Abstract:
The present invention relates to agricultural emulsion concentrates which form stable oil-in-water emulsions when diluted with water. More specifically, the invention relates to stable oil-in-water emulsions which include cinnamaldehyde and diallyl disulfide with a Calsogen® EH and Surfonic® CO 36 emulsion system. The increased stability of the emulsion allows for efficient mixing of the emulsion ingredients and effective storage and application of the cinnamaldehyde and diallyl disulfide to areas in need of nematode protection or treatment.

Description:
PRIORITY 
       [0001]    This application is a Continuation-in-Part of U.S. patent application Ser. No. 12/580,391, filed Oct. 16, 2009, which claims the benefit of U.S. Provisional Application No. 61/106,186, filed Oct. 17, 2008, the contents of each are herein incorporated by reference. 
     
    
     FIELD OF THE INVENTION 
       [0002]    The present invention relates to stable emulsions containing cinnamaldehyde and diallyl disulfide. Specifically, the stable emulsions utilize Emulsogen® EH and Surfonic® CO 36 to form a superior emulsion stability system. 
       BACKGROUND OF THE INVENTION 
       [0003]    Emulsions generally refer to heterogeneous systems that comprise two immiscible liquids. In agriculture, emulsions provide formulation vehicles for delivery of herbicides, insecticides, fungicides, bactericides, and fertilizers. 
         [0004]    Mechanical agitation, such as shaking or stirring, or another energy input is required to form an emulsion. Emulsions are inherently unstable, meaning that once they are formed, the immiscible liquids tend to revert or separate. Emulsifying agents, such as surface-active agents, can be used to increase the stability of the emulsions. In the context of emulsions, “stable” or “stability” means that the droplet particles of one liquid are uniformly distributed into another liquid and that this status is maintained for a desirable amount of time. 
         [0005]    Emulsions are especially useful in the field of agriculture wherein numerous lipophilic active ingredients must be dissolved and suspended into water prior to application to the plants. An oil-in-water emulsion (O/W emulsion) is an emulsion wherein liquid oil droplets are finely dispersed in water. Preparing stable O/W emulsions in very difficult and frequently involves extensive experimentation to determine formulations that provide stable concentrated products for end-use diluted emulsions. 
         [0006]    The emulsion system plays an essential role in providing stable emulsions, but identification of a proper system is complex and not easy to identify because of the required optimization of many different formulation characteristics, such as interfacial tension, viscosity, relative density, and temperature. 
         [0007]    In addition, there are hundreds of different emulsifiers and surfactants commercially available with vastly different properties. The available emulsifiers and surfactants could be used in formulations in varying combinations and amounts to produce thousands of different potential formulations, each producing unpredictable stability characteristics. When more than one emulsifier or surfactant are combined in a formulation, they produce an emulsion system. 
         [0008]    Calsogen® EH (available from Clariant) is an emulsifier, specifically, an iso-C12 alkyl benzene sulphonate calcium salt. 
         [0009]    Surfonic® CO 36 (available from Huntsman, Inc.) is a surfactant and it contains polyglycol esters of castor oil. 
         [0010]    Cinnamaldehyde is a naturally occurring organic compound that can be derived from the bark of trees of the genus  Cinnamomum . Cinnamaldehyde is a viscous oil that has low solubility in water. Cinnamaldehyde does not present any known risk to humans or the environment and is considered to have a minimal safety risk. For this reason, it is not regulated by the Environmental Protection Agency (“EPA”) because it is exempt from the Federal Insecticide, Fungicide, and Rodenticide Act (“FIFRA”). See 40 C.F.R. §152.25(f). 
         [0011]    Cinnamaldehyde is known to have pesticidal activity. For example, cinnamaldehyde is effective against nematodes. See, for example, U.S. Pat. No. 6,251,951 B1. 
         [0012]    Diallyl disulfide (4,5-dithia-1,7-octadiene) is a naturally occurring organosulfur compound that can be derived from garlic and plants of the genus  Allium . Diallyl disulfide is an oil that has low solubility in water. Diallyl disulfide does not present any known risk to humans or the environment and is considered to have a minimal safety risk. For this reason, it is not regulated by the Environmental Protection Agency (“EPA”) because it is exempt from the Federal Insecticide, Fungicide, and Rodenticide Act (“FIFRA”). See 40 C.F.R. §152.25(f). 
         [0013]    There is a need to improve the safety characteristics of pesticides that are applied to plants intended for human and animal consumption. In order to achieve the goal of providing a safer pesticide, users must: (1) use environmentally safe actives, such as essential oils; and (2) if using essential oils, then they must include an environmentally safe emulsion system. 
         [0014]    In prior art formulations, the use of environmentally harmful organic, solvents or other components were required to produce stable and effective dilutable emulsions if they contained plant essential oils, such as cinnamaldehyde and dially disulfide. Although organic solvents are very effective in forming emulsions, they are also often flammable, corrosive or toxic to living systems and are of environmental concern. For example, ProGuard® 30% is a commercially available insecticide, miticide and fungicide that contains cinnamaldehyde. However, ProGuard® 30% also contains the undesirable ingredient o-Phenylphenol. 
         [0015]    Therefore, there is a need for environmentally safe pesticidal formulations that contain effective but safe actives. 
       SUMMARY OF THE INVENTION 
       [0016]    Applicants unexpectedly discovered that an emulsion system comprising Emulsogen® EH and Surfonic® CO 36 provided excellent emulsion stability for cinnamaldehyde and diallyl disulfide formulations. 
         [0017]    In one aspect, the invention is directed to improved and stable formulations containing  cinnamaldehyde  and diallyl disulfide with the emulsion system of Emulsogen® and Surfonic® CO 36. 
         [0018]    In another aspect, the invention is directed to a specific agricultural formulation comprising about 61.0% cinnamaldehyde about 6.0 to about 8.5% diallyl disulfide, from about 13.0 to about 15.5% soybean oil, about 7.0% Calsogen® EH, and about 10.5% Surfonic® CO 36. 
         [0019]    In a further aspect, the invention is directed to methods for suppressing plant damage by plant pathogens comprising applying the formulations of the invention to the locus, soil or seeds of plants in need of said treatment. 
         [0020]    In a final aspect, the invention is directed to agricultural formulations comprising a synergistic amount of cinnamaldehyde and diallyl disulfide. 
     
    
     DETAILED DESCRIPTION 
       [0021]    in one embodiment of the invention, the invention is an agricultural formulation comprising cinnamaldehyde, diallyl disulfide, Surfonic® CO 36, and an iso-C12 alkylbenzene sulphonate calcium salt. 
         [0022]    In another embodiment, the iso-C12 alkyl benzene sulphonate calcium salt is Calsogen® EH. In a further embodiment, the formulation may contain from about 5 to about 9% by weight of the iso-C12 alkyl benzene sulphonate calcium salt or Calsogen® EH, preferably from about 6.0 to about 8.0%, and most preferably about 7.0% of the iso-C12 alkyl benzene sulphonate calcium salt or Calsogen® EH. 
         [0023]    in a further embodiment, the formulation may contain a lipophilic solvent. In a preferred embodiment, the lipophilic solvent is soybean oil. The formulation may contain from about 10.0 to about 20.0% by weight, preferably from about 12.0 to 16.0%, and most preferably from about 13.0 to about 15.5% of the lipophilic solvent or soybean oil. 
         [0024]    In yet another embodiment, the formulation may contain from about 50 to about 70% by weight of cinnamaldehyde, preferably from about 58 to about 63% of cinnamaldehyde, and most preferably about 61% cinnamaldehyde. 
         [0025]    In a further embodiment, the formulation may contain from about 5 to about 10% by weight of diallyl disulfide, preferably from about 5.5 to about 9.0%, and most preferably about from about 6.0 to about 8.5% of diallyl disulfide. 
         [0026]    The formulation may contain from about 8 to about 12% of Surfonic® CO 36 by weight in one embodiment. Preferably, the formulation contains from about 9.0 to about 11.0% of Surfonic® CO 36, and more preferably, about 10.5% of Surfonic® CO 36. 
         [0027]    In a preferred embodiment, the invention is directed to an agricultural formulation comprising: from about 59.5 to about 61.5% cinnamaldehyde; from about 6.0 to about 8.5% diallyl disulfide from about 13.0 to about 15.5% soybean oil; about 7.0% Calsogen® EH; and about 10.5% Surfonic® CO 36. In a more preferred embodiment, the formulation contains about 61.0% cinnamaldehyde. 
         [0028]    An alternative embodiment is directed to methods for suppressing plant damage by plant pathogens comprising applying the formulation of the present invention to the locus, soil or seeds of plants in need of said treatment, in a preferred embodiment, the plant pathogens are nematodes. 
         [0029]    In U.S. patent application Ser. No. 12/580,391, Applicants discussed the synergy between cinnamaldehyde and diallyl disulfide (see Example 3). Specifically, Applicants revealed that when cinnamaldehyde and diallyl disulfide are combined, nematodes are suppressed at bio-control levels far below those needed when the each component is applied alone. Applicants unexpectedly found that this effect was more than merely additive and was synergistic. Accordingly, in an embodiment, this invention is directed to agricultural formulations which contain a synergistic amount of cinnamaldehyde and diallyl disulfide. 
         [0030]    The emulsifying system utilized in formulations of the present invention is a unique combination of two emulsifiers, Calsogen® EH and Surfonic® CO 36. This system can be used in the formulation with a total % weight from about 10 to about 30% of the formulation, preferably from about 15 to about 19% of the formulation, and most preferably at about 17.5% of the formulation. 
         [0031]    As mentioned above, formulations of the present invention may contain lipophilic solvents. The preferred solvent is soybean oil, however, other solvents may be used as long as the solvents are “environmentally safe,” meaning that they are exempt from volatile organic compound (“VOC”) regulation by the EPA. For example, the following solvents may be used: methyl oleate, ethyl lactate, and methyl soyate. The agricultural formulations of the present invention explicitly exclude organic solvents which are considered to have unsatisfactory VOC levels as defined by California Environmental Protection Agency. The agricultural formulations of the present invention explicitly exclude ingredients which are considered by the state of California to cause cancer or reproductive toxicity under the The Safe Drinking Water and Toxic Enforcement Act of 1986 (see Health and Safety Code Section 25249.8(b)). 
         [0032]    Formulations of the present invention contain an iso-C12 alkyl benzene sulfonate calcium salt. As previously mentioned, Calsogen® EH is preferred. However, other iso-C12 alkyl benzene sulfonate calcium salts known by those of skill in the art may be used in formulations of the invention, such as Phenylsulfonat CA or Phenylsulfonat CA 62 (both available from Clariant). 
         [0033]    The trade names used herein are used to describe a type of component with specific chemistries. When a trade name is used herein, a component, with the same of very similar chemistry may be suitable unless indicated otherwise. 
         [0034]    The terms “emulsion concentrate,” “emulsifiable concentrate” and “formulation” are used interchangeably throughout the application. 
         [0035]    The terms “emulsion system” and “emulsifying system” are used interchangeably throughout the application. 
         [0036]    As used herein, all numerical values relating to amounts, weight percentages and the like, are defined as “about” or “approximately” each particular values plus or minus 10% (±10%). For example, the phrase “greater than 0.1%” is to be understood as encompassing values greater than 0.09%. Therefore, amounts within 10% of the claimed values are encompassed by the scope of the invention. 
         [0037]    The percentages of the components in the formulations and comparative formulations are listed by weight percentage. 
         [0038]    It is understood that the foregoing detailed description and accompanying examples are merely illustrative and are not to be taken as limitations upon the scope of the invention, which is defined solely by the appended claims and their equivalents. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications, including without limitation those relating to the active agents and excipients of the invention, may be made without departing from the spirit and scope hereof. 
         [0039]    The following examples are offered by way of illustration only, not to limit the scope of this invention, as represented by the claims list attached herein. 
       EXAMPLES 
     Example 1 
     Preparation of a Cinnamaldehyde and Diallyl Disulfide Emulsion Concentrate Formulation 
       [0040]    A cinnamaldehyde and diallyl disulfide emulsion concentrate was prepared. The following components, in the amounts indicated below (in weight % of the component/total weight % of the formulation), were added in the order listed. The formulation was then mixed well with a magnetic stirrer until a homogeneous emulsion was formed.
       61.0% cinnamaldehyde   21.5% diallyl disulfide and soybean oil (about 6 to 8.5% diallyl disulfide and 13.0 to   15.5% soybean oil)   7.0% Calsogen® EH   10.5% Surfonic® CO 36       
 
         [0046]    The amount of diallyl disulfide added will vary depending upon the purity of the technical grade diallyl disulfide. Soybean oil may be used in varying amounts to accommodate the strength of the technical grade diallyl disulfide. 
       Example 2 
     Stability Study 
       [0047]    The Formulation of Example 1 was compared with 16 other formulations containing the same amount of cinnamaldehyde, diallyl disulfide, and solvent but with different emulsifying systems. The 16 comparative emulsion concentrate formulations were prepared in a manner similar to the manner in which the Formulation of Example 1 was prepared as described above. 
         [0048]    A standard emulsion stability test was utilized. Specifically, 5 mL of each emulsion concentrate formulation was added to 95 mL of water in a 100 mL graduated cylinder. The cylinder was stopped and inverted repeatedly until a homogeneous O/W emulsion was produced. The cylinder was then observed to detect phase separation or other indications of instability. 
         [0049]    The results can be seen below in “Table 1. Emulsion Stability of Cinnamaldehyde and Diallyl Disulfide Formulations.” 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Emulsion Stability of Cinnamaldehyde and Diallyl Disulfide Formulation 
               
             
          
           
               
                   
                   
                 Emulsifying 
                 % in 
                   
                   
                   
                   
               
               
                 Form. 
                 Exp# 
                 System 
                 Form. 
                 0 min 
                 2 hr 
                 4 hr 
                 24 hr 
               
               
                   
               
             
          
           
               
                 Form. 
                 38C 
                 Calsogen ® EH 
                 7 
                 Bloom: 
                 Emulsion: Excellent, 
                 Emulsion: 
                 Emulsion: 
               
               
                 of Ex. 1 
                   
                 Surfonic ® CO 36 
                 10.5 
                 Excellent; 
                 uniform, thick; 
                 Excellent, uniform, 
                 Excellent, uniform, 
               
               
                   
                   
                   
                   
                 Inversion: 0.5 
                 Separation: None 
                 thick; Separation: 
                 thick; Separation: 
               
               
                   
                   
                   
                   
                   
                   
                 None 
                 None 
               
               
                  2 
                 38A 
                 Calsogen ® EH 
                 7 
                 Bloom: 
                 Emulsion: Excellent, 
                 Emulsion: Good; 
                 Emulsion: Good; 
               
               
                   
                   
                 Emulsogen ® EL 
                 10.5 
                 Excellent; 
                 uniform, thick; 
                 Separation: 2 mL 
                 Separation: 4 mL 
               
               
                   
                   
                 360 
                   
                 Inversion: 0.5 
                 Separation: None 
                 clear layer on 
                 clear yellow layer 
               
               
                   
                   
                   
                   
                   
                   
                 bottom 
                 on bottom; 
               
               
                   
                   
                   
                   
                   
                   
                   
                 Reconstitute: 0.5 
               
               
                   
                   
                   
                   
                   
                   
                   
                 inversion 
               
               
                  3 
                 38B 
                 Atlox ™ 4838B 
                 7 
                 Bloom: 
                 Emulsion: Excellent, 
                 Emulsion: Good; 
                 Emulsion: Good; 
               
               
                   
                   
                 Emulsogen ® EL 
                 10.5 
                 Excellent; 
                 uniform, thick; 
                 Separation: 1 mL 
                 Separation: 3 mL 
               
               
                   
                   
                 360 
                   
                 Inversion: 0.5 
                 Separation: None 
                 clear layer on 
                 clear yellow layer 
               
               
                   
                   
                   
                   
                   
                   
                 bottom 
                 on bottom; 
               
               
                   
                   
                   
                   
                   
                   
                   
                 Reconstitute: 0.5 
               
               
                   
                   
                   
                   
                   
                   
                   
                 inversion 
               
               
                  4 
                 38D 
                 Atlas ™ G-1086 
                 17.5 
                 Bloom: 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
               
               
                   
                   
                   
                   
                 Unacceptable; 
                 out; Separation: 8.5 mL 
                 out; Separation: 7 mL 
                 out; Separation: 7 mL 
               
               
                   
                   
                   
                   
                 Settling: Settled 
                 white 
                 white 
                 white 
               
               
                   
                   
                   
                   
                 at 0 min; 
                 precipitate on 
                 precipitate on 
                 precipitate on 
               
               
                   
                   
                   
                   
                 Inversion: 1 
                 bottom. 
                 bottom. 
                 bottom. 
               
               
                   
                   
                   
                   
                   
                   
                   
                 Reconstitute: 5 
               
               
                   
                   
                   
                   
                   
                   
                   
                 inversions 
               
               
                  5 
                 38E 
                 Atlox ™ 4838B 
                 7 
                 Bloom: 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
               
               
                   
                   
                 Atlas ™ G-1086 
                 10.5 
                 Unacceptable; 
                 out; Separation: 6 mL 
                 out; Separation: 2 mL 
                 out; Separation: 
               
               
                   
                   
                   
                   
                 Settling: Settled 
                 white 
                 yellow layer 
                 3.5 mL yellow 
               
               
                   
                   
                   
                   
                 at 0 min; 
                 precipitate on 
                 on bottom. 
                 layer on bottom; 
               
               
                   
                   
                   
                   
                 Inversion: 1 
                 bottom. 
                   
                 Reconstitute: 0.5 
               
               
                   
                   
                   
                   
                   
                   
                   
                 inversion 
               
               
                  6 
                 38F 
                 Synperonic ® A20 
                 17.5 
                 Bloom: Poor; 
                 Emulsion: Thinned 
                 Emulsion: None, 
                 Emulsion: None; 
               
               
                   
                   
                   
                   
                 Settling: Settled 
                 out; Separation: 5 mL 
                 top 10% 
                 Separation: 5 mL 
               
               
                   
                   
                   
                   
                 on bottom at 0 min; 
                 white 
                 clear; Separation: 
                 white precipitate on 
               
               
                   
                   
                   
                   
                 Inversion: 5 
                 precipitate on 
                 5 mL white 
                 bottom; 
               
               
                   
                   
                   
                   
                   
                 bottom. 
                 precipitate on 
                 Reconstitute: Did 
               
               
                   
                   
                   
                   
                   
                   
                 bottom. 
                 not in 5 inversions 
               
               
                  7 
                 38G 
                 Atlox ™ 4838B 
                 7 
                 Bloom: None, 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
               
               
                   
                   
                 Synperonic ® A20 
                 10.5 
                 Unacceptable; Settling: 
                 out; Separation: 5 mL 
                 out; Separation: 
                 out; Separation: 
               
               
                   
                   
                   
                   
                 Settled 
                 white on 
                 5 mL white on 
                 6 mL white 
               
               
                   
                   
                   
                   
                 on bottom at 0 min; 
                 bottom. 
                 bottom. 
                 precipitate on 
               
               
                   
                   
                   
                   
                 Inversion: 5 
                   
                   
                 bottom; 
               
               
                   
                   
                   
                   
                   
                   
                   
                 Reconstitute: Did 
               
               
                   
                   
                   
                   
                   
                   
                   
                 not in 5 inversions 
               
               
                  8 
                 38H 
                 Calsogen ® EH 
                 7 
                 Bloom: None, 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
               
               
                   
                   
                 Synperonic ® A20 
                 10.5 
                 Unacceptable; 
                 out; Separation: 5 mL 
                 out; Separation: 5 mL 
                 out; Separation: 7 mL 
               
               
                   
                   
                   
                   
                 Settling: Settled 
                 white 
                 white 
                 white 
               
               
                   
                   
                   
                   
                 on bottom at 0 min; 
                 precipitate on 
                 precipitate on 
                 precipitate on 
               
               
                   
                   
                   
                   
                 Inversion: 5 
                 bottom. 
                 bottom. 
                 bottom; 
               
               
                   
                   
                   
                   
                   
                   
                   
                 Reconstitute: Did 
               
               
                   
                   
                   
                   
                   
                   
                   
                 not in 5 inversions 
               
               
                  9 
                 38I 
                 Atlas ™ G-5000 
                 17.5 
                 Bloom: 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
               
               
                   
                   
                   
                   
                 Acceptable; 
                 out; Separation: 12 mL 
                 out; Separation: 
                 out; Separation: 13 mL 
               
               
                   
                   
                   
                   
                 Settling: Milky 
                 white 
                 12 mL white 
                 white 
               
               
                   
                   
                   
                   
                 film on walls at 
                 precipitate on 
                 precipitate on 
                 precipitate on 
               
               
                   
                   
                   
                   
                 0 min; Inversion: 4 
                 bottom. 
                 bottom. 
                 bottom; 
               
               
                   
                   
                   
                   
                   
                   
                   
                 Reconstitute: Did 
               
               
                   
                   
                   
                   
                   
                   
                   
                 not in 5 inversions 
               
               
                 10 
                 38J 
                 Atlox ™ 4838B 
                 7 
                 Bloom: 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
               
               
                   
                   
                 Atlas ™ G-5000 
                 10.5 
                 Acceptable; 
                 out; Separation: 10 mL 
                 out; Separation: 
                 out; Separation: 12 mL 
               
               
                   
                   
                   
                   
                 Settling: Grit on 
                 white 
                 11 mL white 
                 white 
               
               
                   
                   
                   
                   
                 walls at 0 min; 
                 precipitate on 
                 precipitate on 
                 precipitate on 
               
               
                   
                   
                   
                   
                 Inversion: 5 
                 bottom, white film 
                 bottom, white film 
                 bottom; 
               
               
                   
                   
                   
                   
                   
                 on walls. 
                 on walls 
                 Reconstitute: Did 
               
               
                   
                   
                   
                   
                   
                   
                   
                 not in 5 inversions 
               
               
                 11 
                 38K 
                 Brij ® S20 
                 17.5 
                 Bloom: None, 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
               
               
                   
                   
                   
                   
                 Unacceptable; Settling: 
                 out; Separation: 5 mL 
                 out; Separation: 5 mL 
                 out; Separation: 
               
               
                   
                   
                   
                   
                 Settled 
                 white 
                 white 
                 5.5 mL white 
               
               
                   
                   
                   
                   
                 on bottom at 0 min + 
                 precipitate on 
                 precipitate on 
                 precipitate on 
               
               
                   
                   
                   
                   
                 grit; 
                 bottom. 
                 bottom. 
                 bottom; 
               
               
                   
                   
                   
                   
                 Inversion: 5, grit 
                   
                   
                 Reconstitute: Did 
               
               
                   
                   
                   
                   
                 remains. 
                   
                   
                 not in 5 inversions 
               
               
                 12 
                 38L 
                 Atlox ™ 4838B 
                 7 
                 Bloom: None, 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
               
               
                   
                   
                 Brij ® S20 
                 10.5 
                 Unacceptable; 
                 out; Separation: 5 mL 
                 out; Separation: 5 mL 
                 out; Separation: 6 mL 
               
               
                   
                   
                   
                   
                 Settling: Settled 
                 white 
                 white 
                 white 
               
               
                   
                   
                   
                   
                 on bottom at 0 min + 
                 precipitate on 
                 precipitate on 
                 precipitate on 
               
               
                   
                   
                   
                   
                 grit; 
                 bottom. 
                 bottom. 
                 bottom; 
               
               
                   
                   
                   
                   
                 Inversion: 5, grit 
                   
                   
                 Reconstitute: Did 
               
               
                   
                   
                   
                   
                 gone. 
                   
                   
                 not in 5 inversions 
               
               
                 13 
                 38M 
                 Tween ® 80 
                 17.5 
                 Bloom: None, 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
               
               
                   
                   
                   
                   
                 Unacceptable; Settling: 
                 out; Separation: 9 mL 
                 out; Separation: 
                 out; Separation: 11 mL 
               
               
                   
                   
                   
                   
                 Settled 
                 white 
                 11 mL white 
                 white 
               
               
                   
                   
                   
                   
                 on bottom at 0 min; 
                 precipitate on 
                 precipitate on 
                 precipitate on 
               
               
                   
                   
                   
                   
                 Inversion: 2 
                 bottom. 
                 bottom. 
                 bottom; 
               
               
                   
                   
                   
                   
                   
                   
                   
                 Reconstitute: Did 
               
               
                   
                   
                   
                   
                   
                   
                   
                 not in 5 inversions 
               
               
                 14 
                 38N 
                 Atlox ™ 4838B 
                 7 
                 Bloom: 
                 Emulsion: 
                 Emulsion: 
                 Emulsion: 
               
               
                   
                   
                 Tween ® 80 
                 10.5 
                 Acceptable; 
                 Acceptable; 
                 Acceptable; 
                 Acceptable; 
               
               
                   
                   
                   
                   
                 Settling: None at 
                 Separation: 3 mL 
                 Separation: 4 mL 
                 Separation: 5 mL 
               
               
                   
                   
                   
                   
                 0 min; Inversion: 1 
                 yellow layer on 
                 yellow layer on 
                 yellow layer on 
               
               
                   
                   
                   
                   
                   
                 bottom. 
                 bottom. 
                 bottom; 
               
               
                   
                   
                   
                   
                   
                   
                   
                 Reconstitute: 1 
               
               
                   
                   
                   
                   
                   
                   
                   
                 inversion 
               
               
                 15 
                 38O 
                 Calsogen ® EH 
                 7 
                 Bloom: Very 
                 Emulsion: 
                 Emulsion: 
                 Emulsion: 
               
               
                   
                   
                 Tween ® 80 
                 10.5 
                 good; Settling: 
                 Acceptable; 
                 Acceptable; 
                 Acceptable; 
               
               
                   
                   
                   
                   
                 None at 0 min; 
                 Separation: 4 mL 
                 Separation: 4 mL 
                 Separation: 4 mL 
               
               
                   
                   
                   
                   
                 Inversion: 1 
                 yellow layer on 
                 yellow layer on 
                 yellow layer on 
               
               
                   
                   
                   
                   
                   
                 bottom. 
                 bottom. 
                 bottom; 
               
               
                   
                   
                   
                   
                   
                   
                   
                 Reconstitute: 1 
               
               
                   
                   
                   
                   
                   
                   
                   
                 inversion 
               
               
                 16 
                 38P 
                 Tergitol ™ XD 
                 17.5 
                 Bloom: None, 
                 Emulsion: Poor; 
                 Emulsion: None; 
                 Emulsion: None 
               
               
                   
                   
                   
                   
                 roping, 
                 Separation: 9 mL 
                 Separation: 9 mL 
                 Separation: 9 mL 
               
               
                   
                   
                   
                   
                 Unacceptable; Settling: 
                 precipitate on 
                 precipitate + 2 mL 
                 precipitate + 3 mL 
               
               
                   
                   
                   
                   
                 Settled 
                 bottom. 
                 white layer above 
                 white layer above 
               
               
                   
                   
                   
                   
                 on bottom at 0 min; 
                   
                 it, both on bottom. 
                 it, both on bottom; 
               
               
                   
                   
                   
                   
                 Inversion: 5 
                   
                   
                 Reconstitute: Did 
               
               
                   
                   
                   
                   
                   
                   
                   
                 not in 5 inversions 
               
               
                 17 
                 38Q 
                 Calsogen ® EH 
                 7 
                 Bloom: Poor, 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
                 Emulsion: Thinned 
               
               
                   
                   
                 Tergitol ™ XD 
                 10.5 
                 Unacceptable; Settling: 
                 out; Separation: 5 mL 
                 out; Separation: 6 mL 
                 out; Separation: 
               
               
                   
                   
                   
                   
                 Settled 
                 precipitate on 
                 precipitate on 
                 7.5 mL precipitate 
               
               
                   
                   
                   
                   
                 on bottom at 0 min; 
                 bottom. 
                 bottom. 
                 on bottom; 
               
               
                   
                   
                   
                   
                 Inversion: 2 
                   
                   
                 Reconstitute: Did 
               
               
                   
                   
                   
                   
                   
                   
                   
                 not in 5 inversions 
               
               
                   
               
             
          
         
       
     
         [0050]    In Table 1, the experimental properties of the emulsion are defined as follows: (a) “bloom” refers to the spontaneous visible dispersion and emulsification of the Emulsifiable Concentrate phase, when added into the water phase; (b) “inversion” refers to the number of times the cylinder was inverted to achieve an emulsion; (c) “separation” refers to the reversion of immiscible liquids into separate phases; (d) “thinned out” refers to the emulsion appearing thinner; (e) “reconstitute” refers to the number of inversion necessary to form an emulsion; (f) “settling” refers to the component which was deposited on the bottom of the cylinder; (g) “milky film” refers to a thick white film; and (h) “grit” refers to fine particulate-looking appearance. 
         [0051]    Applicants unexpectedly discovered that the Formulation of Example 1 had superior stability, even after 24 hours. The Formulation of Example 1 quickly produced an emulsion. Throughout the observation period, the Formulation of Example 1 remained uniform and thick without separating. All of the other emulsion systems failed to produce satisfactory results. Achieving excellent stability after 24 hours is extremely rare in emulsion concentrate dilutions. 
         [0052]    The unpredictability of the emulsion systems can be seen by comparing the stability of the Formulation of Example 1 with Formulation 2. Both formulations contained Calsogen® EH and the only difference between the formulations was that the Formulation of Example 1 contained Surfonic® CO 36 and Formulation 2 contained Emulsogen® EL 360. Surfonic® CO 36 and Emulsogen® EL 360 are both castor oil ethoxylates (36 EO), however, the Formulation of Example 1 had superior emulsion stability after 24 hours when compared to Formulation 2. Therefore, these formulations illustrate how emulsion systems with very similar chemistries may have different stability properties that cannot be predicted by one skilled in the art. 
         [0053]    Further details regarding the alternative emulsion systems can be found below in “Table 2: Components in Emulsifying Systems.” 
         [0000]    
       
         
               
             
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Components in Emulsifying Systems 
               
             
          
           
               
                 Trade Name 
                 Chemistry 
               
               
                   
               
               
                 Calsogen ® EH 
                 iso-C12 alkylbenzene sulphonate-calcium salt 
               
               
                 Emulsogen ® EL 360 
                 Castor oil ethoxylate (36 EO) 
               
               
                 Atlox ™ 4838B 
                 Calcium alkylaryl sulphonate 
               
               
                 Surfonic ® CO 36 
                 Castor oil ethoxylate (36 EO) 
               
               
                 Atlas ™ G-1086 
                 Polyoxyethylene (40) sorbitol hexaoleate 
               
               
                 Synperonic ® A20 
                 Polyoxyethylene (20) C12-C15 alcohol 
               
               
                 Atlas ™ G-5000 
                 Polyalklene oxide block (EO/PO) copolymer 
               
               
                 Brij ® S20 
                 Polyoxyethylene (20) oleyl ether 
               
               
                 Tween ® 20 
                 Polyoxyethylene (20) sorbitan monooleate 
               
               
                 Tergitol ™ XD 
                 Alkyl EO/PO copolymer