Abstract:
A synergistic antimicrobial composition containing flumetsulam and an isothiazolone biocide chosen from among 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one and N-n-butyl-1,2-benzisothiazolin-3-one. A synergistic antimicrobial composition containing diclosulam and an isothiazolone biocide chosen from 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and 2-n-octyl-4-isothiazolin-3-one.

Description:
[0001]    This invention relates to combinations of biocides, the combinations having greater activity than would be observed for the individual antimicrobial compounds. 
         [0002]    Use of combinations of at least two antimicrobial compounds can broaden potential markets, reduce use concentrations and costs, and reduce waste. In some cases, commercial antimicrobial compounds cannot provide effective control of microorganisms, even at high use concentrations, due to weak activity against certain types of microorganisms, e.g., those resistant to some antimicrobial compounds. Combinations of different antimicrobial compounds are sometimes used to provide overall control of microorganisms in a particular end use environment. For example, U.S. Pat. No. 5,591,760 discloses a combination of 3-iodo-2-propynyl-butylcarbamate (IPBC) and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT), but this reference does not suggest any of the combinations claimed herein. Moreover, there is a need for additional combinations of antimicrobial compounds having enhanced activity against various strains of microorganisms to provide effective control of the microorganisms, especially in dry film coatings. The problem addressed by this invention is to provide such additional combinations of antimicrobial compounds. 
       STATEMENT OF THE INVENTION 
       [0003]    The present invention is directed to a synergistic antimicrobial composition comprising: (a) flumetsulam; and (b) an isothiazolone biocide selected from the group consisting of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one (OIT) and N-n-butyl-1,2-benzisothiazolin-3-one (BBIT); wherein a weight ratio of flumetsulam to 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one is from 15:1 to 1:15, a weight ratio of flumetsulam to 2-n-octyl-4-isothiazolin-3-one is from 7:1 to 1:5 and a weight ratio of flumetsulam to N-n-butyl-1,2-benzisothiazolin-3-one is from 15:1 to 1:15. 
         [0004]    The present invention is further directed to a synergistic antimicrobial composition comprising: (a) diclosulam; and (b) an isothiazolone biocide selected from the group consisting of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and 2-n-octyl-4-isothiazolin-3-one; wherein a weight ratio of diclosulam to 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one is from 7:1 to 1:3 and a weight ratio of diclosulam to 2-n-octyl-4-isothiazolin-3-one is from 7:1 to 1:1.5 or 1:3 to 1:7. 
     
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0005]    As used herein, the following terms have the designated definitions, unless the context clearly indicates otherwise. Fluometsulam is N-(2,6-difluorophenyl)-5-methyl[1,2,4]triazolo[1,5-a]pyrimidine-2-sulfonamide. Diclosulam is N-(2,6-dichlorophenyl)-5-ethoxy-7-fluoro[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide. The term “antimicrobial compound” refers to a compound capable of inhibiting the growth of or controlling the growth of microorganisms; antimicrobial compounds include bactericides, bacteristats, fungicides, fungistats, algaecides and algistats, depending on the dose level applied, system conditions and the level of microbial control desired. The term “microorganism” includes, for example, fungi (such as yeast and mold), bacteria and algae. The following abbreviations are used throughout the specification: ppm=parts per million by weight (weight/weight), mL=milliliter, ATCC=American Type Culture Collection, and MIC=minimum inhibitory concentration. Unless otherwise specified, temperatures are in degrees centigrade (° C.), and references to percentages are by weight (wt %). Percentages of antimicrobial compounds in the composition of this invention are based on the total weight of active ingredients in the composition, i.e., the antimicrobial compounds themselves, exclusive of any amounts of solvents, carriers, dispersants, stabilizers or other materials which may be present. 
         [0006]    Preferably, when the antimicrobial composition comprises flumetsulam and DCOIT, a weight ratio of flumetsulam to DCOIT is from 15:1 to 1:12, preferably from 12:1 to 1:12, preferably from 12:1 to 1:10; preferably from 10:1 to 1:10. 
         [0007]    Preferably, when the antimicrobial composition comprises flumetsulam and OIT, a weight ratio of flumetsulam to OIT is from 7:1 to 1:4; preferably from 6:1 to 1:4; preferably from 7:1 to 1:3; preferably from 6:1 to 1:3; preferably from 5:1 to 1:3. 
         [0008]    Preferably, when the antimicrobial composition comprises flumetsulam and BBIT, a weight ratio of a weight ratio of flumetsulam to BBIT is from 15:1 to 1:12; preferably from 12:1 to 1:12; preferably from 12:1 to 1:10; preferably from 10:1 to 1:10. 
         [0009]    Preferably, when the antimicrobial composition comprises diclosulam and DCOIT, a weight ratio of diclosulam to DCOIT is from 6:1 to 1:3; preferably from 5:1 to 1:3; preferably from 6:1 to 1:2; preferably from 5:1 to 1:2. 
         [0010]    Preferably, when the antimicrobial composition comprises diclosulam and OIT, a weight ratio of diclosulam to OIT is from 7:1 to 1:1.5 or 1:3 to 1:6; preferably from 6:1 to 1:1.5 or 1:3 to 1:6; preferably from 5:1 to 1:1.5 or 1:3 to 1:5; preferably from 7:1 to 1:1 or 1:3 to 1:5; preferably from 6:1 to 1:1 or 1:3 to 1:5; preferably from 5:1 to 1:1 or 1:3 to 1:5; preferably from 5:1 to 1:1; preferably from 5:1 to 2:1. 
         [0011]    Preferably, flumetsulam in combination with DCOIT and/or OIT is used to inhibit growth of fungi in an aqueous medium. Preferably, the ratio of flumetsulam to DCOIT is from 15:1 to 1:4; preferably from 12:1 to 1:4; preferably from 12:1 to 1:3; preferably from 10:1 to 1:3; preferably from 10:1 to 1:2. Preferably, the ratio of flumetsulam to OIT is from from 7:1 to 1:4; preferably from 6:1 to 1:4; preferably from 7:1 to 1:3; preferably from 6:1 to 1:3; preferably from 5:1 to 1:3. 
         [0012]    The antimicrobial compositions described above may contain more than one of the listed isothiazolone biocides and/or other biocides. 
         [0013]    Preferably, the antimicrobial combinations of this invention are incorporated into liquid compositions, especially dispersions of polymers in aqueous media. The biocide combinations are particularly useful in preservation of building materials, e.g., adhesives, caulk, joint compound, sealant, wallboard, etc), paints, coatings, polymers, plastics, synthetic and natural rubber, paper products, fiberglass sheets, insulation, exterior insulating finishing systems, roofing and flooring felts, building plasters, wood products and wood-plastic composites. Preferably, the antimicrobial compositions are latex paints or other liquid coating compositions containing the biocide combinations disclosed herein. The biocide combinations are useful for preservation of the dry film coating resulting after application of a paint or other liquid coating composition. Preferably, the antimicrobial composition is an acrylic latex paint comprising one or more of the biocide combinations disclosed herein, or the dry film coating resulting from application of the paint to a surface. 
         [0014]    Typically, the amount of the biocide combinations of the present invention to control the growth of microorganisms is from 100 ppm to 10,000 ppm active ingredient. Preferably, the active ingredients of the composition are present in an amount of at least 300 ppm, preferably at least 500 ppm, preferably at least 600 ppm, preferably at least 700 ppm. Preferably, the active ingredients of the composition are present in an amount of no more than 8,000 ppm, preferably no more than 6,000 ppm, preferably no more than 5,000 ppm, preferably no more than 4,000 ppm, preferably no more than 3,000 ppm, preferably no more than 2500 ppm, preferably no more than 2,000 ppm, preferably no more than 1,800 ppm, preferably no more than 1,600 ppm. Concentrations mentioned above are in a liquid composition containing the biocide combinations; biocide levels in the dry film coating will be higher. 
         [0015]    The present invention also encompasses a method for preventing microbial growth in building materials, especially in dry film coatings, by incorporating any of the claimed biocide combinations into the materials. 
       EXAMPLES 
       [0016]    Sample preparation: A single or blend of biocides was post added into white acrylic latex paint free of biocides to give a maximum total active ingredient/s concentration tested. This paint was then diluted with a biocide free acrylic latex paint to give targeted concentrations for the testing. Depending on the type of biocide blends tested, the total biocides concentrations varies from 200 to 5000 ppm. After biocides addition or dilution, each sample was hand mixed for at least a minute until uniformity is achieved. Each of the paint samples as well as a control sample (containing no biocide) were used to prepare films on black plastic-vinyl chloride/acetate copolymer panels (LENETA, Mahwah, N.J.) using a 3 mil (0.0762 mm) bird bar applicator. The panels were thoroughly dried for at least 2 days avoiding direct exposure to sunlight. Square discs (0.5 inch; 1.27 cm 2 ) were cut out from each panel and were used as the substrate for fungal and algal efficacy tests. This sample size allowed for an agar border when the sample disc was placed into the well of the test plate. Each sample was tested in duplicate 
         [0017]    Test conditions: The appropriate media (BOLD&#39;S 3N for Chlorophytes, BG-11 for Cyanobacteria, and PDA for fungi) were used to support microbial growth. The test plates were maintained at room temp (25° C.-26° C.), in a cycled light-dark environment, for four weeks for algae. Plates for fungal challenge tests were maintained at 30C for four weeks. At the end of the incubation period the samples were scored for percent area covered by visible microbial growth. 
         [0018]    Algal Inoculum 
         [0000]    
       
         
               
               
               
               
               
             
           
               
                   
               
               
                   
                   
                   
                   
                 Medium 
               
               
                   
                   
                   
                   
                 for 
               
               
                 Organisms 
                 abbreviation 
                   
                 Type 
                 testing 
               
               
                   
               
             
             
               
                 
                   Gloeocapsa 
                 
                 Gs 
                 ATCC 29159 
                 Unicellular, 
                 BG-11 
               
               
                 sp. 
                   
                   
                 Colonial 
               
               
                   
                   
                   
                 Cyanobacteria 
               
               
                 
                   Oscillatoria 
                 
                 Os 
                 ATCC 29135 
                 Filamentous 
                 BG-11 
               
               
                 sp. 
                   
                   
                 Cyanobacteria 
               
               
                 
                   Nostoc 
                 
                 Nc 
                 CCAP 1453/29 
                 Unicellular, 
                 Bold 
               
               
                 
                   commune 
                 
                   
                   
                 Cenobial 
               
               
                   
                   
                   
                 Chlorophyte 
               
               
                 
                   Trentepohlia 
                 
                 Ta + To 
                 UTEX LB 429 + 
                 Filamentous 
                 Bold 
               
               
                   aurea  + 
                   
                 CCAP 483/4 
                 Chlorophyte 
               
               
                 
                   Trentepohlia 
                 
               
               
                 
                   odorata 
                 
               
               
                   Chlorella  sp. 
                 Cs + Ck 
                 ATCC 30582 + 
                 Unicellular 
                 Bold 
               
               
                 UTEX + 
                   
                 ATCC 11468 
                 Chlorophyte 
               
               
                 
                   Chlorella 
                 
               
               
                 
                   kessleri 
                 
               
               
                 
                   Calothrix 
                 
                 Cp 
                 UTEX LB 1952 
                 Filamentous 
                 Bold 
               
               
                 
                   parientina 
                 
                   
                   
                 Cyanobacteria 
               
               
                   
               
             
          
         
       
     
         [0019]    Fungal Inoculum 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                   
                   
                   
                 Medium for 
               
               
                   
                   
                   
                 Growth and 
               
               
                 Organisms 
                 abbreviation 
                 ATCC# 
                 Testing 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 
                   Aspergillus niger 
                 
                 An 
                 9642 
                 PDA 
               
               
                 
                   Penicillium funiculosum 
                 
                 Pf 
                 11797 
                 PDA 
               
               
                 
                   Cladosporium herbarum 
                 
                 Ch 
                 11281 
                 PDA 
               
               
                 
                   Aureobasidium pullulans 
                 
                 Ap 
                 9348 
                 PDA 
               
               
                 
                   Trichoderma viride 
                 
                 Tv 
                 32630 
                 PDA 
               
               
                 
                   Alternaria alternata 
                 
                 Aa 
                 20084 
                 PDA 
               
               
                   
               
             
          
         
       
     
         [0020]    Algal Efficacy Testing—Modified ASTM 5589 
         [0021]    ASTM 5589 is a standard accelerated test method for determining resistance of various coatings (including paints) to algal defacement. To accommodate for high-throughput screening, this method was scaled down from petri plates to 6-well plates. A single coupon was placed with a pair of sterile forceps at the center of the agar plug (on top) with the painted surface facing upwards. Algal inoculums were prepared by mixing equal concentrations (1×10 6  cfu/ml) and equal volumes (depending on number of samples to be inoculated) of like growing organisms. 
         [0022]    In Flumetsulam+various IT synergy study, three pool of mixed algae were prepared as the test inoculum,  Gloeocapsa  sp. and  Oscillatoria  sp. a mix of cyanobacteria grown on BG-11 media;  Chlorella  sp.,  Chlorella kessleri,  and  Nostoc commune  are unicellular chlorphytes that were mixed and grown on Bold media;  Trentepohlia aurea, Tretepohlia odorata,  and  Calotrix parientina  are filamentous algae that were mixed and grown on Bold media. 
         [0023]    In Diclosulam+various IT synergy study, only two pools of mixed algae were prepared;  Gloeocapsa  sp. and  Oscillatoria  sp. grown on BG-11 media and  Chlorella  sp.,  Chlorella kessleri, Nostoc commune, Trentepohlia aurea, Tretepohlia odorata,  and  Calotrix parientina  grown on Bold media 
         [0024]    Each well that contains a tested coupon was inoculated with 400 μl of organism mixture (1×10 6  cfu/ml) making sure that the whole surface (paint film as well as the agar surrounding it) was evenly covered. The plates were incubated at room temp (25° C.-26° C.) with cyclic exposure to light (OTT-Lite model #OTL4012P, 40 Watt, 26 KLumen) and dark phases, for a period of four weeks. The total area covered was evaluated at the end of each week according to percent area covered in 5% increments. 
       Fungal Efficacy Testing—Modified ASTM 5590 
       [0025]    ASTM 5590 is a standard accelerated test method for determining resistance of various coatings (including paints) to fungal defacement. To accommodate for high-throughput screening, this method was scaled down from petri plates to 6-well plates. To set up the test, an agar plug was placed at the bottom of each well of the sterile 6-well plate. A single coupon was placed with a pair of sterile forceps at the center of the agar plug (on top) with the painted surface facing upwards. Fungal inoculums were prepared by mixing equal concentrations (1×10 6  cfu/ml) and equal volumes (depending on number of samples to be tested) of like growing organisms. For Flumetsulam+various IT synergy study, three pools of mixed fungi were prepared as the test inoculum.  Cladosporium herbarum  was mixed with  Aureobasidium pullulans; Aspergillus niger  was mixed with  Penicillium funiculosum  and  Alternaria alternata  was mixed with  Trichoderma viride.  For Diclosulam+various IT synergy study, all above fungi were mixed as a single pool. Each well was inoculated with 400 μl of organism mixture (1×10 6  cfu/ml) making sure that the whole surface (paint film as well as the agar surrounding it) was evenly covered. The plates were incubated at 30° C. in presence of moisture, for a period of four weeks. The total percent area covered was evaluated and recorded at the end of each week after the 2 nd  week and recorded in increments of 5%. 
         [0026]    Synergy Index Calculation 
         [0027]    Synergy Index (SI) 
         [0028]    The SI is calculated based on F. C. Kull et. Al. method (Applied Microbiology, Vol. 9 (1961). In this study, SI was calculated based on the following formula with the minimum inhibitory concentration chosen based on the percent inhibitory exhibited by the individual biocide against each microorganisms tested. 
         [0000]    
       
      
       SI=Qa/QA+Qb/QB  
      
       
         
           
             Qa=the concentration of Biocide A in the blend 
             QA=The concentration of Biocide A as the only biocide 
             Qb=The concentration of Biocide B in the blend 
             QB=The concentration of Biocide B as the only biocide 
           
         
       
     
         [0033]    SI value of &lt;1 in the formula indicates a synergism of the blended biocides exists. 
         [0034]    Note: If any of the active with maximum concentration tested did not exhibit some inhibition, this maximum concentration is used to calculate the estimated SI and a sign of less than (&lt;) is included to take into account that higher concentration of the active is needed to achieve the targeted inhibition 
         [0035]    NE=no end point at the concentration tested that will meet the percent inhibition criteria set in each SI calculation 
         [0036]    Flumetsulam: DCOIT Synergy Study 
         [0000]    
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 AaTv 
                 AnPf 
                 ApCh 
                 Cp + To + Ta 
                 Cs + Ck + Nc 
                 Gs + Os 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 1Flumet:1DCOIT 
                   
                   
                   
                   
                   
                   
               
               
                 Total conc, ppm 
                 1150 
                 575 
                 575 
                 575 
                 575 
                 575 
               
               
                 % inhibition 
                 100 
                 95 
                 100 
                 100 
                 100 
                 100 
               
               
                 SI 
                 &lt;1.16 
                 &lt;0.58 
                 0.6 
                 2.7 
                 0.4 
                 2.1 
               
               
                 2Flumet:1DCOIT 
               
               
                 Total conc, ppm 
                 2588 
                 862.5 
                 862.5 
                 431.25 
                 431.25 
                 431.25 
               
               
                 % inhibition 
                 100.0 
                 90 
                 100 
                 95 
                 100 
                 100 
               
               
                 SI 
                 &lt;1.99 
                 &lt;0.66 
                 0.7 
                 1.7 
                 0.3 
                 1.1 
               
               
                 3Flumet:1DCOIT 
               
               
                 Total conc, ppm 
                 1000 
                 1000 
                 1000 
                 1000 
                 1000 
                 1000 
               
               
                 % inhibition 
                 100 
                 100 
                 100 
                 100 
                 95 
                 1000 
               
               
                 SI 
                 &lt;0.65 
                 &lt;0.65 
                 0.7 
                 3.5 
                 0.7 
                 2.0 
               
               
                 5Flumet:1DCOIT 
               
               
                 Total conc, ppm 
                 750 
                 1500 
                 750 
                 750 
                 750 
                 750 
               
               
                 % inhibition 
                 80 
                 90 
                 95 
                 100 
                 100 
                 100 
               
               
                 SI 
                 &lt;0.40 
                 &lt;0.7 
                 0.4 
                 2.3 
                 0.5 
                 1.1 
               
               
                 10Flumet:1DCOIT 
               
               
                 Total conc, ppm 
                 1650 
                 1650 
                 825 
                 825 
                 1650 
                 825 
               
               
                 % inhibition 
                 100 
                 90 
                 100 
                 100 
                 100 
                 100 
               
               
                 SI 
                 &lt;0.69 
                 &lt;0.69 
                 0.3 
                 2.2 
                 1.0 
                 0.8 
               
               
                 1Flumet:2DCOIT 
               
               
                 Total conc, ppm 
                 888 
                 444 
                 444 
                 444 
                 444 
                 444 
               
               
                 % inhibition 
                 90 
                 100 
                 100 
                 95 
                 100 
                 100 
               
               
                 SI 
                 &lt;1.11 
                 &lt;0.56 
                 0.6 
                 2.4 
                 0.3 
                 2.1 
               
               
                 1Flumet:5DCOIT 
               
               
                 Total conc, ppm 
                 1380 
                 690 
                 690 
                 690 
                 690 
                 690 
               
               
                 % inhibition 
                 100 
                 100 
                 100 
                 100 
                 100 
                 100 
               
               
                 SI 
                 &lt;2.1 
                 &lt;1.0 
                 1.0 
                 4.3 
                 0.6 
                 4.0 
               
               
                 1Flumet:10DCOIT 
               
               
                 Total conc, ppm 
                 632.5 
                 632.5 
                 632.5 
                 632.5 
                 632.5 
                 632.5 
               
               
                 % inhibition 
                 90 
                 100 
                 100 
                 100 
                 100 
                 100 
               
               
                 SI 
                 &lt;1.01 
                 &lt;1.0 
                 1.0 
                 4.1 
                 0.5 
                 4.0 
               
               
                 Flumetsulam 
               
               
                 Total conc, ppm 
                 3500 
                 3500 
                 3500 
                 437.5 
                 1750 
                 2625 
               
               
                 % inhibition 
                 0 
                 0 
                 90 
                 95 
                 100 
                 100 
               
               
                 DCOIT 
               
               
                 Total conc, ppm 
                 575 
                 575 
                 862.5 
                 143.75 
                 1150 
                 143.75 
               
               
                 % inhibition 
                 85 
                 100 
                 100 
                 100 
                 100 
                 100 
               
               
                   
               
             
          
         
       
     
         [0037]    Flumetsulam: OTT Synergy Study 
         [0000]    
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 AaTv 
                 AnPf 
                 ApCh 
                 Cp + To + Ta 
                 Cs + Ck + Nc 
                 Gs + Os 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 1Flumet:1OIT 
                   
                   
                   
                   
                   
                   
               
               
                 Total conc, ppm 
                 750 
                 750 
                 750 
                 750 
                 750 
                 750 
               
               
                 % inhibition 
                 100 
                 100 
                 100 
                 100 
                 100 
                 100 
               
               
                 SI 
                 &lt;0.50 
                 0.9 
                 &lt;0.5 
                 1.7 
                 1.0 
                 1.7 
               
               
                 2Flumet:1OIT 
               
               
                 Total conc, ppm 
                 750 
                 750 
                 750 
                 750 
                 750 
                 750 
               
               
                 % inhibition 
                 100.0 
                 100 
                 95 
                 100 
                 100 
                 90 
               
               
                 SI 
                 &lt;0.4 
                 0.7 
                 &lt;0.4 
                 1.7 
                 0.7 
                 1.7 
               
               
                 3Flumet:1OIT 
               
               
                 Total conc, ppm 
                 750 
                 750 
                 1500 
                 750 
                 750 
                 750 
               
               
                 % inhibition 
                 100 
                 95 
                 95 
                 95 
                 100 
                 100 
               
               
                 SI 
                 &lt;0.40 
                 0.6 
                 &lt;0.70 
                 1.7 
                 0.6 
                 7.0 
               
               
                 5Flumet:1OIT 
               
               
                 Total conc, ppm 
                 1800 
                 687.5 
                 1800 
                 687.5 
                 687.5 
                 687.5 
               
               
                 % inhibition 
                 100 
                 95 
                 100 
                 90 
                 100 
                 95 
               
               
                 SI 
                 &lt;0.80 
                 0.3 
                 &lt;0.80 
                 1.6 
                 0.4 
                 1.6 
               
               
                 1Flumet:3OIT 
               
               
                 Total conc, ppm 
                 600 
                 1200 
                 600 
                 600 
                 600 
                 600 
               
               
                 % inhibition 
                 100 
                 100 
                 90 
                 100 
                 100 
                 95 
               
               
                 SI 
                 &lt;0.5 
                 2.1 
                 &lt;0.50 
                 1.3 
                 1.1 
                 1.3 
               
               
                 1Flumet:2OIT 
               
               
                 Total conc, ppm 
                 675 
                 1350 
                 675 
                 675 
                 675 
                 675 
               
               
                 % inhibition 
                 100 
                 100 
                 100 
                 100 
                 100 
                 100 
               
               
                 SI 
                 &lt;0.60 
                 2.1 
                 &lt;0.60 
                 1.5 
                 1.1 
                 1.5 
               
               
                 Flumetsulam 
               
               
                 Total conc, ppm 
                 3500 
                 3500 
                 3500 
                 437.5 
                 2625 
                 437.5 
               
               
                 % inhibition 
                 0 
                 65 
                 0 
                 60 
                 65 
                 90 
               
               
                 OIT 
               
               
                 Total conc, ppm 
                 900 
                 450 
                 900 
                 450 
                 450 
                 450 
               
               
                 % inhibition 
                 100 
                 100 
                 80 
                 100 
                 100 
                 100 
               
               
                   
               
             
          
         
       
     
         [0038]    Flumetsulam: BBIT Synergy Study 
         [0000]    
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 AaTv 
                 AnPf 
                 ApCh 
                 Cp + To + Ta 
                 Cs + Ck + Nc 
                 Gs + Os 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 1Flumet:1BBIT 
                   
                   
                   
                   
                   
                   
               
               
                 Total conc, ppm 
                 NE 
                 575 
                 575 
                 NE 
                 1150 
                 575 
               
               
                 % inhibition 
                   
                 60 
                 80 
                   
                 80 
                 100 
               
               
                 SI 
                   
                 &lt;0.33 
                 &lt;0.58 
                   
                 &lt;0.66 
                 &lt;0.33 
               
               
                 2Flumet:1BBIT 
               
               
                 Total conc, ppm 
                 NE 
                 431 
                 1725 
                 NE 
                 1725 
                 1725 
               
               
                 % inhibition 
                   
                 80 
                 60 
                   
                 80 
                 100 
               
               
                 SI 
                   
                 &lt;0.21 
                 &lt;1.32 
                   
                 &lt;0.83 
                 &lt;0.83 
               
               
                 3Flumet:1BBIT 
               
               
                 Total conc, ppm 
                 NE 
                 1000 
                 NE 
                 NE 
                 1000 
                 3000 
               
               
                 % inhibition 
                   
                 80 
                   
                   
                 60 
                 80 
               
               
                 SI 
                   
                 &lt;0.43 
                   
                   
                 &lt;0.43 
                 &lt;1.30 
               
               
                 5Flumet:1BBIT 
               
               
                 Total conc, ppm 
                 NE 
                 1500 
                 NE 
                 3000 
                 3000 
                 3000 
               
               
                 % inhibition 
                   
                 80 
                   
                 60 
                 60 
                 60 
               
               
                 SI 
                   
                 &lt;0.57 
                   
                 1.2 
                 &lt;1.14 
                 &lt;1.15 
               
               
                 10Flumet:1BBIT 
               
               
                 Total conc, ppm 
                 NE 
                 825 
                 NE 
                 2475 
                 1650 
                 825 
               
               
                 % inhibition 
                   
                 80 
                   
                 100 
                 80 
                 100 
               
               
                 SI 
                   
                 &lt;0.28 
                   
                 &lt;0.84 
                 &lt;0.56 
                 &lt;0.28 
               
               
                 1Flumet:1.8BBIT 
               
               
                 Total conc, ppm 
                 NE 
                 887.5 
                 NE 
                 NE 
                 887.5 
                 887.5 
               
               
                 % inhibition 
                   
                 80 
                   
                   
                 60 
                 60 
               
               
                 SI 
                   
                 &lt;0.59 
                   
                   
                 &lt;0.59 
                 &lt;0.59 
               
               
                 1Flumet:5 BBIT 
               
               
                 Total conc, ppm 
                 NE 
                 1035 
                 NE 
                 NE 
                 690 
                 690 
               
               
                 % inhibition 
                   
                 80 
                   
                   
                 100 
                 60 
               
               
                 SI 
                   
                 &lt;0.8 
                   
                   
                 &lt;0.53 
                 &lt;0.53 
               
               
                 1Flumet:10 BBIT 
               
               
                 Total conc, ppm 
                 NE 
                 949 
                 NE 
                 NE 
                 949 
                 632.5 
               
               
                 % inhibition 
                   
                 80 
                   
                   
                 80 
                 80 
               
               
                 SI 
                   
                 &lt;0.77 
                   
                   
                 &lt;0.77 
                 &lt;0.52 
               
               
                 Flumetsulam 
               
               
                 Total conc, ppm 
                 3500 
                 3500 
                 3500 
                 3500 
                 3500 
                 3500 
               
               
                 % inhibition 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 BBIT 
               
               
                 Total conc, ppm 
                 1150 
                 1150 
                 575 
                 1150 
                 1150 
                 1150 
               
               
                 % inhibition 
                 0 
                 0 
                 80 
                 0 
                 0 
                 0 
               
               
                   
               
             
          
         
       
     
         [0039]    Synergy Study of Diclosulam and DCOIT 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                   
                 Aa + Tv + An + 
                 Cp + To + Ta + 
                   
               
               
                 Ratios 
                 Pf + Ap + Ch 
                 Cs + Ck + Nc 
                 Gs + Os 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 1Diclosulam:1DCOIT 
                   
                   
                   
               
               
                 Total conc, ppm 
                 575 
                 575 
                 575 
               
               
                 % inhibition 
                 85 
                 100 
                 100 
               
               
                 SI 
                 0.5 
                 1.1 
                 1.1 
               
               
                 Dicolosulam:2DCOIT 
               
               
                 Total conc, ppm 
                 887.5 
                 443.75 
                 443.75 
               
               
                 % inhibition 
                 100 
                 100 
                 100 
               
               
                 SI 
                 1.0 
                 0.8 
                 0.8 
               
               
                 1Diclosulam:5DCOIT 
               
               
                 Total conc, ppm 
                 690 
                 690 
                 690 
               
               
                 % inhibition 
                 95 
                 100 
                 100 
               
               
                 SI 
                 1.0 
                 1.1 
                 1.1 
               
               
                 1Diclosulam:10DCOIT 
               
               
                 Total conc, ppm 
                 632.5 
                 632.5 
                 632.5 
               
               
                 % inhibition 
                 95 
                 100 
                 100 
               
               
                 SI 
                 0.9 
                 1.0 
                 1.0 
               
               
                 2Diclosulam:1DCOIT 
               
               
                 Total conc, ppm 
                 862.5 
                 443.75 
                 443.75 
               
               
                 % inhibition 
                 87.5 
                 100 
                 100 
               
               
                 SI 
                 0.6 
                 0.9 
                 0.9 
               
               
                 5Diclosulam:1DCOIT 
               
               
                 Total conc, ppm 
                 1500 
                 750 
                 750 
               
               
                 % inhibition 
                 85 
                 100 
                 100 
               
               
                 SI 
                 0.8 
                 1.6 
                 1.6 
               
               
                 10Diclosulam:1DCOIT 
               
               
                 Total conc, ppm 
                 3300 
                 825 
                 825 
               
               
                 % inhibition 
                 90 
                 100 
                 100 
               
               
                 SI 
                 1.3 
                 1.8 
                 1.8 
               
               
                 Diclosulam 
               
               
                 Total conc, ppm 
                 3500 
                 437.5 
                 437.5 
               
               
                 % inhibition 
                 40 
                 100 
                 100 
               
               
                 DCOIT 
               
               
                 Total conc, ppm 
                 625 
                 625 
                 625 
               
               
                 % inhibition 
                 80 
                 100 
                 100 
               
               
                   
               
             
          
         
       
     
         [0040]    Synergy Study of Diclosulam+OIT 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                   
                 Aa + Tv + 
                 Cp + To + 
                   
               
               
                 Ratios 
                 An + Pf + Ap + Ch 
                 Ta + Cs + Ck + Nc 
                 Gs + Os 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 1Diclosulam:1OIT 
                   
                   
                   
               
               
                 Total conc, ppm 
                 750 
                 2250 
                 750 
               
               
                 % inhibition 
                 100 
                 100 
                 100 
               
               
                 SI 
                 &lt;0.9 
                 3.8 
                 1.3 
               
               
                 2Dicolosulam:1OIT 
               
               
                 Total conc, ppm 
                 750 
                 2250 
                 1500 
               
               
                 % inhibition 
                 80 
                 100 
                 100 
               
               
                 SI 
                 &lt;0.7 
                 4.3 
                 2.8 
               
               
                 3Diclosulam:1OIT 
               
               
                 Total conc, ppm 
                 750 
                 2250 
                 750 
               
               
                 % inhibition 
                 100 
                 100 
                 100 
               
               
                 SI 
                 &lt;0.6 
                 4.5 
                 1.5 
               
               
                 5Diclosulam:1OIT 
               
               
                 Total conc, ppm 
                 687.5 
                 2700 
                 687.5 
               
               
                 % inhibition 
                 100 
                 80 
                 100 
               
               
                 SI 
                 &lt;0.3 
                 5.6 
                 1.5 
               
               
                 1Diclosulam:3OIT 
               
               
                 Total conc, ppm 
                 600 
                 600 
                 600 
               
               
                 % inhibition 
                 100 
                 100 
                 100 
               
               
                 SI 
                 &lt;1.0 
                 1.0 
                 0.8 
               
               
                 1Diclosulam:2OIT 
               
               
                 Total conc, ppm 
                 675 
                 675 
                 675 
               
               
                 % inhibition 
                 100 
                 100 
                 100 
               
               
                 SI 
                 &lt;1.1 
                 1.0 
                 1.0 
               
               
                 1Diclosulam:5OIT 
               
               
                 Total conc, ppm 
                 540 
                 1080 
                 540 
               
               
                 % inhibition 
                 100 
                 100 
                 100 
               
               
                 SI 
                 1.0 
                 1.4 
                 0.7 
               
               
                 1Diclosulam:10OIT 
               
               
                 Total conc, ppm 
                 990 
                 990 
                 990 
               
               
                 % inhibition 
                 100 
                 100 
                 100 
               
               
                 SI 
                 &lt;2.0 
                 1.2 
                 1.2 
               
               
                 Diclosulam 
               
               
                 Total conc, ppm 
                 3500 
                 437.5 
                 437.5 
               
               
                 % inhibition 
                 0 
                 100 
                 100 
               
               
                 OIT 
               
               
                 Total conc, ppm 
                 450 
                 900 
                 900 
               
               
                 % inhibition 
                 100 
                 100 
                 100