US20160219882A1 - Microbicidal composition - Google Patents

Microbicidal composition Download PDF

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Publication number
US20160219882A1
US20160219882A1 US15/026,132 US201415026132A US2016219882A1 US 20160219882 A1 US20160219882 A1 US 20160219882A1 US 201415026132 A US201415026132 A US 201415026132A US 2016219882 A1 US2016219882 A1 US 2016219882A1
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United States
Prior art keywords
surf
nonionic surfactant
atcc
linear alkyl
alkyl groups
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Abandoned
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US15/026,132
Inventor
Usha Gandhi
Christine Mcinnis
Kiran Pareek
Paul O. Schook
Nigel G. Watson
Terry Michael Williams
Bei Yin
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Dow Global Technologies LLC
Rohm and Haas Co
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Dow Global Technologies LLC
Rohm and Haas Co
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Priority to US15/026,132 priority Critical patent/US20160219882A1/en
Publication of US20160219882A1 publication Critical patent/US20160219882A1/en
Abandoned legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
    • A01N33/18—Nitro compounds
    • A01N33/20—Nitro compounds containing oxygen or sulfur attached to the carbon skeleton containing the nitro group
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles

Definitions

  • This invention relates to microbicidal compositions containing cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride (CTAC), 4,4-dimethyloxazolidine (DMO) or tris(hydroxymethyl)nitromethane (Tris Nitro) and a surfactant.
  • CAC cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride
  • DMO 4,4-dimethyloxazolidine
  • Tris Nitro tris(hydroxymethyl)nitromethane
  • a composition containing 5-chloro-2-methylisothiazolin-3-one, 2-methylisothiazolin-3-one and a nonionic dispersant is disclosed in U.S. Pat. No. 4,295,932.
  • the composition contains a 3:1 mixture of 5-chloro-2-methylisothiazolin-3-one and 2-methylisothiazolin-3-one, and a copolymer of ethylene oxide and propylene oxide which appears to have the same composition as PLURONIC L61 or TERGITOL L61 dispersant.
  • PLURONIC L61 or TERGITOL L61 dispersant there is a need for combinations of microbicides having synergistic activity against various strains of microorganisms to provide effective control of the microorganisms.
  • the problem addressed by this invention is to provide such synergistic combinations of microbicides.
  • the present invention is further directed to a synergistic microbicidal composition
  • a synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
  • the present invention is further directed to a synergistic microbicidal composition
  • a synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
  • the present invention is further directed to a synergistic microbicidal composition
  • a synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
  • the present invention is further directed to a synergistic microbicidal composition
  • a synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
  • the present invention is further directed to a synergistic microbicidal composition
  • a synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
  • the present invention is further directed to a synergistic microbicidal composition
  • a synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
  • the present invention is further directed to methods for inhibiting the growth of microorganisms in aqueous media by adding to an aqueous medium a nonionic surfactant as described herein and cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride, 4,4-dimethyloxazolidne or tris(hydroxymethyl)nitromethane in the ratios described herein.
  • CAC CRC
  • DMO 4,4-dimethyloxazolidine
  • Tris Nitro is tris(hydroxymethyl)nitromethane, CAS No. 126-11-4.
  • microbicide refers to a compound capable of inhibiting the growth of or controlling the growth of microorganisms; microbicides include bactericides, fungicides and algaecides.
  • microorganism includes, for example, fungi (such as yeast and mold), bacteria and algae.
  • fungi such as yeast and mold
  • mL milliliter.
  • temperatures are in degrees centigrade (° C.)
  • references to percentages are percentages by weight (wt %) and amounts and ratios are on an active ingredient basis, i.e., total weight of CTAC and the nonionic surfactant.
  • Numbers of polymerized units of propylene oxide or ethylene oxide are number averages.
  • the weight ratio of the nonionic surfactant with structure is preferably 1
  • the present invention is further directed to a method for inhibiting the growth of S. aureus , in an aqueous medium by adding: (a) a nonionic surfactant with structure:
  • the present invention is further directed to a method for inhibiting the growth of S. aureus , in an aqueous medium by adding: (a) a nonionic surfactant with structure:
  • R 2 is a mixture of C 8 -C 14 linear alkyl groups.
  • the C 8 -C 14 linear alkyl groups comprise from 50 to 85 wt % C 8 -C 10 linear alkyl groups and 15 to 50 wt % C 12 -C 14 linear alkyl groups, preferably from 60 to 75 wt % C 8 -C 10 linear alkyl groups and 25 to 40 wt % C 12 -C 14 linear alkyl groups, preferably about 70 wt % C 8 -C 10 linear alkyl groups and about 30 wt % C 12 -C 14 linear alkyl groups.
  • the linear alkyl groups are derived from seed oil.
  • R 1 is 2-ethylhexyl.
  • each of the compositions is substantially free of microbicides other than the nonionic surfactant and CTAC, DMO or Tris Nitro, i.e., it has less than 1 wt % of microbicides other than the nonionic surfactant and CTAC, DMO or Tris Nitro based on total weight of active ingredients, preferably less than 0.5 wt %, preferably less than 0.2 wt %, preferably less than 0.1 wt %.
  • the medium is substantially free of other microbicides, i.e., it has less than 1 wt % of microbicides other than the nonionic surfactant and CTAC, DMO or Tris Nitro based on total weight of active ingredients, preferably less than 0.5 wt %, preferably less than 0.2 wt %, preferably less than 0.1 wt %.
  • compositions of this invention may contain other ingredients, e.g., defoamers and emulsifiers.
  • the microbicidal compositions of the present invention can be used to inhibit the growth of microorganisms or higher forms of aquatic life (such as protozoans, invertebrates, bryozoans, dinoflagellates, crustaceans, mollusks, etc) by introducing a microbicidally effective amount of the compositions into an aqueous medium subject to microbial attack.
  • Suitable aqueous media are found in, for example: industrial process water; electrocoat deposition systems; cooling towers; air washers; gas scrubbers; mineral slurries; wastewater treatment; ornamental fountains; reverse osmosis filtration; ultrafiltration; ballast water; evaporative condensers; heat exchangers; pulp and paper processing fluids and additives; starch; plastics; emulsions; dispersions; paints; latices; coatings, such as varnishes; construction products, such as mastics, caulks, and sealants; construction adhesives, such as ceramic adhesives, carpet backing adhesives, and laminating adhesives; industrial or consumer adhesives; photographic chemicals; printing fluids; household products, such as bathroom and kitchen cleaners; cosmetics; toiletries; shampoos; soaps; personal care products such as wipes, lotions, sunscreen, conditioners, creams, and other leave-on applications; detergents; industrial cleaners; floor polishes; laundry rinse water; metalworking fluids; conveyor lubricants;
  • the specific amount of the microbicidal compositions of this invention necessary to inhibit or control the growth of microorganisms in an application will vary.
  • the amount of the composition of the present invention is sufficient to control the growth of microorganisms if it provides from 300 to 10,000 ppm (parts per million) active ingredients of the composition.
  • the active ingredients i.e., nonionic surfactant and CTAC, DMO or Tris Nitro
  • the active ingredients i.e., nonionic surfactant and CTAC, DMO or Tris Nitro
  • the active ingredients of the composition be present in the locus in an amount of 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 2,500 ppm, preferably no more than 2,000 ppm.
  • a composition is treated to inhibit microbial growth by adding, together or separately, the nonionic surfactant and CTAC, DMO or Tris Nitro, in amounts that would produce the concentrations indicated above.
  • Synergy index was calculated based on minimum inhibitory concentrations (MIC) of two antimicrobial compounds (A and B) alone and in combinations.
  • the tests organisms were Gram negative bacteria ( Pseudomonas aeruginosa ATCC #15442), Gram positive bacteria ( Staphylococcus aureus ATCC #6538), yeast ( Candida albicans ATCC #10203) and mold ( Aspergillus niger ATCC #16404). Contact time for the bacteria was 24 and 48 hours, yeast was 48 and 72 hrs, and 3 and 7 days for mold. The test was carried out in 96 well microtiter plates.
  • R 1 O(CH 2 CH(CH 3 )O) 5 (CH 2 CH 2 O) 9 H, where R 1 is 2-ethylhexyl Surf.
  • D R 2 O(CH 2 CH(CH 3 )O) 3 (CH 2 CH 2 O) 5 H Surf.
  • E R 2 O(CH 2 CH(CH 3 )O) 3 (CH 2 CH 2 O) 7 H
  • R 2 is a mixture of C 8 -C 14 linear alkyl groups (70% C 8 -C 10 linear alkyl and 30% C 12 -C 14 linear alkyl)
  • Inoculums Used Inoculum Size of organisms CFU/ml
  • D 1.808E+05 1.156E+08 1.156E+06 5.726E+05 Surf.
  • the pH of the Triptic soy broth was 7.3 and the Potato dextrose broth was 5.1.
  • test results for demonstration of synergy of the MIC combinations are shown in the tables below.
  • Each table shows the results for combinations of two components against the microorganisms tested with incubation times; the end-point activity in ppm measured by the MIC for compound A alone (CA), for component B alone (CB), and the mixture (Ca) and (Cb); the calculated SI value; and the range of synergistic ratios for each combination tested.
  • SI is calculated as follows:
  • Pseudomonas aeruginosa 15442 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714 CTAC with Surf.
  • D Staphylococcus aureus 6538 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714 Aspergillus niger 16404 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
  • Candida albicans 10203 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
  • Pseudomonas aeruginosa 15442 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
  • Pseudomonas 15442 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714 aeruginosa DMO with Surf.
  • D Staphylococcus 6538 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714 aureus Aspergillus 16404 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714 niger
  • Candida 10203 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714 albicans
  • Pseudomonas 15442 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714 aeruginosa
  • TrisNitro with Surf TrisNitro with Surf.
  • Pseudomonas aeruginosa 15442 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714 TrisNitro with Surf.
  • D Staphylococcus aureus 6538 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714 Aspergillus niger 16404 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
  • Candida albicans 10203 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
  • Pseudomonas aeruginosa 15442 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
  • aeruginosa >20000 600 20000 500 ⁇ 1.83 1:0.0250 ATCC#15442 >20000 600 10000 500 ⁇ 1.33 1:0.0500 >20000 600 5000 500 ⁇ 1.08 1:0.1000 >20000 600 2500 500 ⁇ 0.96 1:0.2000 >20000 600 1750 500 ⁇ 0.92 1:0.2857 >20000 600 875 500 ⁇ 0.88 1:0.5714 >20000 600 437.5 500 ⁇ 0.86 1:1.1429
  • aeruginosa >20000 800 20000 1000 ⁇ 2.25 1:0.0500 ATCC#15442 >20000 800 10000 1000 ⁇ 1.75 1:0.1000 >20000 800 5000 1000 ⁇ 1.50 1:0.2000 >20000 800 2500 800 ⁇ 1.13 1:0.3200 >20000 800 1750 1000 ⁇ 1.34 1:0.5714 >20000 800 875 800 ⁇ 1.04 1:0.9143 >20000 800 437.5 600 ⁇ 0.77 1:1.3714 >20000 800 437.5 800 ⁇ 1.02 1:1.8286 >20000 800 218.75 800 ⁇ 1.01 1:3.6571 No synergy: S. aureus , A. niger , C. albicans
  • aeruginosa >20000 1000 20000 1000 ⁇ 2.00 1:0.0500 ATCC#15442 >20000 1000 10000 1000 ⁇ 1.50 1:0.1000 >20000 1000 5000 1000 ⁇ 1.25 1:0.2000 >20000 1000 2500 1000 ⁇ 1.13 1:0.4000 >20000 1000 1750 1000 ⁇ 1.09 1:0.5714 >20000 1000 875 1000 ⁇ 1.04 1:1.1429 >20000 1000 437.5 800 ⁇ 0.82 1:1.8286 >20000 1000 437.5 1000 ⁇ 1.02 1:2.2857 >20000 1000 218.75 800 ⁇ 0.81 1:3.6571 >20000 1000 218.75 1000 ⁇ 1.01 1:4.5714 A: Surf.
  • a B DMO Media: PDB Inoculum size: 1.156E+06 CFU/ml PPM AI MIC Values (3 rd Day) Test Alone Combination Organism
  • CA CB Ca Cb S.I. Ratio (Ca:Cb) C. albicans >20000 1000 10000 800 ⁇ 1.30 1:0.0800 ATCC#10231 >20000 1000 5000 800 ⁇ 1.05 1:0.1600 >20000 1000 2500 800 ⁇ 0.93 1:0.3200 >20000 1000 875 800 ⁇ 0.84 1:0.9143
  • D B DMO Media: PDB Inoculum size: 5.726E+05 CFU/ml PPM AI MIC Values (48 hrs) Test Alone Combination Organism CA CB Ca Cb S.I. Ratio (Ca:Cb) C. albicans >20000 1000 10000 800 ⁇ 1.30 1:0.0800 ATCC#10231 >20000 1000 5000 800 ⁇ 1.05 1:0.1600 A: Surf. D B: 1135 Media: 1/10 TSB Inoculum size: 1.16E+08 PPM AI MIC Values (24 hrs) Test Alone Combination Organism CA CB Ca Cb S.I. Ratio (Ca:Cb) S.
  • E B DMO Media: PDB Inoculum size: 1.56E+06 CFU/ml PPM AI MIC Values (3 rd Day) Test Alone Combination Organism CA CB Ca Cb S.I. Ratio (Ca:Cb) A. niger >20000 800 10000 600 ⁇ 1.25 1:0.0600 ATCC#16404 >20000 800 5000 600 ⁇ 1.00 1:0.1200 >20000 800 437.5 600 ⁇ 0.77 1:1.3714 A: Surf.
  • the ratio of surfactant to biocide where synergy was observed were not commercially relevant, i.e., a ratio of 1:0.2 or greater (less biocide relative to surfactant). At these ratios, the biocide levels in a formulated product would be too low to be practical:

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Abstract

A synergistic microbicidal composition having two components. The first component is a nonionic surfactant with structure: R1O(CH2CH(CH3)O)5(CH2CH2O)9H, where R1 is a C8 alkyl group. The second component is cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride. The weight ratio of the nonionic surfactant to cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride is from 1:0.2 to 1:1.1429.

Description

  • This invention relates to microbicidal compositions containing cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride (CTAC), 4,4-dimethyloxazolidine (DMO) or tris(hydroxymethyl)nitromethane (Tris Nitro) and a surfactant.
  • A composition containing 5-chloro-2-methylisothiazolin-3-one, 2-methylisothiazolin-3-one and a nonionic dispersant is disclosed in U.S. Pat. No. 4,295,932. The composition contains a 3:1 mixture of 5-chloro-2-methylisothiazolin-3-one and 2-methylisothiazolin-3-one, and a copolymer of ethylene oxide and propylene oxide which appears to have the same composition as PLURONIC L61 or TERGITOL L61 dispersant. However, there is a need for combinations of microbicides having synergistic activity against various strains of microorganisms to provide effective control of the microorganisms. Moreover, there is a need for such combinations containing lower levels of individual microbicides for environmental and economic benefit. The problem addressed by this invention is to provide such synergistic combinations of microbicides.
    • STATEMENT OF THE INVENTION
  • The present invention is directed to a synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
      • R1O(CH2CH(CH3)O)5(CH2CH2O)9H
        where R1 is a C8 alkyl group; and (b) cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride; wherein a weight ratio of said nonionic surfactant to cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride is from 1:0.2 to 1:1.1429.
  • The present invention is further directed to a synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
      • R2O(CH2CH(CH3)O)3(CH2CH2O)5H
        where R2 is a mixture of C8-C14 linear alkyl groups; and (b) cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride; wherein a weight ratio of said nonionic surfactant to cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride is from 1:0.04 to 1:0.9143.
  • The present invention is further directed to a synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
      • R2O(CH2CH(CH3)O)3(CH2CH2O)7H
        where R2 is a mixture of C8-C14 linear alkyl groups; and (b) cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride; wherein a weight ratio of said nonionic surfactant to cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride is from 1:0.016 to 1:0.0571.
  • The present invention is further directed to a synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
      • R1O(CH2CH(CH3)O)5(CH2CH2O)9H
        where R1 is a C8 alkyl group; and (b) 4,4-dimethyloxazolidine; wherein a weight ratio of said nonionic surfactant to 4,4-dimethyloxazolidine is from 1:0.0286 to 1:0.1143 or 1:0.32 to 1:0.9143.
  • The present invention is further directed to a synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
      • R2O(CH2CH(CH3)O)3(CH2CH2O)5H
        where R2 is a mixture of C8-C14 linear alkyl groups; and (b) 4,4-dimethyloxazolidine; wherein a weight ratio of said nonionic surfactant to 4,4-dimethyloxazolidine is from 1:0.06 to 1:0.6857.
  • The present invention is further directed to a synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
      • R2O(CH2CH(CH3)O)3(CH2CH2O)7H
        where R2 is a mixture of C8-C14 linear alkyl groups; and (b) 4,4-dimethyloxazolidine; wherein a weight ratio of said nonionic surfactant to 4,4-dimethyloxazolidine is from 1:0.024 to 1:0.2743.
  • The present invention is further directed to a synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
      • R2O(CH2CH(CH3)O)3(CH2CH2O)7H
        where R2 is a mixture of C8-C14 linear alkyl groups; and (b) tris(hydroxymethyl)nitromethane; wherein a weight ratio of said nonionic surfactant to tris(hydroxymethyl)nitromethane is from 1:0.16 to 1:1.8286.
  • The present invention is further directed to methods for inhibiting the growth of microorganisms in aqueous media by adding to an aqueous medium a nonionic surfactant as described herein and cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride, 4,4-dimethyloxazolidne or tris(hydroxymethyl)nitromethane in the ratios described herein.
    • DETAILED DESCRIPTION OF THE INVENTION
  • “CTAC” is cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride, CAS No. 51229-78-8, “DMO” is 4,4-dimethyloxazolidine, CAS No. 51200-87-4, and “Tris Nitro” is tris(hydroxymethyl)nitromethane, CAS No. 126-11-4. As used herein, the following terms have the designated definitions, unless the context clearly indicates otherwise. The term “microbicide” refers to a compound capable of inhibiting the growth of or controlling the growth of microorganisms; microbicides include bactericides, fungicides and algaecides. 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. Unless otherwise specified, temperatures are in degrees centigrade (° C.), references to percentages are percentages by weight (wt %) and amounts and ratios are on an active ingredient basis, i.e., total weight of CTAC and the nonionic surfactant. Numbers of polymerized units of propylene oxide or ethylene oxide are number averages.
  • Preferably, the weight ratio of the nonionic surfactant with structure:
      • R1O(CH2CH(CH3)O)5(CH2CH2O)9H
        where R1 is a C8 alkyl group to CTAC is from 1:0.2857 to 1:1.1429, preferably from 1:0.5714 to 1:1.1429. Preferably, the weight ratio of the nonionic surfactant with structure:
      • R2O(CH2CH(CH3)O)3(CH2CH2O)5H
        where R2 is a mixture of C8-C14 linear alkyl groups to CTAC is from 1:0.0457 to 1:0.9143.
  • The present invention is further directed to a method for inhibiting the growth of S. aureus, in an aqueous medium by adding: (a) a nonionic surfactant with structure:
      • R2O(CH2CH(CH3)O)3(CH2CH2O)5H
        where R2 is a mixture of C8-C14 linear alkyl groups; and (b) CTAC; wherein a weight ratio of said nonionic surfactant to CTAC is from 1:0.0457 to 1:0.9143.
  • The present invention is further directed to a method for inhibiting the growth of S. aureus, in an aqueous medium by adding: (a) a nonionic surfactant with structure:
      • R2O(CH2CH(CH3)O)3(CH2CH2O)7H
        where R2 is a mixture of C8-C14 linear alkyl groups; and (b) Tris Nitro; wherein a weight ratio of said nonionic surfactant to Tris Nitro is from 1:0.16 to 1:1.8286.
  • R2 is a mixture of C8-C14 linear alkyl groups. Preferably, the C8-C14 linear alkyl groups comprise from 50 to 85 wt % C8-C10 linear alkyl groups and 15 to 50 wt % C12-C14 linear alkyl groups, preferably from 60 to 75 wt % C8-C10 linear alkyl groups and 25 to 40 wt % C12-C14 linear alkyl groups, preferably about 70 wt % C8-C10 linear alkyl groups and about 30 wt % C12-C14 linear alkyl groups. Preferably, the linear alkyl groups are derived from seed oil. Preferably, R1 is 2-ethylhexyl.
  • Preferably, each of the compositions is substantially free of microbicides other than the nonionic surfactant and CTAC, DMO or Tris Nitro, i.e., it has less than 1 wt % of microbicides other than the nonionic surfactant and CTAC, DMO or Tris Nitro based on total weight of active ingredients, preferably less than 0.5 wt %, preferably less than 0.2 wt %, preferably less than 0.1 wt %. Preferably, when the nonionic surfactant and CTAC, DMO or Tris Nitro are added to an aqueous medium, the medium is substantially free of other microbicides, i.e., it has less than 1 wt % of microbicides other than the nonionic surfactant and CTAC, DMO or Tris Nitro based on total weight of active ingredients, preferably less than 0.5 wt %, preferably less than 0.2 wt %, preferably less than 0.1 wt %.
  • The compositions of this invention may contain other ingredients, e.g., defoamers and emulsifiers. The microbicidal compositions of the present invention can be used to inhibit the growth of microorganisms or higher forms of aquatic life (such as protozoans, invertebrates, bryozoans, dinoflagellates, crustaceans, mollusks, etc) by introducing a microbicidally effective amount of the compositions into an aqueous medium subject to microbial attack. Suitable aqueous media are found in, for example: industrial process water; electrocoat deposition systems; cooling towers; air washers; gas scrubbers; mineral slurries; wastewater treatment; ornamental fountains; reverse osmosis filtration; ultrafiltration; ballast water; evaporative condensers; heat exchangers; pulp and paper processing fluids and additives; starch; plastics; emulsions; dispersions; paints; latices; coatings, such as varnishes; construction products, such as mastics, caulks, and sealants; construction adhesives, such as ceramic adhesives, carpet backing adhesives, and laminating adhesives; industrial or consumer adhesives; photographic chemicals; printing fluids; household products, such as bathroom and kitchen cleaners; cosmetics; toiletries; shampoos; soaps; personal care products such as wipes, lotions, sunscreen, conditioners, creams, and other leave-on applications; detergents; industrial cleaners; floor polishes; laundry rinse water; metalworking fluids; conveyor lubricants; hydraulic fluids; leather and leather products; textiles; textile products; wood and wood products, such as plywood, chipboard, flakeboard, laminated beams, oriented strandboard, hardboard, and particleboard; petroleum processing fluids; fuel; oilfield fluids, such as injection water, fracture fluids, and drilling muds; agriculture adjuvant preservation; surfactant preservation; medical devices; diagnostic reagent preservation; food preservation, such as plastic or paper food wrap; food, beverage, and industrial process pasteurizers; toilet bowls; recreational water; pools; and spas.
  • The specific amount of the microbicidal compositions of this invention necessary to inhibit or control the growth of microorganisms in an application will vary. Typically, the amount of the composition of the present invention is sufficient to control the growth of microorganisms if it provides from 300 to 10,000 ppm (parts per million) active ingredients of the composition. It is preferred that the active ingredients (i.e., nonionic surfactant and CTAC, DMO or Tris Nitro) of the composition be present in the medium to be treated in an amount of at least 500 ppm, preferably at least 600 ppm, preferably at least 800 ppm. It is preferred that the active ingredients of the composition be present in the locus in an amount of 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 2,500 ppm, preferably no more than 2,000 ppm. In a method of this invention, a composition is treated to inhibit microbial growth by adding, together or separately, the nonionic surfactant and CTAC, DMO or Tris Nitro, in amounts that would produce the concentrations indicated above.
    • EXAMPLES
  • Surfactants and biocides were evaluated for synergy by determining the synergy index (S.I.) of the combination. Synergy index was calculated based on minimum inhibitory concentrations (MIC) of two antimicrobial compounds (A and B) alone and in combinations. The tests organisms were Gram negative bacteria (Pseudomonas aeruginosa ATCC #15442), Gram positive bacteria (Staphylococcus aureus ATCC #6538), yeast (Candida albicans ATCC #10203) and mold (Aspergillus niger ATCC #16404). Contact time for the bacteria was 24 and 48 hours, yeast was 48 and 72 hrs, and 3 and 7 days for mold. The test was carried out in 96 well microtiter plates.
  • Surf. A R1O(CH2CH(CH3)O)5(CH2CH2O)9H, where R1 is 2-ethylhexyl
    Surf. D R2O(CH2CH(CH3)O)3(CH2CH2O)5H
    Surf. E R2O(CH2CH(CH3)O)3(CH2CH2O)7H
    In Surf. D and Surf. E, R2 is a mixture of C8-C14 linear alkyl groups (70% C8-C10 linear alkyl and 30% C12-C14 linear alkyl)
  • Inoculums Used
    Inoculum Size of organisms (CFU/ml)
    Aspergillus Candida
    Staphylococcus Pseudomonas niger albicans
    Surfac- aureus aeruginosa ATCC# ATCC#
    tants ATCC# 6538 ATCC # 15442 16404 10203
    Surf. A 1.156E+06 8.134E+07 1.156E+06 1.156 +06
    Surf. D 1.808E+05 1.156E+08 1.156E+06 5.726E+05
    Surf. E 1.808E+06 5.727E+07 5.726E+05 1.808E+06
  • TABLE 4
    Media Used
    Media Used for testing
    Staphylococcus Pseudomonas Aspergillus Candida
    aureus aeruginosa ATCC # niger albicans
    ATCC# 6538 15442 ATCC# 16404 ATCC# 10203
    10% Tryptic soy 10% Tryptic soy Potato dextrose Potato dextrose
    broth broth broth broth
  • The pH of the Triptic soy broth was 7.3 and the Potato dextrose broth was 5.1.
  • The test results for demonstration of synergy of the MIC combinations are shown in the tables below. Each table shows the results for combinations of two components against the microorganisms tested with incubation times; the end-point activity in ppm measured by the MIC for compound A alone (CA), for component B alone (CB), and the mixture (Ca) and (Cb); the calculated SI value; and the range of synergistic ratios for each combination tested. SI is calculated as follows:

  • Ca/CA+Cb/CB=Synergy Index (“SI”)
  • Wherein:
      • CA=concentration of compound A in ppm, acting alone, which produced an end point (MIC of Compound A).
      • Ca=concentration of compound A in ppm, in the mixture, which produced an end point.
      • CB=concentration of compound B in ppm, acting alone, which produced an end point (MIC of Compound B).
      • Cb=concentration of compound B in ppm, in the mixture, which produced an end point.
        When the sum of Ca/CA and Cb/CB is greater than one, antagonism is indicated. When the sum is equal to one, additivity is indicated, and when less than one, synergism is demonstrated.
  • The ratio ranges at which CTAC, DMO or Tris Nitro and the surfactants were tested are as summarized in the following tables:
  • Organism ATCC# From To Ratio Range
    CTAC with Surf. A
    Staphylococcus aureus 6538 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    Aspergillus niger 16404 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    Candida albicans 10203 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    Pseudomonas aeruginosa 15442 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    CTAC with Surf. E
    Staphylococcus aureus 6538 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    Aspergillus niger 16404 2.0:20,000 10,000:218.75   1:0.0001-1:45.7143
    Candida albicans 10203 2.0:20,000 10,000:218.75   1:0.0001-1:45.7143
    Pseudomonas aeruginosa 15442 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    CTAC with Surf. D
    Staphylococcus aureus 6538 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    Aspergillus niger 16404 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    Candida albicans 10203 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    Pseudomonas aeruginosa 15442 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
  • Organism ATCC# From To Ratio Range
    DMO with Surf. A
    Staphylococcus 6538 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    aureus
    Aspergillus 16404 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    niger
    Candida 10203 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    albicans
    Pseudomonas 15442 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    aeruginosa
    DMO with Surf. E
    Staphylococcus 6538 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    aureus
    Aspergillus 16404 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    niger
    Candida 10203 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    albicans
    Pseudomonas 15442 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    aeruginosa
    DMO with Surf. D
    Staphylococcus 6538 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    aureus
    Aspergillus 16404 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    niger
    Candida 10203 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    albicans
    Pseudomonas 15442 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    aeruginosa
  • Organism ATCC# From To Ratio Range
    TrisNitro with Surf. A
    Staphylococcus aureus 6538 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    Aspergillus niger 16404 0.02:20,000    100:218.75 1:0.000001-1:0.45714
    Candida albicans 10203 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    Pseudomonas aeruginosa 15442 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    TrisNitro with Surf. E
    Staphylococcus aureus 6538 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    Aspergillus niger 16404 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    Candida albicans 10203 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    Pseudomonas aeruginosa 15442 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    TrisNitro with Surf. D
    Staphylococcus aureus 6538 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    Aspergillus niger 16404 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    Candida albicans 10203 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
    Pseudomonas aeruginosa 15442 0.2:20,000 1,000:218.75 1:0.00001-1:4.5714
  • A: Surf. A
    B: CTAC
    Media: PDB
    Inoculum size: 1.156E+06
    A. niger ATCC#16404 No Synergy
    C. albicans ATCC#10203 No Synergy
    A: Surf. A
    B: CTAC
    Media: 1/10 TSB
    Inoculum size: 1.156E+06
    S. aureus ATCC# 6538 No Synergy
    A: Surf. A
    B: CTAC
    Media: 1/10 TSB
    Inoculum size: 1.156E+06
    PPM AI MIC Values (3rd Day)
    Test Alone Combination
    Organism CA CB Ca Cb S.I. Ratio (Ca:Cb)
    P. aeruginosa >20000 600 20000 500 <1.83 1:0.0250
    ATCC#15442 >20000 600 10000 500 <1.33 1:0.0500
    >20000 600 5000 500 <1.08 1:0.1000
    >20000 600 2500 500 <0.96 1:0.2000
    >20000 600 1750 500 <0.92 1:0.2857
    >20000 600 875 500 <0.88 1:0.5714
    >20000 600 437.5 500 <0.86 1:1.1429
  • A: Surf. D
    B: CTAC
    Media: PDB
    Inoculum size: 1.156E+06
    PPM AI MIC Values (3rd day)
    Test Alone Combination
    Organism CA CB Ca Cb S.I. Ratio (Ca:Cb)
    A. niger >20000 1000 10000 600 <1.10 1:0.0600
    >20000 1000 10000 800 <1.30 1:0.0800
    ATCC#16404 >20000 1000 5000 800 <1.05 1:0.1600
    >20000 1000 2500 800 <0.93 1:0.3200
    >20000 1000 1750 800 <0.89 1:0.4571
    >20000 1000 875 800 <0.84 1:0.9143
    A: Surf. D
    B: CTAC
    Media: PDB
    Inoculum size: 5.726E+05 CFU/ml
    PPM AI MIC Values (48 hrs)
    Test Alone Combination
    Organism CA CB Ca Cb S.I. Ratio (Ca:Cb)
    C. albicans >20000 1000 10000 400 <0.90 1:0.0400
    ATCC#10203 >20000 1000 10000 500 <1.00 1:0.0500
    >20000 1000 10000 600 <1.10 1:0.0600
    >20000 1000 10000 800 <1.30 1:0.0800
    >20000 1000 5000 400 <0.65 1:0.0800
    >20000 1000 5000 500 <0.75 1:0.1000
    >20000 1000 5000 600 <0.85 1:0.1200
    >20000 1000 5000 800 <1.05 1:0.1600
    A: Surf. D
    B: CTAC
    Media: 1/10 TSB
    Inoculum size: 1.808E+05
    PPM AI MIC Values (24 hrs)
    Test Alone Combination Ratio
    Organism CA CB Ca Cb S.I. (Ca:Cb)
    S. aureus >20000 300 10000 80 <0.77 1:0.0080
    ATCC# 6538 >20000 300 10000 100 <0.83 1:0.0100
    >20000 300 10000 200 <1.17 1:0.0200
    >20000 300 5000 200 <0.92 1:0.0400
    >20000 300 5000 80 <0.52 1:0.0160
    >20000 300 5000 100 <0.58 1:0.0200
    >20000 300 1750 80 <0.35 1:0.0457
    >20000 300 1750 100 <0.42 1:0.0571
    >20000 300 1750 200 <0.75 1:0.1143
    >20000 300 875 200 <0.71 1:0.2286
    >20000 300 437.5 200 <0.69 1:0.9143
    >20000 300 218.75 200 <0.68 1:0.2286
    A: Surf. D
    B: CTAC
    Media: 1/10 TSB
    Inoculum size: 1.156E+06
    P. aeruginosa ATCC#15442 No Synergy
  • A: Surf. E
    B: CTAC
    Media: PDB
    Inoculum 1.808E+05
    A. niger ATCC 16404 No synergy
    A: Surf. E
    B: CTAC
    Media: PDB
    Inoculum 1.808E+05
    PPM AI MIC Values (48 hrs)
    Test Alone Combination
    Organism CA CB Ca Cb S.I. Ratio (Ca:Cb)
    C. albicans >20000 2997 10000 1999 <1.17 1:0.1999
    ATCC 10203
    A: Surf. E
    B: CTAC
    Media: 1/10 TSB
    Inoculum size: 5.72E+07
    P. aeruginosa ATCC#15442 No synergy
    A: Surf. E
    B: CTAC
    Media: 1/10 TSB
    Inoculum size: 1.8E+06
    PPM AI MIC Values (24 hrs)
    Test Alone Combination
    Organism CA CB Ca Cb S.I. Ratio (Ca:Cb)
    S. aureus >20000 200 10000 80 <0.90 1:0.0080
    ATCC# 6538 >20000 200 10000 100 <1.00 1:0.0100
    >20000 200 5000 80 <0.65 1:0.0160
    >20000 200 5000 100 <0.75 1:0.0200
    >20000 200 2500 100 <0.63 1:0.0400
    >20000 200 1750 100 <0.59 1:0.0571
  • A: Surf. A
    B: Tris Nitro
    No synergy:
    S. aureus, A. niger, C. albicans, Ps. aeruginosa
    A: Surf. D
    B: TrisNitro
    Media: 1/10 TSB
    Inoculum size: 1.16E+08
    PPM AI MIC Values (24 hrs)
    Test Alone Combination Ratio
    Organism CA CB Ca Cb S.I. (Ca:Cb)
    Ps. aeruginosa >20000 800 20000 1000 <2.25 1:0.0500
    ATCC#15442 >20000 800 10000 1000 <1.75 1:0.1000
    >20000 800 5000 1000 <1.50 1:0.2000
    >20000 800 2500 800 <1.13 1:0.3200
    >20000 800 1750 1000 <1.34 1:0.5714
    >20000 800 875 800 <1.04 1:0.9143
    >20000 800 437.5 600 <0.77 1:1.3714
    >20000 800 437.5 800 <1.02 1:1.8286
    >20000 800 218.75 800 <1.01 1:3.6571
    No synergy: S. aureus, A. niger, C. albicans
  • A: Surf. E
    B: TrisNitro
    Media: 1/10TSB
    Inoculum size: 5.727E+07 CFU/ml
    PPM AI MIC Values (24 hrs)
    Test Alone Combination Ratio
    Organism CA CB Ca Cb S.I. (Ca:Cb)
    Ps. aeruginosa >20000 1000 20000 1000 <2.00 1:0.0500
    ATCC#15442 >20000 1000 10000 1000 <1.50 1:0.1000
    >20000 1000 5000 1000 <1.25 1:0.2000
    >20000 1000 2500 1000 <1.13 1:0.4000
    >20000 1000 1750 1000 <1.09 1:0.5714
    >20000 1000 875 1000 <1.04 1:1.1429
    >20000 1000 437.5 800 <0.82 1:1.8286
    >20000 1000 437.5 1000 <1.02 1:2.2857
    >20000 1000 218.75 800 <0.81 1:3.6571
    >20000 1000 218.75 1000 <1.01 1:4.5714
    A: Surf. E
    B: TrisNitro
    Media: 1/10TSB
    Inoculum size: 1.808E+06 CFU/ml
    PPM AI MIC Values (24 hrs)
    Test Alone Combination Ratio
    Organism CA CB Ca Cb S.I. (Ca:Cb)
    S. aureus >20000 500 20000 500 <2.00 1:0.0250
    ATCC# 6538 >20000 500 10000 400 <1.30 1:0.0400
    >20000 500 5000 400 <1.05 1:0.0800
    >20000 500 2500 400 <0.93 1:0.1600
    >20000 500 1750 300 <0.69 1:0.1714
    >20000 500 1750 400 <0.89 1:0.2286
    >20000 500 875 400 <0.84 1:0.4571
    >20000 500 437.5 400 <0.82 1:0.9143
    >20000 500 218.75 400 <0.81 1:1.8286
    >20000 500 218.75 500 <1.01 1:2.2857
    No synergy: A. niger, C. albicans
  • A: Surf. A
    B: DMO
    Media: PDB
    Inoculum size: 1.156E+06 CFU/ml
    PPM AI MIC Values (3rd Day)
    Test Alone Combination
    Organism CA CB Ca Cb S.I. Ratio (Ca:Cb)
    A. niger >20000 60 10000 50 <1.33 1:0.0050
    ATCC#16404 >20000 60 5000 50 <1.08 1:0.0100
    >20000 60 2500 50 <0.96 1:0.0200
    >20000 60 1750 50 <0.92 1:0.0286
    >20000 60 875 50 <0.88 1:0.0571
    >20000 60 437.5 50 <0.86 1:0.1143
    A: Surf. A
    B: DMO
    Media: PDB
    Inoculum size: 1.156E+06 CFU/ml
    PPM AI MIC Values (3rd Day)
    Test Alone Combination
    Organism CA CB Ca Cb S.I. Ratio (Ca:Cb)
    C. albicans >20000 1000 10000 800 <1.30 1:0.0800
    ATCC#10231 >20000 1000 5000 800 <1.05 1:0.1600
    >20000 1000 2500 800 <0.93 1:0.3200
    >20000 1000 875 800 <0.84 1:0.9143
    A: Surf. A
    B: DMO
    Media: 1/10 TSB
    Inoculum size: 8.134+07 CFU/ml
    PPM AI MIC Values (24 hrs)
    Test Alone Combination
    Organism CA CB Ca Cb S.I. Ratio (Ca:Cb)
    P. aeruginosa >20000 80 20000 60 <1.75 1:0.0030
    ATCC#15442
    A: Surf. A
    B: DMO
    Media: 1/10 TSB
    Inoculum size: 1.156E+06 CFU/ml
    PPM AI MIC Values (24 hrs)
    Test Alone Combination
    Organism CA CB Ca Cb S.I. Ratio (Ca:Cb)
    S. aureua >20000 50 20000 40 <1.80 1:0.0020
    ATCC#6538
  • A: Surf. D
    B: DMO
    Media: 1/10 TSB
    Inoculum size: 1.16E+08
    P. aeruginosa ATCC#15442 No Synergy
    A: Surf. D
    B: DMO
    Media: PDB
    Inoculum size: 1.156E+06
    PPM AI MIC Values (3rd day)
    Test Alone Combination
    Organism CA CB Ca Cb S.I. Ratio (Ca:Cb)
    A. niger >20000 400 10000 300 <1.25 1:0.0300
    ATCC#16404 >20000 400 5000 300 <1.0 1:0.0600
    >20000 400 437.5 300 <0.77 1:0.6857
    A: Surf. D
    B: DMO
    Media: PDB
    Inoculum size: 5.726E+05 CFU/ml
    PPM AI MIC Values (48 hrs)
    Test Alone Combination
    Organism CA CB Ca Cb S.I. Ratio (Ca:Cb)
    C. albicans >20000 1000 10000 800 <1.30 1:0.0800
    ATCC#10231 >20000 1000 5000 800 <1.05 1:0.1600
    A: Surf. D
    B: 1135
    Media: 1/10 TSB
    Inoculum size: 1.16E+08
    PPM AI MIC Values (24 hrs)
    Test Alone Combination
    Organism CA CB Ca Cb S.I. Ratio (Ca:Cb)
    S. aureus >20000 80 10000 50 >1.13 1:0.0050
    ATCC#6538 >20000 80 10000 60 >1.25 1:0.0060
    >20000 80 5000 50 <0.88 1:0.0100
    >20000 80 5000 60 <1.00 1:0.0025
    >20000 80 2500 60 <0.88 1:0.0120
    >20000 80 1750 50 <0.71 1:0.0240
    >20000 80 1750 60 <0.84 1:0.0286
    >20000 80 875 50 <0.67 1:0.0343
    >20000 80 875 60 <0.79 1:0.0571
    >20000 80 437.5 50 <0.65 1:0.0686
    >20000 80 437.5 60 <0.77 1:0.1143
    >20000 80 218.75 60 <0.76 1:0.1371
  • A: Surf. E
    B: DMO
    Media: PDB
    Inoculum size: 1.808E+06
    PPM AI MIC Values (48 hrs)
    Test Alone Combination
    Organism CA CB Ca Cb S.I. Ratio (Ca:Cb)
    C. albicans >20000 1000 10000 600 <1.10 1:0.0600
    ATCC#10203 >20000 1000 10000 800 <1.30 1:0.0800
    >20000 1000 5000 600 <0.85 1:0.1200
    >20000 1000 5000 800 <1.05 1:0.1600
    A: Surf. E
    B: DMO
    Media: PDB
    P. aeruginosa ATCC#15442 No Synergy
    A: Surf. E
    B: DMO
    Media: PDB
    Inoculum size: 1.56E+06 CFU/ml
    PPM AI MIC Values (3rd Day)
    Test Alone Combination
    Organism CA CB Ca Cb S.I. Ratio (Ca:Cb)
    A. niger >20000 800 10000 600 <1.25 1:0.0600
    ATCC#16404 >20000 800 5000 600 <1.00 1:0.1200
    >20000 800 437.5 600 <0.77 1:1.3714
    A: Surf. E
    B: DMO
    Media: 1/10 TSB
    Inoculum size: 1.80E+06 CFU/ml
    PPM AI MIC Values (24 hrs)
    Test Alone Combination
    Organism CA CB Ca Cb S.I. Ratio (Ca:Cb)
    ATCC#6538 >20000 80 10000 50 <1.13 1:0.0050
    >20000 80 10000 60 <1.25 1:0.0060
    >20000 80 5000 50 <0.88 1:0.0100
    >20000 80 5000 60 <1.00 1:0.0120
    >20000 80 2500 60 <0.88 1:0.0240
    >20000 80 1750 60 <0.84 1:0.0343
    >20000 80 875 60 <0.79 1:0.0686
    >20000 80 437.5 50 <0.65 1:0.1143
    >20000 80 437.5 60 <0.77 1:0.1371
    >20000 80 218.75 60 <0.76 1:0.2743
  • The following biocides had no synergy against any organism tested when paired with the following surfactants:
  • Surf. A
    • Sodium Benzoate, TRIS NITRO
  • Surf. E
    • DMDMH
  • Surf. D
    • CS-1246, OPP, DMDMH
  • In the following combinations, the ratio of surfactant to biocide where synergy was observed were not commercially relevant, i.e., a ratio of 1:0.2 or greater (less biocide relative to surfactant). At these ratios, the biocide levels in a formulated product would be too low to be practical:
  • Surf. A
    • DIDAC, IPBC
  • Surf. E
    • CMIT/MIT, IPBC, OIT, TTPC, WSCP
  • Surf. D
    • CMIT/MIT, OIT, DIDAC
  • (MBIT, IPBC, WSCP were synergistic only at 1:0.05 or worse except for one data point)

Claims (10)

1. A synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
R1O(CH2CH(CH3)O)5(CH2CH2O)9H
where R1 is a C8 alkyl group; and (b) cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride; wherein a weight ratio of said nonionic surfactant to cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride is from 1:0.2 to 1:1.1429.
2. The synergistic microbicidal composition of claim 1 in which R1 is 2-ethylhexyl.
3. A synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
R2O(CH2CH(CH3)O)3(CH2CH2O)5H
where R2 is a mixture of C8-C14 linear alkyl groups; and (b) cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride; wherein a weight ratio of said nonionic surfactant to cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride is from 1:0.04 to 1:0.9143.
4. The synergistic microbicidal composition of claim 3 in which said mixture of C8-C14 linear alkyl groups comprises from 60 to 75 wt % C8-C10 linear alkyl groups and 25 to 40 wt % C12-C14 linear alkyl groups.
5. A synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
R1O(CH2CH(CH3)O)5(CH2CH2O)9H
where R1 is a C8 alkyl group; and (b) 4,4-dimethyloxazolidine; wherein a weight ratio of said nonionic surfactant to 4,4-dimethyloxazolidine is from 1:0.0286 to 1:0.1143 or 1:0.32 to 1:0.9143.
6. The synergistic microbicidal composition of claim 5 in which R1 is 2-ethylhexyl.
7. A synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
R2O(CH2CH(CH3)O)3(CH2CH2O)5H
where R2 is a mixture of C8-C14 linear alkyl groups; and (b) 4,4-dimethyloxazolidine; wherein a weight ratio of said nonionic surfactant to 4,4-dimethyloxazolidine is from 1:0.06 to 1:0.6857.
8. The synergistic microbicidal composition of claim 7 in which said mixture of C8-C14 linear alkyl groups comprises from 60 to 75 wt % C8-C10 linear alkyl groups and 25 to 40 wt % C12-C14 linear alkyl groups.
9. A synergistic microbicidal composition comprising: (a) a nonionic surfactant with structure:
R2O(CH2CH(CH3)O)3(CH2CH2O)7H
where R2 is a mixture of C8-C14 linear alkyl groups; and (b) tris(hydroxymethyl)nitromethane; wherein a weight ratio of said nonionic surfactant to tris(hydroxymethyl)nitromethane is from 1:0.16 to 1:1.8286.
10. The synergistic microbicidal composition of claim 9 in which. said mixture of C8-C14 linear alkyl groups comprises from 60 to 75 wt % C8-C10 linear alkyl groups and 25 to 40 wt % C12-C14 linear alkyl groups.
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Family Cites Families (16)

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Publication number Priority date Publication date Assignee Title
US4295932A (en) 1980-07-14 1981-10-20 Naloc Chemical Company Synergistic blend of biocides
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US6969698B2 (en) * 2004-04-13 2005-11-29 S. C. Johnson & Son, Inc. Aerosol cleaner
WO2007100776A2 (en) * 2006-02-28 2007-09-07 Becton, Dickinson And Company Antimicrobial compositions and methods for locking catheters
CN101578130A (en) * 2007-01-11 2009-11-11 陶氏环球技术公司 Alkoxylate blend surfactants
EP2117300B1 (en) * 2007-01-12 2017-04-19 ANGUS Chemical Company Aminoalcohol and biocide compositions for aqueous based systems
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CN101754685B (en) * 2007-07-24 2015-09-16 陶氏环球技术公司 For reducing with suppress the method and formulation that in water-based fluid and the system that uses together with them, microorganism concn increases
CN102066540A (en) * 2008-06-18 2011-05-18 陶氏环球技术公司 Cleaning compositions containing mid-range alkoxylates
BRPI0910177B1 (en) * 2008-06-27 2017-09-26 Dow Global Technologies Inc. A biocidal composition and method for inhibiting bacterial growth in a medium
CN102361553B (en) * 2009-03-26 2015-04-01 陶氏环球技术有限责任公司 Biocidal composition of 2,6-dimethyl-m-dioxane-4-ol acetate and methods of use
AR076348A1 (en) * 2009-04-22 2011-06-01 Dow Global Technologies Inc BIOCIDES COMPOSITIONS AND METHODS OF USE
RU2499387C2 (en) * 2009-07-27 2013-11-27 Дау Глоубл Текнолоджиз Ллк Synergetic antimicrobial composition
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