
                 Mass of surfactant 
               
               
                 Detergent 
                 wash (oz.) 
                 wash (g) 
                 in dose (g) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 Commercial HDL 
                 3.125 
                 96.9 
                 6.69 
               
               
                 (control) 
               
               
                 9-1 
                 2.37 
                 100.0 
                 4.80 
               
               
                 9-1 
                 1.56 
                 65.9 
                 3.16 
               
               
                   
               
            
           
         
       
     
     Therefore, the levels of surfactant in the experimental detergent doses were less than that in the standard detergent. 
     The following swatches were evaluated: 
     
       
         
           
               
               
               
               
               
             
               
                   
               
             
            
               
                 Soil 
                 Dust-Sebum 
                 Cotton #400 
                 Scientific 
                   
               
               
                 Swatches 
                   
                   
                 Services 
               
               
                   
                 Dust-Sebum 
                 Style 7435WRL 
                 Scientific 
               
               
                   
                   
                 65/35 Polyester/ 
                 Services 
               
               
                   
                   
                 Cotton 
               
               
                   
                   
                 Shirting 
               
               
                   
                 Ground - in - 
                 Cotton #400 
                 Scientific 
               
               
                   
                 Clay 
                   
                 Services 
               
               
                   
                 Ground - in - 
                 Style 7435WRL 
                 Scientific 
               
               
                   
                 Clay 
                 65/35 Polyester/ 
                 Services 
               
               
                   
                   
                 Cotton 
               
               
                   
                   
                 Shirting 
               
               
                   
                 Standard Soil 
                 Cotton S/493 
                 Test Fabrics 
               
               
                   
                 Carbon Black/ 
                 Cotton 
                 Test Fabrics 
                 EMPA 
               
               
                   
                 Olive Oil 
                   
                   
                 101 
               
               
                   
                 Carbon Black/ 
                 Polyester/ 
                 Test Fabrics 
                 EMPA 
               
               
                   
                 Olive Oil 
                 Cotton 
                   
                 104 
               
               
                   
                   
                 67/33 
               
               
                 Stain 
                 Grass 
                 Cotton #400 
                 Scientific 
               
               
                 Swatches 
                   
                   
                 Services 
               
               
                   
                 Coffee 
                 Cotton #400 
                 Scientific 
               
               
                   
                   
                   
                 Services 
               
               
                   
                 Beef Gravy 
                 Cotton #400 
                 Scientific 
               
               
                   
                   
                   
                 Services 
               
               
                   
                 Ketchup 
                 Cotton #400 
                 Scientific 
               
               
                   
                   
                   
                 Services 
               
               
                   
                 Makeup 
                 Cotton #400 
                 Test Fabrics 
               
               
                   
                 Blood/Milk/ 
                 Cotton 
                 Test Fabrics 
                 EMPA 
               
               
                   
                 Carbon Black 
                   
                   
                 116 
               
               
                   
                 Blood/Milk/ 
                 Polyester/ 
                 Test Fabrics 
                 EMPA 
               
               
                   
                 Carbon Black 
                 Cotton 
                   
                 117 
               
               
                   
                   
                 67/33 
               
               
                   
                 Cocoa 
                 Cotton 
                 Test Fabrics 
                 EMPA 
               
               
                   
                   
                   
                   
                 112 
               
               
                   
                 Red Wine 
                 Cotton #400 
                 Scientific 
               
               
                   
                   
                   
                 Services 
               
               
                   
                 Chocolate Ice 
                 Cotton #400 
                 Scientific 
               
               
                   
                 Cream 
                   
                 Services 
               
               
                   
                 Mustard 
                 Cotton #400 
                 Scientific 
               
               
                   
                   
                   
                 Services 
               
               
                   
                 Blueberry 
                 Cotton #400 
                 Scientific 
               
               
                   
                   
                   
                 Services 
               
               
                   
                 Blood 
                 Cotton #400 
                 Scientific 
               
               
                   
                   
                   
                 Services 
               
               
                   
               
            
           
         
       
     
     Four total replicates of each swatch were run by fastening one swatch of each type to a pillowcase (for a total of four pillowcases). Two pillowcases were washed in one washer while the remaining two pillowcases were washed in another washer of the same make and model. The water hardness was carefully controlled at 100 ppm and the temperature was kept constant at 88° F. 
     Degrees of soil removal were evaluated as noted in the previous terg-o-tometer results. Results are summarized below. In tests of statistical significance, % SR (% Soil or % Stain Removal) results significantly higher than the control are denoted with (+), less than the control as (−), and equal as (=): 
     
       
         
           
               
               
            
               
                   
                   
               
               
                   
                 Percent Stain/Soil Removal 
               
            
           
           
               
               
               
               
            
               
                   
                   
                 9-1 High 
                 9-1 High 
               
               
                   
                   
                 Ash Formula 
                 Ash Formula 
               
               
                   
                 Control 
                 (4.80 g 
                 (3.16 g 
               
               
                   
                 (6.69 g 
                 surfactant) 
                 surfactant) 
               
               
                   
                 surfactant) 
                 2.37 oz dose 
                 1.56 oz dose 
               
               
                   
                 96.9 g 
                 100.0 g 
                 65.9 g 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
            
               
                 STAINS 
                   
                   
                   
                   
               
               
                 Grass 
                 Cotton 
                 28.6 
                 27.3= 
                 19.5− 
               
               
                 Coffee 
                 Cotton 
                 57.7 
                 55.1= 
                 53.3− 
               
               
                 Beef Gravy 
                 Cotton 
                 78.2 
                 78.0= 
                 77.8= 
               
               
                 Ketchup 
                 Cotton 
                 88.7 
                 89.4= 
                 89.0= 
               
               
                 Makeup 
                 Cotton 
                 44.3 
                 46.5= 
                 42.2= 
               
               
                 EMPA 116 
                 Cotton 
                 20.8 
                 23.2= 
                 23.0= 
               
               
                 EMPA 112 
                 Cotton 
                 29.7 
                 24.9− 
                 23.0− 
               
               
                 Red Wine 
                 Cotton 
                 69.3 
                 61.0− 
                 60.8− 
               
               
                 Choc Ice Cream 
                 Cotton 
                 75.2 
                 72.8= 
                 71.1− 
               
               
                 Mustard 
                 Cotton 
                 46.4 
                 66.6+ 
                 61.7+ 
               
               
                 Blueberry 
                 Cotton 
                 79.2 
                 77.2= 
                 77.5= 
               
               
                 Blood 
                 Cotton 
                 73.5 
                 78.6+ 
                 75.4+ 
               
               
                 EMPA 117 
                 PolyCotton 
                 18.5 
                 21.0+ 
                 18.7= 
               
               
                 TOTAL STAINS 
                   
                 710.1 
                 721.4 
                 692.9 
               
               
                 SOILS 
               
               
                 Dust Sebum 
                 Cotton 
                 47.7 
                 56.6+ 
                 49.1= 
               
               
                 Standard Soil 
                 Cotton 
                 16.4 
                 14.7= 
                 11.5− 
               
               
                 EMPA 101 
                 Cotton 
                 27.6 
                 30.5+ 
                 28.0= 
               
               
                 Clay 
                 Cotton 
                 52.1 
                 48.8− 
                 47.7− 
               
               
                 Dust Sebum 
                 PolyCotton 
                 49.9 
                 72.9+ 
                 56.4+ 
               
               
                 EMPA 104 
                 Polycotton 
                 22.2 
                 21.1= 
                 19.5= 
               
               
                 Clay 
                 Polycotton 
                 72.4 
                 75.3= 
                 73.3= 
               
               
                 TOTAL SOILS 
                   
                 288.0 
                 319.8 
                 285.5 
               
               
                 WHITNESS 
               
               
                 INDEX 
               
               
                 delta b 
                   
                 −1.2 
                 −0.4− 
                 −0.4− 
               
               
                 delta WIE 
                   
                 5.9 
                 2.1− 
                 2.0− 
               
               
                 pH 10 Min. 
                   
                 9.4 
                 10.3 
                 10.1 
               
               
                 into wash 
               
               
                 Total 
                   
                 998.1 
                 1041.2 
                 978.4 
               
               
                 (stain + soil) 
               
            
           
           
               
               
               
               
            
               
                 OVERALL STAIN REMOVAL 
                 54.6 
                 55.5= 
                 53.3= 
               
               
                 OVERALL SOIL REMOVAL 
                 41.1 
                 45.7+ 
                 40.8= 
               
            
           
           
               
               
               
               
               
            
               
                 Washer 
                   
                 6, 7 
                 1, 4 
                 3, 5 
               
               
                   
               
               
                 EMPA 116 = Blood, Milk and Carbon Black on Cotton, EMPA 101 = Carbon Black and Olive Oil on Cotton EMPA 117 = Blood, Milk and Carbon Black on Poly/Cotton, EMPA 104 = Carbon Black and Olive Oil on Poly/Cotton EMPA 112 = Cocoa on Cotton 
               
            
           
         
       
     
     At the 2.37 oz. dose, overall stain removal was about the same as that of the control, while overall soil removal was higher. At the 1.56 oz. dose, performance was at about parity with the control. Among the different stain and soil types, some examples of higher and lower comparative performance levels were seen.