WO2007139950A2 - Isothiazolinone biocides enhanced by zinc ions - Google Patents

Isothiazolinone biocides enhanced by zinc ions Download PDF

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Publication number
WO2007139950A2
WO2007139950A2 PCT/US2007/012518 US2007012518W WO2007139950A2 WO 2007139950 A2 WO2007139950 A2 WO 2007139950A2 US 2007012518 W US2007012518 W US 2007012518W WO 2007139950 A2 WO2007139950 A2 WO 2007139950A2
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WIPO (PCT)
Prior art keywords
zinc
composition
isothiazolin
combinations
group
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Ceased
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PCT/US2007/012518
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French (fr)
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WO2007139950A8 (en
WO2007139950A3 (en
Inventor
Nicholas Edward Thompson
Malcolm Greenhalgh
Fitzgerald Clarke
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Arch Chemicals Inc
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Arch Chemicals Inc
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Priority to MX2008014734A priority Critical patent/MX2008014734A/en
Priority to AU2007267842A priority patent/AU2007267842B2/en
Priority to EP07809194A priority patent/EP2023736A4/en
Priority to PL17171739T priority patent/PL3262941T3/en
Priority to CA2653212A priority patent/CA2653212C/en
Priority to CN2007800193089A priority patent/CN101453899B/en
Priority to BRPI0711226-2A priority patent/BRPI0711226A2/en
Priority to JP2009512168A priority patent/JP2009538319A/en
Application filed by Arch Chemicals Inc filed Critical Arch Chemicals Inc
Priority to PL14150293T priority patent/PL2742803T3/en
Priority to KR1020157020398A priority patent/KR20150094782A/en
Priority to EP17171739.0A priority patent/EP3262941B1/en
Priority to NZ572556A priority patent/NZ572556A/en
Priority to EP14150293.0A priority patent/EP2742803B1/en
Publication of WO2007139950A2 publication Critical patent/WO2007139950A2/en
Publication of WO2007139950A8 publication Critical patent/WO2007139950A8/en
Publication of WO2007139950A3 publication Critical patent/WO2007139950A3/en
Anticipated expiration legal-status Critical
Priority to US13/850,672 priority patent/US9717250B2/en
Ceased 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
    • 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
    • A01N43/80—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 1,2
    • 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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/41—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having five-membered rings with two or more ring hetero atoms, at least one of which being nitrogen, e.g. tetrazole
    • A61K31/425—Thiazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/555—Heterocyclic compounds containing heavy metals, e.g. hemin, hematin, melarsoprol
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/24—Heavy metals; Compounds thereof
    • A61K33/30—Zinc; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides

Definitions

  • Isothiazolinones such as l,2-benzisothiazolin-3-one (also referred to as "BIT")
  • BIT l,2-benzisothiazolin-3-one
  • ZC zinc chloride
  • DTP 2,2'-dithiopyridine-l,l '-dioxide
  • Example 3 of '190A publication compares compositions containing BIT plus ZC plus DTP against a control example containing only BIT plus ZC.
  • the results given in Example 3 and Table 3 of the publication indicate that inclusion of DTP allows decreased usage of BIT in the composition. Nonetheless, the amount of BIT (2.5 ppm) employed in the control example has been found by the present inventors to be insufficient for antimicrobial efficacy in real-world applications.
  • the present invention relates to an antimicrobial composition
  • an antimicrobial composition comprising (a) at least one isothiazolin-3-one and (b) at least one zinc compound selected from the group consisting of zinc salts, zinc oxides, zinc hydroxides, and combinations thereof.
  • Illustrative zinc salts are zinc chloride, zinc sulfide, zinc carbonate, basic zinc carbonate, and combinations thereof.
  • the zinc compound provides a source of metal ion in the antimicrobial composition.
  • the isothiazolin-3-one is present in an amount of from 1 to 500 ppm (preferably from 5 to 500 ppm), the zinc compound is present in an amount from 5 to 200,000 ppm (preferably from 5 to 500 ppm), and the weight ratio of the isothiazolin-3-one to the zinc compound is from 1 :2000 to 100:1 (preferably from 1 : 100 to 100:1).
  • the antimicrobial composition additionally comprises a pyrithione salt or pyrithione acid.
  • Useful pyrithione salts include copper pyrithione, zinc pyrithione, sodium pyrithione, pyrithione disulfide, and combinations thereof.
  • the present invention relates to an antimicrobial composition concentrate that, upon dilution with water, provides antimicrobial efficacy in a functional fluid.
  • the concentrate comprises (a) at least one isothiazolin-3-one and (b) at least one zinc compound selected from the group consisting of zinc salts, zinc oxides, zinc hydroxides, and combinations thereof.
  • component (a) is present in an amount of from 1 to 95 %w/w
  • component (b) is present in an amount of from 1 to 50 %w/w based on the total weight of the concentrate, with the proviso that the weight percent of (a) plus (b) does not exceed 100% by weight.
  • the present invention relates to functional fluid that comprises a base medium plus (a) at least one isothiazolin-3-one and (b) at least one zinc compound selected from the group consisting of zinc salts, zinc oxides, zinc hydroxides, and combinations thereof.
  • zinc salts are zinc chloride, zinc sulfide, zinc carbonate, basic zinc carbonate, and combinations thereof.
  • the isothiazolin-3-one is present in an amount of from 1 to 500 ppm (preferably from 5 to 500 ppm), the metal compound is present in an amount of from 5 to 200,00 ppm (preferably from 5 to 500 ppm), and the weight ratio of the isothiazolin-3-one to zinc ion is from 1:2000 to 100:1 (preferably from 100:1 to 1:100).
  • the antimicrobial composition additionally comprises a pyrithione salt or pyrithione acid.
  • Useful pyrithione salts include copper pyrithione, zinc pyrithione, sodium pyrithione, and pyrithione disulfide.
  • the base medium for the functional fluid can be, for example, a polymer useful in polymer emulsions.
  • polymer systems are lattices, such as acrylic and substituted (meth)acrylates, styrene/butadiene, ethylene vinyl acetate, polyvinyl acetate, styrene/butadiene/N-methylol acrylamide, nitrile and copolymers of the aforementioned.
  • Typical functional fluids include coating compositions, such as paints, adhesives, sealants, caulks, mineral and pigment slurries, printing inks, agricultural pesticide formulations, household products, personal care, metal working fluids and other aqueous based systems.
  • Figure 1 provides a graphical depiction of an Isobologram showing Antimicrobial Activity of Mixtures of l,2-Benzisothiazolin-3-one ("BIT") and Zinc Chloride against Ps .aeruginosa based on Fractional Inhibitory Concentration values.
  • BIT l,2-Benzisothiazolin-3-one
  • Zinc Chloride against Ps .aeruginosa based on Fractional Inhibitory Concentration values.
  • Figure 2 provides a graphical depiction of an Isobologram showing
  • Figure 3 provides a graphical depiction of an Isobologram showing
  • Figure 4 provides a graphical depiction of an Isobologram showing Antimicrobial Activity of Mixtures of N-(n-butyl)- 1 ,2-benzisothiazolin-3-one ("BBIT”) and Zinc Chloride against Ps. aeruginosa based on Fractional Inhibitory Concentration values.
  • BBIT N-(n-butyl)- 1 ,2-benzisothiazolin-3-one
  • Figure 5 provides a graphical depiction of an Isobologram showing Antimicrobial Activity of Mixtures of BIT and Sodium Chloride against Ps. aeruginosa based on Fractional Inhibitory Concentration values.
  • an antimicrobial composition containing an isothiazolin-3-one, plus a zinc compound selected from the group consisting of zinc salts, zinc oxides, zinc hydroxides, and combinations thereof exhibits enhanced antimicrobial efficacy, as compared to isothiazolin-containing compositions that do not contain the metal compound.
  • Enhanced efficacy are suitably provided in antimicrobial compositions over a wide range of pHs of
  • the antimicrobial composition of the present invention is suitably incorporated into a functional fluid.
  • the functional fluid suitably comprises a base medium plus (a) at least one isothiazolin-3-one and (b) at least one zinc compound selected from the group consisting of zinc salts of organic acids, zinc salts of inorganic acids, zinc oxides, zinc hydroxides, and combinations thereof, llustrative zinc salts include zinc chloride, zinc sulfide, zinc carbonate, basic zinc carbonate (also known as "hydroxy-containing zinc carbonate", also know as "zinc hydroxy carbonate” which is further identified by the empirical formula ZnS(OH) 6 (COa) 2 ), and combinations thereof.
  • the isothiazolinone useful in the present invention is preferably an isothiazolin- 3-one that is selected from: l,2-benzisothiazolin-3-one ("BIT"), N-(n-butyl)-l,2- benzisothiazolin-3-one ("BBIT”), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one ("DCOIT”), 2-rnethyl-4-isothiazolin-3-one (“MIT”), mixtures of 5-chloro-2-methyl-4-isothiazolin-3- one (“ClMIT”) plus MIT (available from Rohm and Haas Company, Philadelphia, PA under the tradename Kathon ® ) dithio-2,2'-bis(benzmethylamide), and combinations thereof.
  • Particularly preferred isothiazolins are BIT, MIT and BBIT, and combinations thereof.
  • the isothiazolin-3-one is present in an amount of from 1 to 500 ppm (preferably from 5 to 500 ppm), the zinc compound is present in an amount of from 5 to 200,000 ppm (preferably from 5 to 500 ppm), and the weight ratio of the isothiazolin-3-one to the zinc compound is from 1:2000 to 100:1 (preferably from 100:1 to 1 :100).
  • the antimicrobial composition additionally comprises a pyrithione salt or pyrithione acid.
  • Useful pyrithione salts include copper pyrithione, zinc pyrithione, sodium pyrithione. If used, the pyrithione salt or pyrithione acid is suitably present in the composition in an amount of from about 0.001% w/w to about 1.0% w/w.
  • the combination of antimicrobial components for the antimicrobial composition can be provided in the form of an antimicrobial composition concentrate that, upon dilution with water, provides antimicrobial efficacy in a functional fluid.
  • the concentrate comprises (a) at least one isothiazolin-3-one and (b) at least one zinc compound selected from the group consisting of zinc salts, zinc oxides, zinc hydroxides, and combinations thereof.
  • component (a) is present in an amount of from 1 to 95 %w/w
  • component (b) is present in an amount of from 1 to 50% w/w.
  • the antimicrobial compositions of the present invention are suitably used in functional fluids such as polymer emulsions, or other coating compositions, to impart both wet state and dry film preservation.
  • the base medium can be, for example, a polymer useful in polymer emulsions wherein the polymer is selected from the group consisting of acrylic and substituted (meth)acrylates, styrene/butadiene, ethylene vinyl acetate, polyvinyl acetate, styrene/butadiene/N-methylol acrylamide, nitrile and copolymers of the aforementioned.
  • Typical functional fluids include coating compositions, such as paints, adhesives, sealants, caulks, mineral and pigment slurries, printing inks, agricultural pesticide formulations, household products, personal care, metal working fluids and other aqueous based systems.
  • coating compositions such as paints, adhesives, sealants, caulks, mineral and pigment slurries, printing inks, agricultural pesticide formulations, household products, personal care, metal working fluids and other aqueous based systems.
  • NCIMB 8295 Providencia rettgeri, NCIMB 10842 Serratia marcescens, NCIMB 9523 Aeromonas hydrophila, NCIMB9233 Alcaligenes spp. (Wet State Preservation isolate) Burkholderia cepacia, ATCC 25416 Pseudomonas putida, NCIMB9494
  • AU test species were cultured onto nutrient agar and incubated for 24 hours at 30 0 C. After this period individual suspensions of each test organism were prepared at a concentration of 10 6 colony forming units per ml in saline solution by means of a Thoma counting chamber, achieved by mixing equal volumes of the individual suspensions. The concentration of bacteria in each aliquot after each challenge was 2 x 10 6 per ml.
  • the antimicrobial additive-containing paint samples were stored at 4O 0 C for 7 days prior to commencing the test.
  • the paint samples were challenged with l%v/v of bacterial suspension as described above. All test samples were incubated at 30 0 C for the duration of the test and examined for viable bacteria after 1, 3 and 7 days after each challenge. Viable bacteria were detected by streaking aliquots onto nutrient agar followed by incubation at 30°C for 2 days.
  • Table I presents the results obtained after the third inoculation days 1 , 3 and 7.
  • Results demonstrate a potentiating effect of BIT in combination with a zinc containing salt when compared against a commercial product, namely PROXEL BD20 a product of Arch Chemicals, Inc. containing only BIT for the preservation of a commercial latex in that only 100 ppm of BIT is required in the presence of a zinc containing salt compared to 250 ppm of BIT for sample containing only BIT.
  • a commercial product namely PROXEL BD20 a product of Arch Chemicals, Inc. containing only BIT for the preservation of a commercial latex in that only 100 ppm of BIT is required in the presence of a zinc containing salt compared to 250 ppm of BIT for sample containing only BIT.
  • NCIB 10421 Pseudomonas aeruginosa maintained on nutrient agar, were used to study the synergy between BIT and ZnCb.
  • Bacteria were grown to stationary phase (approximately 24 hours) in nutrient broth (approximately 10 9 organisms per ml). A 0.1%(v/v) inoculum was used to seed fresh medium and 100 ⁇ l of the inoculum was then added to each well of a microtitre plate, except for the first well which contained 200 ⁇ l. .
  • the concentration of the compounds under investigation were varied in each well along the ordinate axis. The presence or absence of growth was recorded by visual inspection after 24 hours incubation at 37°C.
  • Microtitre plates were used for this assay.
  • a simple matrix was constructed with varied concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • As the microtitre plate has only 96 wells, the combinations of the two compounds that made up the extreme concentrations (highest and lowest) were omitted. Solutions were made up in broth at two times the final concentrations after pre-dissolving the compounds in distilled water.
  • ZnCl 2 300 450 375 450 BIT is l,2-benzisothiazolin-3 -one available from Arch Limited PROXEL GXL.
  • the Minimum Inhibitory Concentration is the lowest concentration of biocide which showed growth inhibition when used alone.
  • FIC Fractional Inhibitory Concentration
  • a Fractional Inhibitory Concentration is the concentration of biocide which controlled growth in the mixture divided by the MIC of that biocide. FIC values for both compounds in the mixture were calculated and the results are shown in Table 3. The sum of these two figures gives an indication of the action of the two biocides. A value less than one indicates an enhanced effect, if the total is unity or greater the action is additive and if the value is greater than two the biocides are antagonistic.
  • NCIB 10421 Pseudomonas aeruginosa maintained on nutrient agar, were used to study the synergy of Kathon ® and ZnCb.
  • Bacteria were grown to stationary phase (approximately 24 hours) in nutrient broth (approximately 10 9 organisms per ml). A 0.1%(v/v) inoculum was used to seed fresh medium and 100 ⁇ l of the inoculum was then added to each well of a microtitre plate, except for the first well which contained 200 ⁇ l.
  • the concentration of the compounds under investigation were varied in each well along the ordinate axis. The presence or absence of growth was recorded by visual inspection after 24 hours incubation at 37°C.
  • Microtitre plates were used for this assay.
  • a simple matrix was constructed with varied concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • As the microtitre plate has only 96 wells, the combinations of the two compounds that made up the extreme concentrations (highest and lowest) were omitted. Solutions were made up in broth at two times the final concentrations after pre-dissolving the compounds in distilled water.
  • ZnCl 2 294 294 210 600 The mixture of CIMIT and MIT is available from Rohm and Haas Company, Philadelphia, PA under the tradename Kathon ® .
  • the Minimum Inhibitory Concentration is the lowest concentration of biocide which showed growth inhibition when used alone.
  • FIC Fractional Inhibitory Concentration
  • a Fractional Inhibitory Concentration is the concentration of biocide which controlled growth in the mixture divided by the MIC of that biocide. FIC values for both compounds in the mixture were calculated and the results are shown in Table 5. The sum of these two figures gives an indication of the action of the two biocides. A value less than one indicates an enhanced effect, if the total is unity or greater the action is additive and if the value is greater than two the biocides are antagonistic.
  • NCIB 10421 Pseudomonas aeruginosa maintained on nutrient agar, were used to study the synergy between MIT and ZnCl 2 .
  • Bacteria were grown to stationary phase (approximately 24 hours) in nutrient broth (approximately 10 9 organisms per ml). A 0.1%(v/v) inoculum was used to seed fresh medium and 100 ⁇ l of the inoculum was then added to each well of a microtitre plate, except for the first well which contained 200 ⁇ l.
  • the concentration of the compounds under investigation were varied in each well along the ordinate axis. The presence or absence of growth was recorded by visual inspection after 24 hours incubation at 37°C.
  • Microtitre plates were used for this assay.
  • a simple matrix was constructed with varied concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • As the microtitre plate has only 96 wells, the combinations of the two compounds that made up the extreme concentrations (highest and lowest) were omitted. Solutions were made up in broth at two times the final concentrations after pre-dissolving the compounds in distilled water.
  • the Minimum Inhibitory Concentration is the lowest concentration of biocide which showed growth inhibition when used alone.
  • FIC Fractional Inhibitory Concentration
  • a Fractional Inhibitory Concentration is the concentration of biocide which controlled growth in the mixture divided by the MIC of that biocide. FIC values for both compounds- in the mixture were calculated and the results are shown in Table 7. The sum of these two figures gives an indication of the action of the two biocides. A value less than one indicates an enhanced effect, if the total is unity or greater the action is additive and if the value is greater than two the biocides are antagonistic.
  • NCIB 10421 Pseudomonas aeruginosa maintained on nutrient agar, were used to study the synergy between BBIT and ZnCl 2
  • Bacteria were grown to stationary phase (approximately 24 hours) in nutrient broth (approximately 10 9 organisms per ml). A 0.1%(v/v) inoculum was used to seed fresh medium and 100 ⁇ l of the inoculum was then added to each well of a microtitre plate, except for the first well which contained 200 ⁇ l.
  • the concentration of the compounds under investigation were varied in each well along the ordinate axis. The presence or absence of growth was recorded by visual inspection after 24 hours incubation at 37°C.
  • Microtitre plates were used for this assay.
  • a simple matrix was constructed with varied concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • As the microtitre plate has only 96 wells, the combinations of the two compounds that made up the extreme concentrations (highest and lowest) were omitted. Solutions were made up in broth at two times the final concentrations after pre- dissolving the compounds in distilled water.
  • BBIT is N-(n-butyl)-l,2-benzisothiazolin-3-one.
  • the Minimum Inhibitory Concentration is the lowest concentration of biocide which showed growth inhibition when used alone.
  • a value less than one indicates an enhanced effect, if the total is unity or greater the action is additive and if the value is greater than two the biocides are antagonistic.
  • the two biocides on linear scales is constructed, when the combination is additive the isobole (i.e. the line joining the points that represent all combinations with the same effect including the equally effective concentrations of the biocides used alone) is straight, enhanced combinations give concave isoboles and antagonistic combinations give convex isoboles.
  • the combination of BBIT and ZnCl 2 has an enhanced effect
  • NCIB 10421 Pseudomonas aeruginosa maintained on nutrient agar, were used to study the efficacy of the combination of BIT with sodium chloride.
  • Bacteria were grown to stationary phase (approximately 24 hours) in nutrient broth (approximately 10 9 organisms per ml). A 0.1%(v/v) inoculum was used to seed fresh medium and 100 ⁇ l of the inoculum was then added to each well of a microtitre plate, except for the first well which contained 200 ⁇ l.
  • the concentration of the compounds under investigation were varied in each well along the ordinate axis. The presence or absence of growth was recorded by visual inspection after 24 hours incubation at 37°C.
  • Microtitre plates were used for this assay.
  • a simple matrix was constructed with varied concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array.
  • As the microtitre plate has only 96 wells, the combinations of the two compounds that made up the extreme concentrations (highest and lowest) were omitted. Solutions were made up in broth at two times the final concentrations after pre-dissolving the compounds in distilled water.
  • BIT is l,2 ⁇ benzisothiazolin-3-one available from Arch Limited as PROXEL R K T 1 M M , GXL
  • the Minimum Inhibitory Concentration is the lowest concentration of biocide which showed growth inhibition when used alone.
  • FIC Fractional Inhibitory Concentration
  • a Fractional Inhibitory Concentration is the concentration of biocide which controlled growth in the mixture divided by the MIC of that biocide. FIC values for both compounds in the mixture were calculated and the results are shown in Table 11. The sum of these two figures gives an indication of the action of the two biocides. A value less than one indicates an enhanced effect, if the total is unity or greater the action is additive and if the value is greater than two the biocides are antagonistic.
  • Example 2 shows unexpected potentiation results against Ps. aeruginosa.

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Abstract

The present invention relates to an antimicrobial composition comprising an isothiazolinone, such as l,2-benzisothiazolin-3-one, and a zinc compound selected from zinc salts, zinc oxides, zinc hydroxides or combinations thereof. Useful zinc salts include for example, oxides, sulfates, chlorides, and combinations thereof. In use, the zinc from the zinc compound enhances the antimicrobial activity to the isothiazolin-containing composition. This enhancement permits achieving the desired antimicrobial activity at a lower usage rate than is achieved using the isothiazolinone in the absence of the zinc compound. The antimicrobial composition can also contain co-biocides, such as pyrithiones, including zinc pyrithione or copper pyrithione.

Description

ISOTHIAZOLINONE BIOCIDES ENHANCED BY ZINC IONS
BACKGROUND OF THE INVENTION
[001] Isothiazolinones, such as l,2-benzisothiazolin-3-one (also referred to as "BIT"), are know to be effective antimicrobials. BIT, as disclosed for example in formulations described in European patent EP 0 703 726, is widely used as a bactericide in a variety of applications. Illustratively, British patent publication GB2,230, 19OA discloses a •preservative composition containing BIT and an adduct of zinc chloride ("ZC"), together with 2,2'-dithiopyridine-l,l '-dioxide ("DTP"). Example 3 of '190A publication compares compositions containing BIT plus ZC plus DTP against a control example containing only BIT plus ZC. The results given in Example 3 and Table 3 of the publication indicate that inclusion of DTP allows decreased usage of BIT in the composition. Nonetheless, the amount of BIT (2.5 ppm) employed in the control example has been found by the present inventors to be insufficient for antimicrobial efficacy in real-world applications.
[002] While BIT has proven useful in a wide range of applications, the useful amount of BIT that can be added to a commercial product is limited by efficacy and economic considerations and to a lesser extent by environmental and toxicological concerns. Accordingly, alternative antimicrobial compositions are needed for wet state applications that are cost-effective and minimize the likelihood of adverse environmental and toxicological effects. The present invention provides one such alternative.
SUMMARY OF THE INVENTION
[003] In one aspect, the present invention relates to an antimicrobial composition comprising (a) at least one isothiazolin-3-one and (b) at least one zinc compound selected from the group consisting of zinc salts, zinc oxides, zinc hydroxides, and combinations thereof. Illustrative zinc salts are zinc chloride, zinc sulfide, zinc carbonate, basic zinc carbonate, and combinations thereof. The zinc compound provides a source of metal ion in the antimicrobial composition. In the composition, the isothiazolin-3-one is present in an amount of from 1 to 500 ppm (preferably from 5 to 500 ppm), the zinc compound is present in an amount from 5 to 200,000 ppm (preferably from 5 to 500 ppm), and the weight ratio of the isothiazolin-3-one to the zinc compound is from 1 :2000 to 100:1 (preferably from 1 : 100 to 100:1). Optionally, the antimicrobial composition additionally comprises a pyrithione salt or pyrithione acid. Useful pyrithione salts include copper pyrithione, zinc pyrithione, sodium pyrithione, pyrithione disulfide, and combinations thereof.
[004] In another aspect, the present invention relates to an antimicrobial composition concentrate that, upon dilution with water, provides antimicrobial efficacy in a functional fluid. The concentrate comprises (a) at least one isothiazolin-3-one and (b) at least one zinc compound selected from the group consisting of zinc salts, zinc oxides, zinc hydroxides, and combinations thereof. In the concentrate, component (a) is present in an amount of from 1 to 95 %w/w, and component (b) is present in an amount of from 1 to 50 %w/w based on the total weight of the concentrate, with the proviso that the weight percent of (a) plus (b) does not exceed 100% by weight.
[005] In yet another aspect, the present invention relates to functional fluid that comprises a base medium plus (a) at least one isothiazolin-3-one and (b) at least one zinc compound selected from the group consisting of zinc salts, zinc oxides, zinc hydroxides, and combinations thereof. Illustrative zinc salts are zinc chloride, zinc sulfide, zinc carbonate, basic zinc carbonate, and combinations thereof. In the composition, the isothiazolin-3-one is present in an amount of from 1 to 500 ppm (preferably from 5 to 500 ppm), the metal compound is present in an amount of from 5 to 200,00 ppm (preferably from 5 to 500 ppm), and the weight ratio of the isothiazolin-3-one to zinc ion is from 1:2000 to 100:1 (preferably from 100:1 to 1:100). Optionally, the antimicrobial composition additionally comprises a pyrithione salt or pyrithione acid. Useful pyrithione salts include copper pyrithione, zinc pyrithione, sodium pyrithione, and pyrithione disulfide. The base medium for the functional fluid can be, for example, a polymer useful in polymer emulsions. Examples of polymer systems are lattices, such as acrylic and substituted (meth)acrylates, styrene/butadiene, ethylene vinyl acetate, polyvinyl acetate, styrene/butadiene/N-methylol acrylamide, nitrile and copolymers of the aforementioned. Typical functional fluids include coating compositions, such as paints, adhesives, sealants, caulks, mineral and pigment slurries, printing inks, agricultural pesticide formulations, household products, personal care, metal working fluids and other aqueous based systems. [006] These and other aspects will become apparent upon reading the following detailed description of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[007] Figure 1 provides a graphical depiction of an Isobologram showing Antimicrobial Activity of Mixtures of l,2-Benzisothiazolin-3-one ("BIT") and Zinc Chloride against Ps .aeruginosa based on Fractional Inhibitory Concentration values.
[008] Figure 2 provides a graphical depiction of an Isobologram showing
Antimicrobial Activity of Mixtures of Kathon® (a mixture of 5-chloro-2-methyl-4- isothiazolin-3-one ("CIMIT") and 2-methyl-4-isothiazolin-3-one ("MIT")) and Zinc Chloride against Ps. aeruginosa based on Fractional Inhibitory Concentration values.
[009] Figure 3 provides a graphical depiction of an Isobologram showing
Antimicrobial Activity of Mixtures of MIT and Zinc Chloride against Ps. aeruginosa based on Fractional Inhibitory Concentration values.
[0010] Figure 4 provides a graphical depiction of an Isobologram showing Antimicrobial Activity of Mixtures of N-(n-butyl)- 1 ,2-benzisothiazolin-3-one ("BBIT") and Zinc Chloride against Ps. aeruginosa based on Fractional Inhibitory Concentration values.
[0011] Figure 5 provides a graphical depiction of an Isobologram showing Antimicrobial Activity of Mixtures of BIT and Sodium Chloride against Ps. aeruginosa based on Fractional Inhibitory Concentration values.
DETAILED DESCRIPTION OF THE INVENTION
[0012] It has now been surprisingly found in accordance with the present invention that an antimicrobial composition containing an isothiazolin-3-one, plus a zinc compound selected from the group consisting of zinc salts, zinc oxides, zinc hydroxides, and combinations thereof, exhibits enhanced antimicrobial efficacy, as compared to isothiazolin-containing compositions that do not contain the metal compound. Enhanced efficacy are suitably provided in antimicrobial compositions over a wide range of pHs of
Figure imgf000006_0001
[0013] The antimicrobial composition of the present invention is suitably incorporated into a functional fluid. The functional fluid suitably comprises a base medium plus (a) at least one isothiazolin-3-one and (b) at least one zinc compound selected from the group consisting of zinc salts of organic acids, zinc salts of inorganic acids, zinc oxides, zinc hydroxides, and combinations thereof, llustrative zinc salts include zinc chloride, zinc sulfide, zinc carbonate, basic zinc carbonate (also known as "hydroxy-containing zinc carbonate", also know as "zinc hydroxy carbonate" which is further identified by the empirical formula ZnS(OH)6(COa)2 ), and combinations thereof.
[0014] The isothiazolinone useful in the present invention is preferably an isothiazolin- 3-one that is selected from: l,2-benzisothiazolin-3-one ("BIT"), N-(n-butyl)-l,2- benzisothiazolin-3-one ("BBIT"), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one ("DCOIT"), 2-rnethyl-4-isothiazolin-3-one ("MIT"), mixtures of 5-chloro-2-methyl-4-isothiazolin-3- one ("ClMIT") plus MIT (available from Rohm and Haas Company, Philadelphia, PA under the tradename Kathon®) dithio-2,2'-bis(benzmethylamide), and combinations thereof. Particularly preferred isothiazolins are BIT, MIT and BBIT, and combinations thereof.
[0015] In the composition, the isothiazolin-3-one is present in an amount of from 1 to 500 ppm (preferably from 5 to 500 ppm), the zinc compound is present in an amount of from 5 to 200,000 ppm (preferably from 5 to 500 ppm), and the weight ratio of the isothiazolin-3-one to the zinc compound is from 1:2000 to 100:1 (preferably from 100:1 to 1 :100).
[0016] Optionally, the antimicrobial composition additionally comprises a pyrithione salt or pyrithione acid. Useful pyrithione salts include copper pyrithione, zinc pyrithione, sodium pyrithione. If used, the pyrithione salt or pyrithione acid is suitably present in the composition in an amount of from about 0.001% w/w to about 1.0% w/w. [0017] In one embodiment, the combination of antimicrobial components for the antimicrobial composition can be provided in the form of an antimicrobial composition concentrate that, upon dilution with water, provides antimicrobial efficacy in a functional fluid. The concentrate comprises (a) at least one isothiazolin-3-one and (b) at least one zinc compound selected from the group consisting of zinc salts, zinc oxides, zinc hydroxides, and combinations thereof. In the concentrate, component (a) is present in an amount of from 1 to 95 %w/w, and component (b) is present in an amount of from 1 to 50% w/w.
[0018] The antimicrobial compositions of the present invention are suitably used in functional fluids such as polymer emulsions, or other coating compositions, to impart both wet state and dry film preservation. The base medium can be, for example, a polymer useful in polymer emulsions wherein the polymer is selected from the group consisting of acrylic and substituted (meth)acrylates, styrene/butadiene, ethylene vinyl acetate, polyvinyl acetate, styrene/butadiene/N-methylol acrylamide, nitrile and copolymers of the aforementioned. Typical functional fluids include coating compositions, such as paints, adhesives, sealants, caulks, mineral and pigment slurries, printing inks, agricultural pesticide formulations, household products, personal care, metal working fluids and other aqueous based systems.
[0019] The invention is further described in the Examples given below. All percentages given herein are weight percents based on the total weight of the composition, unless otherwise stated.
Example 1
In this example, samples of a commercial water based acrylic latex, trade name REVACRYL IA, supplied by the Harlow Chemical Company, pH 8.1, containing antimicrobial additives in amounts as identified in Table I below, were challenged with a bacterial suspension consisting of
Pseudomonas aeruginosa, NCIMB 8295 Providencia rettgeri, NCIMB 10842 Serratia marcescens, NCIMB 9523 Aeromonas hydrophila, NCIMB9233 Alcaligenes spp. (Wet State Preservation isolate) Burkholderia cepacia, ATCC 25416 Pseudomonas putida, NCIMB9494
AU test species were cultured onto nutrient agar and incubated for 24 hours at 30 0C. After this period individual suspensions of each test organism were prepared at a concentration of 106 colony forming units per ml in saline solution by means of a Thoma counting chamber, achieved by mixing equal volumes of the individual suspensions. The concentration of bacteria in each aliquot after each challenge was 2 x 106per ml.
The antimicrobial additive-containing paint samples were stored at 4O0C for 7 days prior to commencing the test. The paint samples were challenged with l%v/v of bacterial suspension as described above. All test samples were incubated at 300C for the duration of the test and examined for viable bacteria after 1, 3 and 7 days after each challenge. Viable bacteria were detected by streaking aliquots onto nutrient agar followed by incubation at 30°C for 2 days.
Table I presents the results obtained after the third inoculation days 1 , 3 and 7.
Table I
Figure imgf000009_0001
Assessments are rated as: no growth detected +++ heavy growth — coalescing colonies visible throughout
T 0-5 colonies present C confluent heavy growth
S 5-10 colonies
1+ 20 - 100 colonies
+ light growth - no specified number of colonies
-H- moderate growth — colonies visible, some coalescence
Results demonstrate a potentiating effect of BIT in combination with a zinc containing salt when compared against a commercial product, namely PROXEL BD20 a product of Arch Chemicals, Inc. containing only BIT for the preservation of a commercial latex in that only 100 ppm of BIT is required in the presence of a zinc containing salt compared to 250 ppm of BIT for sample containing only BIT. Example 2
Investigation of potentiation between l,2-Benzisothiazolin-3-one (BIT) and Zinc Chloride (ZnCh) against Pseudomonas aeruginosa.
Bacteria
Pseudomonas aeruginosa (NCIB 10421) maintained on nutrient agar, were used to study the synergy between BIT and ZnCb.
Calculation of Minimum Inhibitory Concentrations Against Mono-cultures
Bacteria were grown to stationary phase (approximately 24 hours) in nutrient broth (approximately 109 organisms per ml). A 0.1%(v/v) inoculum was used to seed fresh medium and 100 μl of the inoculum was then added to each well of a microtitre plate, except for the first well which contained 200 μl. .
Using doubling dilutions, the concentration of the compounds under investigation were varied in each well along the ordinate axis. The presence or absence of growth was recorded by visual inspection after 24 hours incubation at 37°C.
Calculation of Antimicrobial Activity Against Mono-cultures
Microtitre plates were used for this assay. A simple matrix was constructed with varied concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array. As the microtitre plate has only 96 wells, the combinations of the two compounds that made up the extreme concentrations (highest and lowest) were omitted. Solutions were made up in broth at two times the final concentrations after pre-dissolving the compounds in distilled water.
The mixture (100 μl) was added to the plate so that the total volume in each well was 200 μl. Nutrient broth was used for Ps. aeruginosa . .Plates were incubated for 16-24 hours at 37°. The presence or absence of growth was determined by visual inspection. Results for Example 2
Table 2: Antimicrobial Activity of Compounds Under Investigation
Table 2
COMPOUND MIC ( >pm) against Ps.aeruginosa
1 2 3 4
BIT 30 42 42 30
ZnCl2 300 450 375 450 BIT is l,2-benzisothiazolin-3 -one available from Arch Limited PROXEL GXL.
Calculation of activity Against Mono-cultures
The Minimum Inhibitory Concentration (MIC) is the lowest concentration of biocide which showed growth inhibition when used alone. For the purpose of Fractional Inhibitory Concentration (FIC) calculations, if a single biocide did not control growth, the MIC was taken as the highest concentration used. A Fractional Inhibitory Concentration is the concentration of biocide which controlled growth in the mixture divided by the MIC of that biocide. FIC values for both compounds in the mixture were calculated and the results are shown in Table 3. The sum of these two figures gives an indication of the action of the two biocides. A value less than one indicates an enhanced effect, if the total is unity or greater the action is additive and if the value is greater than two the biocides are antagonistic.
Table 3: Fractional Inhibitory Concentrations for l,2-Benzisothiazolin-3-one (BIT) and Zinc Chloride (ZnCh) against Ps. aerueinos a
Table 3
Figure imgf000011_0001
If a graph with the axes representing the biocide Fractional Inhibitory Concentrations for the two biocides on linear scales is constructed, when the combination is additive the isobole ( i.e. the line joining the points that represent all combinations with the same effect including the equally effective concentrations of the biocides used alone) is straight, enhanced combinations give concave isoboles and antagonistic combinations give convex isoboles. As shown in FIG. 1, the combination of BIT and ZnCl2 has an enhanced effect against Ps.aeruginosa as confirmed by the concave isobole on the graph of FIG.l . Example 3
Investigation of potentiation between Kathon® (CIMIT/MIT) and Zinc Chloride (ZnCh) against Pseudomonas aeruginosa.
Bacteria
Pseudomonas aeruginosa (NCIB 10421) maintained on nutrient agar, were used to study the synergy of Kathon® and ZnCb.
Calculation of Minimum Inhibitory Concentrations Against Mono-cultures
Bacteria were grown to stationary phase (approximately 24 hours) in nutrient broth (approximately 109 organisms per ml). A 0.1%(v/v) inoculum was used to seed fresh medium and 100 μl of the inoculum was then added to each well of a microtitre plate, except for the first well which contained 200 μl.
Using doubling dilutions, the concentration of the compounds under investigation were varied in each well along the ordinate axis. The presence or absence of growth was recorded by visual inspection after 24 hours incubation at 37°C.
Calculation of Antimicrobial Activity Against Mono-cultures
Microtitre plates were used for this assay. A simple matrix was constructed with varied concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array. As the microtitre plate has only 96 wells, the combinations of the two compounds that made up the extreme concentrations (highest and lowest) were omitted. Solutions were made up in broth at two times the final concentrations after pre-dissolving the compounds in distilled water.
The mixture (100 μl) was added to the plate so that the total volume in each well was 200 μl. Nutrient broth was used for Ps. aeruginosa . Plates were incubated for 16-24 hours at 37°. The presence or absence of growth was determined by visual inspection. Results of Example 3
Table 4: Antimicrobial Activity of Compounds Under Investigation
Table 4
COMPOUND MIC ( ppm) against Ps. aeruginosa
1 2 3 4
Kathon 0.9 0.9 0.9 0.53
ZnCl2 294 294 210 600 The mixture of CIMIT and MIT is available from Rohm and Haas Company, Philadelphia, PA under the tradename Kathon®.
Calculation of Synergy Against Mono-cultures
The Minimum Inhibitory Concentration (MIC) is the lowest concentration of biocide which showed growth inhibition when used alone. For the purpose of Fractional Inhibitory Concentration (FIC) calculations, if a single biocide did not control growth, the MIC was taken as the highest concentration used. A Fractional Inhibitory Concentration is the concentration of biocide which controlled growth in the mixture divided by the MIC of that biocide. FIC values for both compounds in the mixture were calculated and the results are shown in Table 5. The sum of these two figures gives an indication of the action of the two biocides. A value less than one indicates an enhanced effect, if the total is unity or greater the action is additive and if the value is greater than two the biocides are antagonistic.
Table 5: Fractional Inhibitory Concentrations for Kathon (CIMIT/MTD and Zinc Chloride (ZnCl?) against Ps.aerusinosa
Table 5
Figure imgf000013_0001
If a graph with the axes representing the biocide Fractional Inhibitory Concentrations for the two biocides on linear scales is constructed, when the combination is additive the isobole (i.e. the line joining the points that represent all combinations with the same effect including the equally effective concentrations of the biocides used alone) is straight, enhanced combinations give concave isoboles and antagonistic combinations give convex isoboles. As shown in FIG. 2, the combination, of Kathon® and ZnCl2 has an enhanced effect against Ps.aeruginosa as confirmed by the concave isobole in FIG. 2. Example 4
Investigation of potentiation between MIT and Zinc Chloride (ZnCb) against Pseudomonas aeruginosa
Bacteria
Pseudomonas aeruginosa (NCIB 10421) maintained on nutrient agar, were used to study the synergy between MIT and ZnCl2.
Calculation of Minimum Inhibitory Concentrations Against Mono-cultures
Bacteria were grown to stationary phase (approximately 24 hours) in nutrient broth (approximately 109 organisms per ml). A 0.1%(v/v) inoculum was used to seed fresh medium and 100 μl of the inoculum was then added to each well of a microtitre plate, except for the first well which contained 200 μl.
Using doubling dilutions, the concentration of the compounds under investigation were varied in each well along the ordinate axis. The presence or absence of growth was recorded by visual inspection after 24 hours incubation at 37°C.
Calculation of Antimicrobial Activity Against Mono-cultures
Microtitre plates were used for this assay. A simple matrix was constructed with varied concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array. As the microtitre plate has only 96 wells, the combinations of the two compounds that made up the extreme concentrations (highest and lowest) were omitted. Solutions were made up in broth at two times the final concentrations after pre-dissolving the compounds in distilled water.
The mixture (100 μl) was added to the plate so that the total volume in each well was 200 μl. Nutrient broth was used for Ps. aeruginosa . Plates were incubated for 16-24 hours at 37°. The presence or absence of growth was determined by visual inspection. Results of Example 4
Table 6: Antimicrobial Activity of Compounds Under Investigation
Table 6
Figure imgf000015_0001
Calculation of Synergy Against Mono-cultures
The Minimum Inhibitory Concentration (MIC) is the lowest concentration of biocide which showed growth inhibition when used alone. For the purpose of Fractional Inhibitory Concentration (FIC) calculations, if a single biocide did not control growth, the MIC was taken as the highest concentration used. A Fractional Inhibitory Concentration is the concentration of biocide which controlled growth in the mixture divided by the MIC of that biocide. FIC values for both compounds- in the mixture were calculated and the results are shown in Table 7. The sum of these two figures gives an indication of the action of the two biocides. A value less than one indicates an enhanced effect, if the total is unity or greater the action is additive and if the value is greater than two the biocides are antagonistic.
Table 7: Fractional Inhibitory Concentrations for (MIT) and Zinc Chloride (ZnCh) against Ps.aeruεinosa
Table 7
Figure imgf000015_0002
If a graph with the axes representing the biocide Fractional Inhibitory Concentrations for the two biocides on linear scales is constructed, when the combination is additive the isobole (i.e. the line joining the points that represent all combinations with the same effect including the equally effective concentrations of the biocides used alone) is straight, enhanced combinations give concave isoboles and antagonistic combinations give convex isoboles. As shown in FIG. 3, the combination of MIT and ZnCl2 has an enhanced effect against Ps.aeruginosaas confirmed by the concave isobole in FIG. 3.
Example 5
Investigation of potentiation between BBIT and Zinc Chloride (ZnCI?) against Pseudomonas aeruginosa.
Bacteria
Pseudomonas aeruginosa (NCIB 10421) maintained on nutrient agar, were used to study the synergy between BBIT and ZnCl2
Calculation of Minimum Inhibitory Concentrations Against Mono-cultures
Bacteria were grown to stationary phase (approximately 24 hours) in nutrient broth (approximately 109 organisms per ml). A 0.1%(v/v) inoculum was used to seed fresh medium and 100 μl of the inoculum was then added to each well of a microtitre plate, except for the first well which contained 200 μl.
Using doubling dilutions, the concentration of the compounds under investigation were varied in each well along the ordinate axis. The presence or absence of growth was recorded by visual inspection after 24 hours incubation at 37°C.
Calculation of Antimicrobial Activity Against Mono-cultures
Microtitre plates were used for this assay. A simple matrix was constructed with varied concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array. As the microtitre plate has only 96 wells, the combinations of the two compounds that made up the extreme concentrations (highest and lowest) were omitted. Solutions were made up in broth at two times the final concentrations after pre- dissolving the compounds in distilled water.
The mixture (100 μl) was added to the plate so that the total volume in each well was 200 μl. Nutrient broth was used for Ps.aeruginosa . Plates were incubated for 16-24 hours at 37°. The presence or absence of growth was determined by visual inspection. Results of Example 5
Table 8; Antimicrobial Activity of Compounds Under Investigation
Table 8
Figure imgf000017_0001
BBIT is N-(n-butyl)-l,2-benzisothiazolin-3-one.
Calculation of Synergy Against Mono-cultures
The Minimum Inhibitory Concentration (MIC) is the lowest concentration of biocide which showed growth inhibition when used alone. For the purpose of Fractional
10 Inhibitory Concentration (FIC) calculations, if a single biocide did not control growth, the MIC was taken as the highest concentration used. A Fractional Inhibitory Concentration is the concentration of biocide which controlled growth in the mixture divided by the MIC of that biocide. FIC values for both compounds in the mixture were calculated and the results are shown in Table 9. The sum of these two figures gives an indication of the
15 action of the two biocides. A value less than one indicates an enhanced effect, if the total is unity or greater the action is additive and if the value is greater than two the biocides are antagonistic.
Table 9: Fractional Inhibitory Concentrations for BBIT and Zinc Chloride (ZnCh) 2.0 against Ps.aerueinosa
Table 9
Figure imgf000017_0002
If a graph with the axes representing the biocide Fractional Inhibitory Concentrations for
25 the two biocides on linear scales is constructed, when the combination is additive the isobole (i.e. the line joining the points that represent all combinations with the same effect including the equally effective concentrations of the biocides used alone) is straight, enhanced combinations give concave isoboles and antagonistic combinations give convex isoboles. As shown in FIG. 4, the combination of BBIT and ZnCl2 has an enhanced effect
30 against Ps. aeruginosa as confirmed by the concave isobole shown in FIG. 4. Comparative Example A
Investigation of potentiation between 1.2-BenzisothiazoIin-3-one (BIT) and Sodium Chloride (NaCh) against Pseudomonas aeruginosa as compared to the Synergy between l,2-Benzisothiazolin-3-one (BIT) and Zinc Chloride (ZnCh) against Pseudomonas aeruginosa (Example 2)
Bacteria
Pseudomonas aeruginosa (NCIB 10421) maintained on nutrient agar, were used to study the efficacy of the combination of BIT with sodium chloride.
Calculation of Minimum Inhibitory Concentrations Against Mono-cultures
Bacteria were grown to stationary phase (approximately 24 hours) in nutrient broth (approximately 109 organisms per ml). A 0.1%(v/v) inoculum was used to seed fresh medium and 100 μl of the inoculum was then added to each well of a microtitre plate, except for the first well which contained 200 μl.
Using doubling dilutions, the concentration of the compounds under investigation were varied in each well along the ordinate axis. The presence or absence of growth was recorded by visual inspection after 24 hours incubation at 37°C.
Calculation of Antimicrobial Activity Against Mono-cultures
Microtitre plates were used for this assay. A simple matrix was constructed with varied concentrations of the two compounds from 2 x MIC (minimum inhibitory concentration) down to zero concentration in a 10 x 10 array. As the microtitre plate has only 96 wells, the combinations of the two compounds that made up the extreme concentrations (highest and lowest) were omitted. Solutions were made up in broth at two times the final concentrations after pre-dissolving the compounds in distilled water.
The mixture (100 μl) was added to the plate so that the total volume in each well was 200 μl. Nutrient broth was used for Ps.aeruginosa . Plates were incubated for 16-24 hours at 37°. The presence or absence of growth was determined by visual inspection. Results of Comparative Example A
Table 10; Antimicrobial Activity of Compounds Under Investigation
Table 10
Figure imgf000019_0001
BIT is l,2~benzisothiazolin-3-one available from Arch Limited as PROXEL RKT1 MM , GXL
Calculation of potentiation Against Mono-cultures
The Minimum Inhibitory Concentration (MIC) is the lowest concentration of biocide which showed growth inhibition when used alone. For the purpose of Fractional Inhibitory Concentration (FIC) calculations, if a single biocide did not control growth, the MIC was taken as the highest concentration used. A Fractional Inhibitory Concentration is the concentration of biocide which controlled growth in the mixture divided by the MIC of that biocide. FIC values for both compounds in the mixture were calculated and the results are shown in Table 11. The sum of these two figures gives an indication of the action of the two biocides. A value less than one indicates an enhanced effect, if the total is unity or greater the action is additive and if the value is greater than two the biocides are antagonistic.
Table 11: Fractional Inhibitory Concentrations for l,2-Benzisothiazolin-3-one (BIT) and Sodium Chloride (NaCl?) against Ps.aerueinosa
Table 11
Figure imgf000019_0002
If a graph with the axes representing the biocide Fractional Inhibitory Concentrations for the two biocides on linear scales is constructed, when the combination is additive the isobole ( i.e. the line joining the points that represent all combinations with the same effect including the equally effective concentrations of the biocides used alone) is straight, enhanced combinations give concave isoboles and antagonistic combinations give convex isoboles. As shown in FIG. 5, the combination of BIT and NaCl2 is additive against Ps. aeruginosa as confirmed by the straight isobole in FIG. 5. Additionally, the results of this Example further illustrate that the combination of an isothiazolin-3-one such as BIT and a zinc compound such as ZnCl2, as shown in Example 2, show unexpected potentiation results against Ps. aeruginosa.

Claims

What is claimed is:
1. An antimicrobial composition comprising (a) at least one isothiazolin-3-one and (b) at least one zinc compound selected from the group consisting of zinc salts, zinc oxides, zinc hydroxides, and combinations thereof, wherein said isothiazolin-3-one is present in an amount of from 1 to 500 ppm, the zinc compound is present in an amount of from 5 to 200,000 ppm, and the weight ratio of the isothiazolin-3-one to the zinc compound is from 1:2000 to 100:1.
2. The composition of claim 1 wherein component (a) is present in an amount of from 1 to 500 ppm, component (b) is present in an amount of from 5 to 200,000 ppm, and the weight ratio is from 1:100 to 100:1.
3. The composition of claim 1 wherein component (a) is present in an amount of from 5 to 500 ppm, and component (b) is present in an amount of from 5 to 500 ppm.
4. The antimicrobial composition of claim 1 wherein said isothiazolin-3-one is selected from the group consisting of l,2-benzisothiazolin-3-one, N-(n-butyl)-l,2-benzisothiazolin- 3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, mixtures of 5-chloro-2-methyl-4-isothiazolin-3-one (ClMIT) and 2-methyl-4-isothiazolin- 3-one, and also dithio-2,2'-bis(benzmethylamide),and combinations thereof.
5. The antimicrobial composition of claim 1 wherein said zinc salt is selected from the group consisting of zinc chloride, zinc sulfide, zinc carbonate, basic zinc carbonate , and combinations thereof.
6. The antimicrobial composition of claim 1 wherein said zinc compound is zinc chloride.
7. The antimicrobial composition of claim 1 which further comprises a co-biocide selected from the group consisting of pyrithione salts, pyrithione acids, and combinations thereof, and wherein said co-biocide is present in said composition in an amount of from about 0.001 to about 1 %w/w based on the total weight of said composition.
8. An antimicrobial composition concentrate, which upon dilution with water provides the amounts of components (a) and (b) as specified in claim 1, said concentrate comprising isothiazolin-3-one in an amount of between 1 and 95% w/w.
9. The antimicrobial composition concentrate of claim 8 which further comprises a co- biocide selected from the group consisting of pyrithione salts, pyrithione acids, and combinations thereof, and wherein said co-biocide is present in said composition in an amount of from about 1 to about 50% w/w based on the total weight of said composition.
10. A composition comprising a polymer emulsion, said composition additionally comprising a wet state preservative comprising a combination of (a) at least one isothiazolin-3-one and (b) at least one zinc compound selected from the group consisting of zinc salts, zinc oxides, zinc hydroxides, and combinations thereof, wherein said combination is present in said composition in a total amount of between about 10 ppm and about 400 ppm, and wherein the molar ratio of component (a) to component (b) is between about 4:1 and about 1 :2.
11. The composition of claim 10 wherein said polymer emulsion comprises a polymer selected from the group consisting of acrylic and substituted (meth)acrylates, styrene/butadiene, ethylene vinyl acetate, polyvinyl acetate, styrene/butadiene/N-methylol acrylamide, nitrile and copolymers thereof.
12. The antimicrobial composition of claim 10 wherein said zinc salt is selected from the group consisting of zinc chloride, zinc sulfide, zinc carbonate, basic zinc carbonate , and combinations thereof.
13. The antimicrobial composition of claim 12 wherein said zinc salt is zinc chloride.
14. The composition of claim 10 wherein said isothiazolin-3-one is selected from the group consisting of: l,2-benzisothiazolin-3-one, N-(n-butyl)-l,2-benzisothiazolin-3-one,
4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, mixtures of 5- chloro-2-methyl-4-isothiazolin-3-one (ClMIT) and 2-methyl-4-isothiazolin-3-one, and also dithio-2,2'-bis(benzmethylamide),and combinations thereof.
15. The composition of claim 10 which further comprises a co-biocide selected from the group consisting of pyrithione salts, pyrithione acids, and combinations thereof, and wherein said co-biocide is present in said composition in an amount of from about 0.001 to about 1.0 % w/w based on the total weight of said composition.
16. The composition of claim 15 wherein said pyrithione salts are selected from the group consisting of copper pyrithione, zinc pyrithione, sodium pyrithione, and combinations thereof.
17. A coating composition selected from the group consisting of paints, adhesives, sealants, caulks, mineral and pigment slurries, printing inks, agricultural pesticide formulations, household coating products, personal care products, metal working fluids, and combinations thereof, wherein said coating composition contains a polymer emulsion as a liquid base medium, and a wet state preservative comprising a combination of (a) at least one isothiazolin-3-one and (b) at least one zinc compound selected from the group consisting of zinc salts, zinc oxides, zinc hydroxides, and combinations thereof, wherein said combination is present in said composition in a total amount of between about 10 ppm and about 400 ppm, and wherein the molar ratio of component (a) to component (b) is between about 4:1 and about 1:2.
18. The coating composition of claim 17 wherein said liquid base medium is selected from the group consisting of acrylic and substituted (meth)acrylates, styrene/butadiene, ethylene vinyl acetate, polyvinyl acetate, styrene/butadiene/N-methylol acrylamide, nitrile and copolymers thereof.
PCT/US2007/012518 2006-05-26 2007-05-25 Isothiazolinone biocides enhanced by zinc ions Ceased WO2007139950A2 (en)

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EP14150293.0A EP2742803B1 (en) 2006-05-26 2007-05-25 Use of zinc ions to enhance an isothiazolinone biocide
AU2007267842A AU2007267842B2 (en) 2006-05-26 2007-05-25 Isothiazolinone biocides enhanced by zinc ions
EP07809194A EP2023736A4 (en) 2006-05-26 2007-05-25 ISOTHIAZOLINONE-BASED BIOCIDES ENHANCED BY ZINC IONS
PL17171739T PL3262941T3 (en) 2006-05-26 2007-05-25 Isothiazolinone biocide enhanced by zinc ions
CA2653212A CA2653212C (en) 2006-05-26 2007-05-25 Isothiazolinone biocides enhanced by zinc ions
CN2007800193089A CN101453899B (en) 2006-05-26 2007-05-25 Isothiazolinone biocides enhanced by zinc ions
BRPI0711226-2A BRPI0711226A2 (en) 2006-05-26 2007-05-25 antimicrobial composition, antimicrobial composition concentrate, composition comprising a polymer emulsion and coating composition
JP2009512168A JP2009538319A (en) 2006-05-26 2007-05-25 Isothiazolinone biocides enhanced by zinc ions
PL14150293T PL2742803T3 (en) 2006-05-26 2007-05-25 Use of zinc ions to enhance an isothiazolinone biocide
MX2008014734A MX2008014734A (en) 2006-05-26 2007-05-25 Isothiazolinone biocides enhanced by zinc ions.
NZ572556A NZ572556A (en) 2006-05-26 2007-05-25 Isothiazolinone biocides enhanced by zinc ions
EP17171739.0A EP3262941B1 (en) 2006-05-26 2007-05-25 Isothiazolinone biocide enhanced by zinc ions
KR1020157020398A KR20150094782A (en) 2006-05-26 2007-05-25 Isothiazolinone biocides enhanced by zinc ions
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