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
  • 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
• • 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
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
  • A01N43/32—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms six-membered rings

Definitions

• the invention relates to biocidal compositions and methods of their use for the control of microorganisms in aqueous and water containing systems.
• Isothiazolinone-based biocides are used extensively for protection of water- containing systems such as: paints and coatings, adhesives, household and industrial cleaners, detergents, dish detergents, mineral slurries and polymer emulsions.
• Formaldehyde releasing biocides have also been extensively used, however, recent public concerns and environmental regulations concerning formaldehyde have begun to limit the use of formaldehyde-releasers as antimicrobial agents.
• the isothiazolinone biocides which are non-formaldehyde releasers, have become increasingly attractive alternatives.
• Isothiazolinones however, also suffer from limitations, such as gaps in efficacy against certain microorganisms and possible potential for skin sensitization. It is desirable, therefore, to develop new formulations based on the existing widely used isothiazolinones but that also address isothiazolinones' limitations. It also desirable that such formulations not be based on formaldehyde releasers.
• the invention provides biocidal compositions.
• the compositions are useful for controlling microorganisms in aqueous or water containing systems.
• the compositions of the invention comprise 2,6-dimethyl-m-dioxane-4-ol acetate (dimethoxane) together with an isothiazolinone biocidal compound.
• the invention provides a method for controlling microorganisms in aqueous or water containing systems. The method comprises treating the system with a biocidal composition as described herein.
• the invention provides biocidal compositions and methods of using them in the control of microorganisms.
• the compositions comprise 2,6-dimethyl-m- dioxane-4-ol acetate (dimethoxane) together with an isothiazolinone biocidal compound.
• dimethoxane and an isothiazolinone are synergistic when used for microorganism control in aqueous or water containing media. That is, the combined materials result in improved biocidal properties than would otherwise be expected based on their individual performance at the particular use-concentration.
• the observed synergy permits reduced amounts of the materials to be used to achieve acceptable biocidal properties, thus potentially reducing environmental impact and materials cost. Reducing the amount of isothiazolinone is also advantages because of the possible potential for skin sensitization with such compounds.
• compositions of the invention are also effective for controlling a broader spectrum of microorganism types than would be possible with isothiazolinones alone, including the control of fungi (isothiazolinones such as BIT have limited antifungal efficacy), control of algae, and control of otherwise isothiazolinone- resistant microorganisms.
• isothiazolinones such as BIT have limited antifungal efficacy
• control of algae control of otherwise isothiazolinone- resistant microorganisms.
• the compositions can be prepared and used in formaldehyde free form, which is especially advantageous where use of formaldehyde is undesirable.
• microorganism includes, but is not limited to, bacteria, fungi, algae, and viruses.
• control and controlling should be broadly construed to include within their meaning, and without being limited thereto, inhibiting the growth or propagation of microorganisms, killing microorganisms, disinfection, and/or preservation against re-growth.
• Preferred isothiazolinone compounds for use in the compositions of the invention have the following formula I:
• R and R 1 are independently hydrogen, halogen or Ci -C 4 alkyl, or R and R 1 together with the carbons to which they are attached from a C 4 -C 7 cycloalkyl ring or an aryl group;
• Y is H, C 1 -C 12 alkyl, C 3 -C 7 cycloalkyl, aryl or aralkyl.
• R is H, or Cl.
• R 1 is H or Cl.
• R and R 1 together with the carbons to which they are attached, form phenyl or cyclopentyl.
• isothiazolinones are 5-chloro-2-methyl-3-isothiazolinone; 2- methyl-3-isothiazolinone; 2-ethyl-3-isothiazolinone; 5-chloro-2-ethyl-3-isothiazolinone; 4,5-dichloro-2-methyl-3-isothiazolinone; 2-n-octyl-3-isothiazolinone; 4,5-dichloro-2-n- octyl-3-isothiazolinone; l,2-benzisothiazol-3-one; 2-methyl-4,5-trimethylene-4-isothiazolin- 3-one; and mixtures of two or more thereof.
• l,2-benzisothiazol-3- one BIT
• 2-methyl-3-isothiazolinone MIT
• mixtures of 5-chloro-2-methyl-3- isothiazolinone/2-methyl-3-isothiazolinone BIT
• isothiazolinone compound can be combined for use in the present invention; in such cases, ratios and concentrations are calculated using the total weight of all isothiazolinone compounds present.
• a particularly preferred combination is 5-chloro-2-methyl-3-isothiazolinone/2-methyl-3-isothiazolinone.
• the dimethoxane: isothiazolinone weight ratio in the compositions of the invention is between about 2000:1 and about 1:1000, more preferably between about 1500: 1 and about 1:500, even more preferably between about 1500:1 and about 1:100.
• the weight ratio is between about 1400:1 and about 1:10 or is between about 1400:1 and about 1:3.
• the weight ratio is between about 1000:1 and about 1:3, between about 500:1 and about 1:3, between about 100:1 and about 1:3, or between about 50: 1 and about 1:3.
• the isothiazolinone biocidal compound is 1,2- benzisothiazol-3-one
• the weight ratio of dimethoxane to the 1,2- benzisothiazol-3-one is between about 50:1 and about 1:4.
• the isothiazolinone biocidal compound is a mixture of 5-chloro-2-methyl-3-isothiazolinone and 2-methyl-3-isothiazolinone
• the weight ratio of dimethoxane to the mixture is between about 900: 1 and about 10:1.
• the weight ratio of dimethoxane to the 2-methyl-3- isothiazolinone is preferably between about 150: 1 and about 2: 1.
• the microorganism being treated is algae and the aqueous or water containing system is latex.
• the biocidal composition for this embodiment preferably comprises: dimethoxane and a mixture of 5-chloro-2-methyl-3-isothiazolinone and 2-methyl-3-isothiazolinone.
• the weight ratio of the dimethoxane to the mixture of 5- chloro-2-methyl-3-isothiazolinone and 2-methyl-3-isothiazolinone is preferably between about 150:1 and about 30:1.
• Isothiazolinones for use in the invention are commercially available or can be readily prepared by those skilled in the art using well known techniques (see e.g., U.S. Patent 5,312,827). Dimethoxane is commercially available.
• a preferred stabilizer is magnesium nitrate.
• compositions of the invention are useful at controlling microorganism growth in a variety of aqueous and water containing systems.
• aqueous and water containing systems include, but are not limited to, paints and coatings, latexes, adhesives, inks, pigment dispersions, household and industrial cleaners, detergents, dish detergents, mineral slurries polymer emulsions, metalworking fluids, construction products, personal care products, textile fluids such as spin finishes, industrial process water (e.g. oilfield water, pulp and paper water, cooling water), oilfield functional fluids such as drilling muds and fracturing fluids, and fuels.
• industrial process water e.g. oilfield water, pulp and paper water, cooling water
• oilfield functional fluids such as drilling muds and fracturing fluids, and fuels.
• a suitable actives concentration (total for both dimethoxane and the isothiazolinone) is between about 5000 and about 100 ppm by weight, based on the total weight of the aqueous or water containing system.
• the active concentration is preferably between about 2500 ppm and about 350 ppm.
• the concentration is preferably between about 1800 ppm and about 300 ppm.
• compositions can be added to the aqueous or water containing system separately, or preblended prior to addition.
• a person of ordinary skill in the art can readily determine the appropriate method of addition.
• the composition can be used in the system with other additives such as, but not limited to, surfactants, ionic/nonionic polymers and scale, corrosion inhibitors, oxygen scavengers, and/or additional biocides.
• 2,6-Dimethyl-m-dioxan-4-ol acetate (dimethoxane) is used as BIOBANTM DXN, 87% active, available from The Dow Chemical Company.
• l,2-benzisothiazol-3-one (BIT) is used as CANGU ARDTM ULTRA BIT 20 LE, 20% active, available from The Dow Chemical Company.
• CMIT/MIT 5-Chloro-2-methyl-4-isothiazolin-3-one/2-methyl-4-isothiazolin-3-one
• Microorganisms Twenty-four hour tryptic soy broth cultures are combined in equal parts for formulation inoculation at a final concentration of 5xlO 6 CFU/ml. Organisms are added to each sample of the 96-well block and mixed until homogenous. Additionally, bacterial challenges of the industrial or household product occur on days 2, 7, and 14 of the 28-day test period.
• Enumeration of Viable Organisms Sample aliquots are removed, at predetermined time points, for the enumeration of surviving microorganisms. Numerical values in the data tables listed below represent the log 10 viable microorganisms recovered from individual samples at specific time points and biocide concentrations post microorganism addition. Biocide concentrations resulting in a > 4 logio kill of microorganisms, as compared to the preservative- free control, were deemed a significant reduction of viable organisms and were subsequently used for calculating synergy index values.
• synergy Calculations The reported synergy indexes are measured and calculated using the formula described below. In this approach, a synergy index of 1 indicates additivity. If the index is less than 1 , synergy has occurred, while a synergy index greater than 1 indicates antagonism.
• C A and C B the concentrations of antimicrobials A and B, in combination, producing a 4 logio microbial kill.
• the antimicrobial profiles dimethoxane, l,2-benzisothiazol-3-one (BIT), and combinations of dimethoxane/BIT are evaluated in a commercial liquid laundry detergent formulation (pH 8.0).
• the detergent formulation is determined to be free of microbial contamination prior to initiation of preservative efficacy evaluations.
• the antimicrobial profiles of dimethoxane, BIT, and combinations of dimethoxane/BIT are evaluated in a commercial (interior eggshell) water-based latex paint formulation (pH 7.4).
• the paint formulation is determined to be free of microbial contamination prior to initiation of preservative efficacy evaluations.
• Organisms for this example Pseudomonas aeruginosa (ATCC#15442), Pseudomonas aeruginosa (ATCC#10145), Enterobacter aerogenes (ATCC#13048), Escherichia coli ( ATCC#11229), Klebsiella pneumoniae (ATCC#8308), Staphylococcus aureus (ATCC#6538), Salmonella choleraesuis (ATCC#10708).
• DMX Dimethoxane
• a.i. active ingredient (i.e., actives concentration) Table 2.
• BIT DMX Dimethoxane dimethoxane, when used alone, requires 1160 ppm (active concentration) to achieve a > 4 logio microbial kill following four bacterial challenges. BIT by itself requires 59 ppm (active concentration) to achieve a > 4 log 10 microbial kill under the same testing conditions. Use of various concentration ratios of BIT and dimethoxane in combination result in an equivalent log 10 reduction in viable microorganisms under the same testing conditions indicating a synergistic combination of biocide actives.
• Dimethoxane when used alone, requires 1160 ppm to achieve a > 4 logio microbial kill following four bacterial challenges. BIT by itself requires greater than 500 ppm to achieve a > 4 logio microbial kill under the same testing conditions. Use of various concentration ratios of BIT and dimethoxane results in an equivalent log 10 reduction in viable microorganisms under the same testing conditions indicating a synergistic combination of biocide actives.
• Example 2
• the antimicrobial profiles of 2,6-dimethyl-m-dioxan-4-ol acetate (dimethoxane), 2- methyl-3-isothiazolinone (MIT), and combinations of dimethoxane/MIT are evaluated in a commercial liquid laundry detergent formulation (pH 8.0).
• the detergent formulation is determined to be free of microbial contamination prior to initiation of preservative efficacy evaluations.
• Organisms for this example Pseudomonas aeruginosa (ATCC#15442), Pseudomonas aeruginosa (ATCC#10145), Enterobacter gergoviae (ATCC#33028), Escherichia coli ( ATCC#11229), Pseudomonas putida (ATCC#49128), Staphylococcus aureus (ATCC#6538).
• the antimicrobial profiles of 2,6-dimethyl-m-dioxan-4-ol acetate (dimethoxane), 5- chloro-2-methyl-4-isothiazolin-3-one/2-methyl-4-isothiazolin-3-one (CMIT/MIT) and combinations of dimethoxane/CMIT/MIT are evaluated in a commercial (interior eggshell) water-based latex paint formulation (pH 7.4).
• the paint formulation is determined to be free of microbial contamination prior to initiation of preservative efficacy evaluations.
• Organisms for this example Pseudomonas aeruginosa (ATCC#15442),
• Dimethoxane when used alone, requires 1740 ppm to achieve a > 4 log 10 microbial kill following four bacterial challenges.
• CMIT/MIT by itself requires 15 ppm to achieve a > 4 logio microbial kill under the same testing conditions.
• Use of various concentration ratios of CMIT/MIT and dimethoxane results in an equivalent logio reduction in viable microorganisms under the same testing conditions indicating a synergistic combination of biocide actives.
• a viscous PVA (poly vinyl acetate) latex diluted with water at 5 to 1 ratio is used for algal efficacy testing.
• This diluted latex is treated with CMIT/MIT and dimethoxane at concentrations as indicated in Table 9.
• Each sample is mixed well by hand and vortex for 2 minutes. 5mL portions of each sample are then placed in a six-well plate and inoculated with 500 ⁇ L of 1X10 cfu/mL wild strain of green algae isolated from contaminated PVA latex.
• the data shows the effectiveness of the dimethoxane/CMIT/MIT combination of the invention compared to the dimethoxane and CMIT/MIT individually.

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• 2009
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