This invention relates to combinations of biocides, the combinations having greater activity than would be observed for the individual antimicrobial compounds.
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, or relatively slow antimicrobial action, or instability under certain conditions such as high temperature and high pH. Combinations of different antimicrobial compounds are sometimes used to provide overall control of microorganisms or to provide the same level of microbial control at lower use rates in a particular end use environment. Additionally, synergy has been found to be an unpredictable phenomenon. Often like compounds display varying synergistic profiles when combined with a particular active. It may be that no synergy is evidenced or it may be that synergy exists but over a different synergistic range. Because of this observation, it is difficult, if not impossible, to draw conclusions regarding the synergistic profile of one compound based upon the synergistic profile of a like compound. Thus more synergistic combinations and their synergistic ranges must be discovered.
One such example of synergy is found in U.S. Pat. No. 5,385,896. This reference discloses combinations of phosphonium salts and aldehydes, but this reference does not suggest any of the combinations claimed herein. There still exists a need for additional combinations of antimicrobial compounds having enhanced activity to provide effective control of microorganisms. The problem addressed by this invention is to provide such combinations of antimicrobial compounds.
The present invention is directed to a synergistic antimicrobial composition comprising: (a) diamine; and (b) dithio-2,2-bis-benzmethylamide; wherein a weight ratio of the diamine to dithio-2,2′-bis-benzmethylamide is from 10:1 to 1:10.
As used herein, the following terms have the designated definitions, unless the context clearly indicates otherwise. The term “antimicrobial compound” refers to a compound capable of inhibiting the growth or propagation of microorganisms, and/or killing microorganisms; antimicrobial compounds include bactericides, bacteriostats, bacteriostatics, bacteriostatins, 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. 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. Lastly, all range value endpoints are inclusive and combinable (e.g. ranges expressed as from 10:1 to 1:10 and alternatively 3:1 and 1:3 may also include, for example 10:3).
As used herein, diamine(s) refers to N-(3-Aminopropyl)-N-dodecylpropane-1,3-diamine, cas #2372-82-9 and dithio-2,2′-bis-benzmethylamide or “DTBMA” corresponds with cas #: 2527-58-4.
In some embodiments of the invention, a weight ratio of the diamine to dithio-2,2′-bis-benzmethylamide (DTBMA) is from 10:1 to 1:10, alternatively from 9:1 to 1:9 and further alternatively from 3:1 to 1:3.
In some embodiments of the invention, the antimicrobial combination is useful for inhibiting microbial growth in an aqueous medium for example as an in-can preservative. The composition also is useful for controlling microorganisms in other aqueous media including but not limited to industrial water and water containing/contaminated media, such as cooling water, air washer, heat exchangers, boiler water, pulp and paper mill water, other industrial process water media such as: ballast water, wastewater, metalworking fluids, oil and gas, latex, paint, coatings, adhesives, inks, tape joint compounds, pigment, water-based slurries, personal care and household products such as detergent, filtration systems (including reverse osmosis and ultrafiltration systems), toilet bowel, textiles, leather and leather production system, or a system used therewith.
Typically, the amount of the biocide combinations of the present invention to control the growth of microorganisms is from 10 ppm to 5,000 ppm active ingredient. In some embodiments of the invention, the active ingredients of the composition are present in an amount of at least 20 ppm, alternatively at least 50 ppm, alternatively at least 100 ppm, alternatively at least 150 ppm, alternatively at least 200 ppm. In some embodiments, the active ingredients of the composition are present in an amount of no more than 2,000 ppm, alternatively no more than 1,000 ppm, alternatively no more than 500 ppm, alternatively no more than 400 ppm, alternatively no more than 300 ppm, alternatively no more than 250 ppm, alternatively no more than 200 ppm, alternatively no more than 100 ppm, alternatively no more than 50 ppm. Concentrations mentioned above are in a liquid composition containing the biocide combinations.
The present invention also encompasses a method for reducing, or inhibiting, or preventing microbial growth in the use areas described above, especially in in-can preservative applications, by incorporating the claimed biocide combination into the materials.
The synergism of the biocides combination of the present invention was determined using the method described by Kull, F. C., et. al in Applied Microbiology 9:538-541 (1961). The formula to calculate the synergy index (SI) is
Qa/QA+Qb/QB=SI
QA=concentration of compound A in ppm, acting alone produced an end point (growth/no growth)
Qa=concentration of compound A in ppm, in the mixture, which produced an end point (growth/no growth)
QB=concentration of compound B in ppm, acting alone produced an end point (growth/no growth)
Qb=concentration of compound B in ppm, in the mixture, which produced an end point (growth/no growth)
In this study, biocide end point is defined as exhibiting at least 4 log bacterial or yeast reduction or maintaining a maximum 2 log bacterial or yeast count at the specified contact time. If end point could not be established, the highest concentration of biocide tested will be used as the end point for the calculation and the SI will be recorded in “less than or <” values
Synergism within two biocides is demonstrated when the SI has a value less than 1. The mixtures showed an additive effect if SI is equal to 1 and antagonistic if SI is greater than 1. The Minimum Inhibitory Test (MIC) is designed to evaluate the lowest concentration of a biocide, biocide blend or biocide combination to prevent bacteria, yeast, or fungi from growing in a defined broth. After incubation, the samples are rated based on visually detectable turbidity.
This test was carried out with a dilution factor of 1.5 for the biocides.
The following biocide products/mixtures were tested against two bacteria strains and one yeast:
Pseudomonas aeruginosa
Staphylococcus aureus
Candida albicans
The results of two biocides exhibiting synergy against the bacteria and yeast are presented in Tables 1-3.
Pseudomonas
aeruginosa DSM # 939
Staphylococcus
Aureus DSM # 799
Candida
Albicans DSM # 1386
Filing Document | Filing Date | Country | Kind |
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PCT/US16/18613 | 2/19/2016 | WO | 00 |
Number | Date | Country | |
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62121943 | Feb 2015 | US | |
62121943 | Feb 2015 | US |