CA2083367A1 - Synergistic microbicidal combinations containing 2-methyl-3-isothiazolone and certain commercial biocides - Google Patents
Synergistic microbicidal combinations containing 2-methyl-3-isothiazolone and certain commercial biocidesInfo
- Publication number
- CA2083367A1 CA2083367A1 CA002083367A CA2083367A CA2083367A1 CA 2083367 A1 CA2083367 A1 CA 2083367A1 CA 002083367 A CA002083367 A CA 002083367A CA 2083367 A CA2083367 A CA 2083367A CA 2083367 A1 CA2083367 A1 CA 2083367A1
- Authority
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- Canada
- Prior art keywords
- component
- composition
- range
- ratio
- isothiazolone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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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
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE
Synergistic microbicidal compositions are disclosed, comprising 2-methyl-3-isothiazolone and one or more of seven known microbicides for more effective, and broader control of microorganisms in various systems.
Synergistic microbicidal compositions are disclosed, comprising 2-methyl-3-isothiazolone and one or more of seven known microbicides for more effective, and broader control of microorganisms in various systems.
Description
2~33~
I. BACKGROUND OF T~E INVENTION
A. Field of the Invention This invention concerns microbicidal compositions which include an isothiazolone and one or more other biocides, and which are intended to provide more effective and broader control of micro-organisms in various industrial systems and for household products, agricultural products, and biomedical products, etc. In particular, the present invention relates to the use of a composition of 2-methyl-isothiazolin-3-one, hereinafter referred to as 2-methyl-3-isothiazolone, with one or more of the following seven compounds: p-chloro-m-xylenol, sodium dichlorophene, bis-(2-hydroxy-5-chlorophenyl) sulfide, benzylbromoacetate, dodecylamine, 4-(2-nitrobutyl~ morpholine and dipropylamine ether.
The term "microbicidal" (or "antimicrobial" or "biocidal") as used herein is intended to encompass, but is not restricted to, all bactericidal, fungicidal and algicidal activity.
B. Prior Art Isothiazolones are described in U.S. Patent Nos. 3,761,488; 4,105,431; 4,252,694;
4,265,899 and 4,279,762, and elsewhere. Their use as microbicides is well known.
2Q833~
It is the principal object of this inverltion to provide synergistic compositions which are more efficacious known microbicidal compositions.
II. SUMMARY OF THE INVENTION
We have folmd that compositions formed from one or more of the seven specified compounds (supra) unexpectedly afford synergistic antimicrobial activity against a wide range of microorganisms: the disruptive action on the organisms by the two compounds together is unexpectedly greater than the sum of both compounds taken alone. This synergy does not arise from the expected activity of the components nor from the expected improvement in activity. As a result of the synergy, the effective dose required can be lowered, which is not only more economical but also increases safety margins. The synergistic compositions of the present invention provide more effective and broader control of microorganisms in a number of systems.
The present invention thus provides a composition having microbicidal activity which includes 2-methyl-3-isothiazolone and a second component selected from one or more of the group consisting of: p-chloro-m-xylenol, sodium dichlorophene, bis-(2-hydroxy-5-chlorophenyl) sulfide, benzylbromoacetate, dodecylamine,4-(2-nitrobutyl) morphollne and dipropylamine ether wherein the weight ratio of 2-methyl-3-isothiazolone to the second component is from about 40:1 2~3~7 to 1:32.
Important applications of the synergistic antimicrobial compositions of the present invention include but are not limited to: inhibiting the growth of bacteria and fungi in aqueous paints and coatings, adhesives, sealants, latex emulsions, and joint cements; preserving wood; preserving cutting fluids, controlling slime-producing bacteria and fungi in pulp and papermills and cooling towers; as a spray or dip treatment for textiles and leather to prevent mold growth; protecting paint films, especially exterior paints, from attack by fungi which occurs during weathering of the paint film; protecting processing equipment from slime deposits during manufacture of cane and beet sugar; preventing microorganism buildup and deposits in air washer or scrubber systems and in industrial fresh water supply systems; preserving fuel; controlling microorganisms contamination and deposits in oil field drilling fluids and muds, and in secondary petroleum recovery processes;
preventing bacterial and fungal growth in paper coatings and coating proces$es;
controlling bacterial and fungal growth and deposits during the manufacture of various specialty boards, e.g., cardboard and particle board; preventing sap stain discoloration on freshly cut wood of various kinds; controlling bacterial and fungal growth in clay and pigment slurries of various types; as a hard surface disinfectant to prevent growth of bacteria and fungi on walls, floors, etc.; as a preservative for 2~3367 cosmetic and toiletry raw materials, floor polishes, fabric softeners, household and industrial cleaners; in swimming pools to prevent algae growth; inhibiting the growth of harmful bacteria, yeasts, fungi on plants, trees, fruits, seeds, or soil;
preserving agricultural formulations, electrodeposition systems, diagnostic and reagent products, medical devices; protecting animal dip compositions against the buildup of microorganisms, and in photoprocessing to prevent buildup of microorganisms, and the like.
The compositions of the invention may be added separately to any system or may be formulated as a simple mixture comprising its essential ingredients, and if desired a suitable carrier or solvent, or as an aqueous emulsion or dispersion.
The invention also provides a method of inhibiting or preventing the growth of bacteria, fungi or algae in a locus subject or susceptible to contamination thereby which comprises incorporating into or onto the locus, in an amount effective to inhibit or prevent said growth, any of the compositions defined above.
General Description of the Preferred Embodiment The composition of the invention can be formulated as a solution in a wide range of solvents. The solutions may contain from 0.01 to 99.9%; but more generally from about 5 ~o 30% by weight of the active composition. It is generally more convenient to provide the compositions in a water-diluted form: t~is may be 2~33~7 accomplished by adding an emulsifier to the organic solution followed by dilution with water.
In general, the weight ratio of 2-methyl-3-isothiazolone to the second component in the composition may be in the range of from about 40:1 to about 1:32.
The other specific and preferred ratios are given in the examples.
The synergism of two-component compositions is demonstrated by testing a wide range of concentrations and ratios of compounds, generated by two-fold serial dilutions in a Trypticase Soy Broth (TSB) growth medium of a microbicide in one dimension and another microbicide in the second dimension, against a bacterium Escherichia coli (ATCC 11229), or fungi Candida albicans (ATCC 11651), Aspergillus ni~er (ATCC 6275), or Aureobasidium pullulan (ATCC 9348). Each test tube was inoculated to make abcut 1-5 x 107 bacteria per ml or 1-5 x 105 fungi per ml. The lowest concentrations of each compound or mixtures to inhibit visible growth (turbidity) at 37 for E. coli and at 30C for the fungi for 7 days were taken as the minimum inhibitory concentration (MIC). The MIC were taken as end points of activity. End points for the mixtures of compound A (2-methyl-3-isothiazolone) and compound B (second component microbicide) were then compared with the end points for the isothiazolone A alone and compound B alone. 5ynergism was determined by a commonly used and accepted method described by Kull, F.C.;
2~83367 Eisman, P.C.; Sylwestrowicz, H.D. and Mayer, R.L., in applied Microbiology 9:538-541 tl961) using the ratio determined by QalQA + Qb/QB = Synergy :[ndex (SI) wherein QA= concentration of compound A in parts per million (ppm), acting alone, which produced an end point;
Qa= concentration of compound A in ppm, in the mixture, which produced an end point;
QB= concentration of compound B in ppm, acting alone, which produced an end point;
Qb= concentration of compound B in ppm, in the mixture, which produced an end point.
When the sum of Qa/QA and Qb/QB 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 test results for demonstration of synergism of microbicide combinations are shown in Tables 1 to 7. Each table concerns the combination of 2-methyl-3-isothiazolone and one other microbicide, and shows:
1. the identity of the second microbicide (compound B);
- 2~833~7 2. test against E. ~ , and C. alb;cans (C. alb~;
I. BACKGROUND OF T~E INVENTION
A. Field of the Invention This invention concerns microbicidal compositions which include an isothiazolone and one or more other biocides, and which are intended to provide more effective and broader control of micro-organisms in various industrial systems and for household products, agricultural products, and biomedical products, etc. In particular, the present invention relates to the use of a composition of 2-methyl-isothiazolin-3-one, hereinafter referred to as 2-methyl-3-isothiazolone, with one or more of the following seven compounds: p-chloro-m-xylenol, sodium dichlorophene, bis-(2-hydroxy-5-chlorophenyl) sulfide, benzylbromoacetate, dodecylamine, 4-(2-nitrobutyl~ morpholine and dipropylamine ether.
The term "microbicidal" (or "antimicrobial" or "biocidal") as used herein is intended to encompass, but is not restricted to, all bactericidal, fungicidal and algicidal activity.
B. Prior Art Isothiazolones are described in U.S. Patent Nos. 3,761,488; 4,105,431; 4,252,694;
4,265,899 and 4,279,762, and elsewhere. Their use as microbicides is well known.
2Q833~
It is the principal object of this inverltion to provide synergistic compositions which are more efficacious known microbicidal compositions.
II. SUMMARY OF THE INVENTION
We have folmd that compositions formed from one or more of the seven specified compounds (supra) unexpectedly afford synergistic antimicrobial activity against a wide range of microorganisms: the disruptive action on the organisms by the two compounds together is unexpectedly greater than the sum of both compounds taken alone. This synergy does not arise from the expected activity of the components nor from the expected improvement in activity. As a result of the synergy, the effective dose required can be lowered, which is not only more economical but also increases safety margins. The synergistic compositions of the present invention provide more effective and broader control of microorganisms in a number of systems.
The present invention thus provides a composition having microbicidal activity which includes 2-methyl-3-isothiazolone and a second component selected from one or more of the group consisting of: p-chloro-m-xylenol, sodium dichlorophene, bis-(2-hydroxy-5-chlorophenyl) sulfide, benzylbromoacetate, dodecylamine,4-(2-nitrobutyl) morphollne and dipropylamine ether wherein the weight ratio of 2-methyl-3-isothiazolone to the second component is from about 40:1 2~3~7 to 1:32.
Important applications of the synergistic antimicrobial compositions of the present invention include but are not limited to: inhibiting the growth of bacteria and fungi in aqueous paints and coatings, adhesives, sealants, latex emulsions, and joint cements; preserving wood; preserving cutting fluids, controlling slime-producing bacteria and fungi in pulp and papermills and cooling towers; as a spray or dip treatment for textiles and leather to prevent mold growth; protecting paint films, especially exterior paints, from attack by fungi which occurs during weathering of the paint film; protecting processing equipment from slime deposits during manufacture of cane and beet sugar; preventing microorganism buildup and deposits in air washer or scrubber systems and in industrial fresh water supply systems; preserving fuel; controlling microorganisms contamination and deposits in oil field drilling fluids and muds, and in secondary petroleum recovery processes;
preventing bacterial and fungal growth in paper coatings and coating proces$es;
controlling bacterial and fungal growth and deposits during the manufacture of various specialty boards, e.g., cardboard and particle board; preventing sap stain discoloration on freshly cut wood of various kinds; controlling bacterial and fungal growth in clay and pigment slurries of various types; as a hard surface disinfectant to prevent growth of bacteria and fungi on walls, floors, etc.; as a preservative for 2~3367 cosmetic and toiletry raw materials, floor polishes, fabric softeners, household and industrial cleaners; in swimming pools to prevent algae growth; inhibiting the growth of harmful bacteria, yeasts, fungi on plants, trees, fruits, seeds, or soil;
preserving agricultural formulations, electrodeposition systems, diagnostic and reagent products, medical devices; protecting animal dip compositions against the buildup of microorganisms, and in photoprocessing to prevent buildup of microorganisms, and the like.
The compositions of the invention may be added separately to any system or may be formulated as a simple mixture comprising its essential ingredients, and if desired a suitable carrier or solvent, or as an aqueous emulsion or dispersion.
The invention also provides a method of inhibiting or preventing the growth of bacteria, fungi or algae in a locus subject or susceptible to contamination thereby which comprises incorporating into or onto the locus, in an amount effective to inhibit or prevent said growth, any of the compositions defined above.
General Description of the Preferred Embodiment The composition of the invention can be formulated as a solution in a wide range of solvents. The solutions may contain from 0.01 to 99.9%; but more generally from about 5 ~o 30% by weight of the active composition. It is generally more convenient to provide the compositions in a water-diluted form: t~is may be 2~33~7 accomplished by adding an emulsifier to the organic solution followed by dilution with water.
In general, the weight ratio of 2-methyl-3-isothiazolone to the second component in the composition may be in the range of from about 40:1 to about 1:32.
The other specific and preferred ratios are given in the examples.
The synergism of two-component compositions is demonstrated by testing a wide range of concentrations and ratios of compounds, generated by two-fold serial dilutions in a Trypticase Soy Broth (TSB) growth medium of a microbicide in one dimension and another microbicide in the second dimension, against a bacterium Escherichia coli (ATCC 11229), or fungi Candida albicans (ATCC 11651), Aspergillus ni~er (ATCC 6275), or Aureobasidium pullulan (ATCC 9348). Each test tube was inoculated to make abcut 1-5 x 107 bacteria per ml or 1-5 x 105 fungi per ml. The lowest concentrations of each compound or mixtures to inhibit visible growth (turbidity) at 37 for E. coli and at 30C for the fungi for 7 days were taken as the minimum inhibitory concentration (MIC). The MIC were taken as end points of activity. End points for the mixtures of compound A (2-methyl-3-isothiazolone) and compound B (second component microbicide) were then compared with the end points for the isothiazolone A alone and compound B alone. 5ynergism was determined by a commonly used and accepted method described by Kull, F.C.;
2~83367 Eisman, P.C.; Sylwestrowicz, H.D. and Mayer, R.L., in applied Microbiology 9:538-541 tl961) using the ratio determined by QalQA + Qb/QB = Synergy :[ndex (SI) wherein QA= concentration of compound A in parts per million (ppm), acting alone, which produced an end point;
Qa= concentration of compound A in ppm, in the mixture, which produced an end point;
QB= concentration of compound B in ppm, acting alone, which produced an end point;
Qb= concentration of compound B in ppm, in the mixture, which produced an end point.
When the sum of Qa/QA and Qb/QB 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 test results for demonstration of synergism of microbicide combinations are shown in Tables 1 to 7. Each table concerns the combination of 2-methyl-3-isothiazolone and one other microbicide, and shows:
1. the identity of the second microbicide (compound B);
- 2~833~7 2. test against E. ~ , and C. alb;cans (C. alb~;
3. the end-point activity in ppm measured by MIC for compound A alone (QA), for compound B alone (QB), for cornpound A in the mixture (Qa), or for compound B in the mixture (Qb);
4. the calculation of synergy inclex (SI) based on the forrmlla SI=Qa/QA +
QblQB, and the weight ratio of 2-methyl-3-isothiazolone (compound A~ to compound B in the particular combination (A:B);
QblQB, and the weight ratio of 2-methyl-3-isothiazolone (compound A~ to compound B in the particular combination (A:B);
5. the range of weight ratios for synergism and the preferred weight ratios. It will be appreciated by those skilled in the art that the ratios given are approximate only.
The MIC values of ea,ch compound tested alone (QA or QB) are end-point activities.
T~,BLE 1 2-Methyl-3-isothiazolone (A~/p-C]hloro-m-xylenol ~B) Combination Tested in TSB with Escherichia coli A B A:BSynergy Index 250 ppm 0 ppm 125 62 2: 10.75 62 125 1: 20.75 31 125 1: 40.62 16 125 1: 80.56 8 125 1 :lS 0.53 4 125 1 :32 0.52 o 250 Tested in TSB with Candida albicans A B A:BSynergy Index 250 ppm 0 ppm 125 31 4:10.75 62 62 1 :10.75 Range of ratios (A:B) is from 4: 1 to 1: 32 2~3367 TABI~
2-Methyl-3-isothiazolone (A)/Sodium dichlorophene (B) Combination Tested in TSB with Escherichia coli B A:BSynergv Index 250 ppm 0 ppm 125 16 8:10.52 125 31 4: 10.75 62 31 2:10.50 31 31 1 :10.37 16 31 1 :20.31 16 62 1: 40.56 8 62 1: 80.53 4 62 1: 16 0.52 Tested in TSB with Candida albicans A B ~Synergy Ind~x.
250 ppm O ppm 125 8 16:10.75 62 16 4:10.75 20833~7 31 16 2: 1 0.62 16 16 1 :1 0.56 8 16 1: 2 0.53 4 16 1 :4 0.52 2 16 1: 8 0.51 16 1 :16 0.50 Range of ratios (A:B) is from 16 :1 to 1 :16 ~o~33~7 TA~]LE 2-Meth~1-3-isothiazolone (A~/Bis-(2-hydroxy-~chlorophen~l~
sulfide (B) Combination Tested in TSB with Escherichia coli A B A:R Synergv Index 250 ppm 0 ppm 125 16 8: 1 0.62 125 31 4:1 0.75 62 62 1: 1 0.75 31. 62 1 :2 0.62 16 62 1: 4 0.56 8 62 1 :8 0.53 Tested in TSB with Candida albicans A B A:B Synergy Index 250 ppm 0 ppm 125 16 8:1 0.75 Range of ratios (A:B) is from 8: 1 to 1: 8 2~833~7 ~E 4 2-Methvl-3-isoth_azolone ~A)/Benzylbromoacetate ~B~ Combination Tested in TSB with Escherichia coli A B A:BSynergy Index 250 ppm 0 ppm 125 6 ~0: 10.53 125 12 10:1 0.56 125 25 5:1 0.62 62 25 2.5:10.37 62 50 1.2:10.50 31 50 1 :1.50.37 31 100 1: 3 0.62 16 100 1: 6 0.56 8 100 1: 120.53 Tested in TSB with Candida albicans A B A:BSvnergy Index 250 ppm 0 ppm 125 3 40: 10.56 2~3~
125 6 20: 1 0.62 125 6 20: 1 0.62 62 6 10:1 0.37 31 6 5:1 0.24 16 ~ ~.5:1 0.18 8 6 1.2: 1 0.15 8 12 1: 1.5 0.28 4 12 1: 3 0.27 4 25 1 :6 0.52 2 25 1: 12 0.51 Range of ratios (A:B) is form 40: 1 to 1: 12 TABL~ 5 2-Methvl-3-isothiazolone (A)/C)odecylamine (B) Comkination Tested in TSB with Escherichia coli A B . A:BSvnergy Index 125 ppm 0 pprn 62 3 20:1 0.62 62 6 10:1 0.75 31 12 2.5:1 0.75 16 12 ~.~: 1 0.62 Tested in TSB with Candida albicans A B ~ Syner~nçlex 250 ppm 0 ppm 125 3 40:1 0.75 62 3 20:1 0.50 62 6 10:1 0.75 31 6 5:1 0.62 16 6 2.5: 1 0.56 Range of ratio (A:B) is from 40: 1 to 1.2: 1 2~833~7 I~,E~ 6 2-Methyl-3-isothiazolone (A)/4-(2-ni~çlbutyl)mo~pholine (B) Combination Tested in TSB with Escherichia coli A B A:B Synergy Index 125 ppm 0 ppm 62 8 8:1 0.53 62 16 4: 1 0.56 62 31 2:1 0.62 62 62 1: 1 0.75 31 62 1 :2 0.50 16 62 1: 4 0.37 16 125 1: 8 0.62 o 250 Tested in TSB with Candida albicans A B A:B Synergy Index 250 ppm 0 ppm 125 ~5 16: 1 0.56 125 16 8: 1 0.62 125 31 4: 1 0.75 2~833~7 62 31 2: 1 0.50 31 31 1 :1 0.37 31 62 1 :2 0.62 16 . 62 1: 4 0.56 8 62 1 :8 0.53 4 62 1: 16 0.52 Range of ratio (A:B) is from 16 :1 to 1 :16 2~833~7 2-Methvl-3-isothiazolone (A?a2~?ropvlamine e~her (B) Combination Tested in TSB with Escherichia coli A B ~ :B Syn~rgY Index 125 ppm 0 ppm 62 6 10:1 0.56 62 12 5:1 0.62 62 25 2.5:1 0.75 31 50 1 :1.6 0.75 o, 100 Tested in TSB with Candida albicans A B A:B Syner~y Index 250 ppm 0 ppm 125 6 20: 1 0.56 125 12 10: 1 0.75 62 12 5:1 0.50 62 25 2.5:1 0.75 Range of ratios (A:B) is from 20: 1 to 1: 1.6 1~
.
2~833~7 The synergistic activities of the compositions of the invention in most cases are applicable to bacteria, fungi, and a mixture of bacteria and fungi. Thus, the combinations not only lower the use-level of biocide but also broaden the spectrum of activity. This is especially useful in situations where either component alone does not achieve the best results due to weak activity against certain organisms.
The MIC values of ea,ch compound tested alone (QA or QB) are end-point activities.
T~,BLE 1 2-Methyl-3-isothiazolone (A~/p-C]hloro-m-xylenol ~B) Combination Tested in TSB with Escherichia coli A B A:BSynergy Index 250 ppm 0 ppm 125 62 2: 10.75 62 125 1: 20.75 31 125 1: 40.62 16 125 1: 80.56 8 125 1 :lS 0.53 4 125 1 :32 0.52 o 250 Tested in TSB with Candida albicans A B A:BSynergy Index 250 ppm 0 ppm 125 31 4:10.75 62 62 1 :10.75 Range of ratios (A:B) is from 4: 1 to 1: 32 2~3367 TABI~
2-Methyl-3-isothiazolone (A)/Sodium dichlorophene (B) Combination Tested in TSB with Escherichia coli B A:BSynergv Index 250 ppm 0 ppm 125 16 8:10.52 125 31 4: 10.75 62 31 2:10.50 31 31 1 :10.37 16 31 1 :20.31 16 62 1: 40.56 8 62 1: 80.53 4 62 1: 16 0.52 Tested in TSB with Candida albicans A B ~Synergy Ind~x.
250 ppm O ppm 125 8 16:10.75 62 16 4:10.75 20833~7 31 16 2: 1 0.62 16 16 1 :1 0.56 8 16 1: 2 0.53 4 16 1 :4 0.52 2 16 1: 8 0.51 16 1 :16 0.50 Range of ratios (A:B) is from 16 :1 to 1 :16 ~o~33~7 TA~]LE 2-Meth~1-3-isothiazolone (A~/Bis-(2-hydroxy-~chlorophen~l~
sulfide (B) Combination Tested in TSB with Escherichia coli A B A:R Synergv Index 250 ppm 0 ppm 125 16 8: 1 0.62 125 31 4:1 0.75 62 62 1: 1 0.75 31. 62 1 :2 0.62 16 62 1: 4 0.56 8 62 1 :8 0.53 Tested in TSB with Candida albicans A B A:B Synergy Index 250 ppm 0 ppm 125 16 8:1 0.75 Range of ratios (A:B) is from 8: 1 to 1: 8 2~833~7 ~E 4 2-Methvl-3-isoth_azolone ~A)/Benzylbromoacetate ~B~ Combination Tested in TSB with Escherichia coli A B A:BSynergy Index 250 ppm 0 ppm 125 6 ~0: 10.53 125 12 10:1 0.56 125 25 5:1 0.62 62 25 2.5:10.37 62 50 1.2:10.50 31 50 1 :1.50.37 31 100 1: 3 0.62 16 100 1: 6 0.56 8 100 1: 120.53 Tested in TSB with Candida albicans A B A:BSvnergy Index 250 ppm 0 ppm 125 3 40: 10.56 2~3~
125 6 20: 1 0.62 125 6 20: 1 0.62 62 6 10:1 0.37 31 6 5:1 0.24 16 ~ ~.5:1 0.18 8 6 1.2: 1 0.15 8 12 1: 1.5 0.28 4 12 1: 3 0.27 4 25 1 :6 0.52 2 25 1: 12 0.51 Range of ratios (A:B) is form 40: 1 to 1: 12 TABL~ 5 2-Methvl-3-isothiazolone (A)/C)odecylamine (B) Comkination Tested in TSB with Escherichia coli A B . A:BSvnergy Index 125 ppm 0 pprn 62 3 20:1 0.62 62 6 10:1 0.75 31 12 2.5:1 0.75 16 12 ~.~: 1 0.62 Tested in TSB with Candida albicans A B ~ Syner~nçlex 250 ppm 0 ppm 125 3 40:1 0.75 62 3 20:1 0.50 62 6 10:1 0.75 31 6 5:1 0.62 16 6 2.5: 1 0.56 Range of ratio (A:B) is from 40: 1 to 1.2: 1 2~833~7 I~,E~ 6 2-Methyl-3-isothiazolone (A)/4-(2-ni~çlbutyl)mo~pholine (B) Combination Tested in TSB with Escherichia coli A B A:B Synergy Index 125 ppm 0 ppm 62 8 8:1 0.53 62 16 4: 1 0.56 62 31 2:1 0.62 62 62 1: 1 0.75 31 62 1 :2 0.50 16 62 1: 4 0.37 16 125 1: 8 0.62 o 250 Tested in TSB with Candida albicans A B A:B Synergy Index 250 ppm 0 ppm 125 ~5 16: 1 0.56 125 16 8: 1 0.62 125 31 4: 1 0.75 2~833~7 62 31 2: 1 0.50 31 31 1 :1 0.37 31 62 1 :2 0.62 16 . 62 1: 4 0.56 8 62 1 :8 0.53 4 62 1: 16 0.52 Range of ratio (A:B) is from 16 :1 to 1 :16 2~833~7 2-Methvl-3-isothiazolone (A?a2~?ropvlamine e~her (B) Combination Tested in TSB with Escherichia coli A B ~ :B Syn~rgY Index 125 ppm 0 ppm 62 6 10:1 0.56 62 12 5:1 0.62 62 25 2.5:1 0.75 31 50 1 :1.6 0.75 o, 100 Tested in TSB with Candida albicans A B A:B Syner~y Index 250 ppm 0 ppm 125 6 20: 1 0.56 125 12 10: 1 0.75 62 12 5:1 0.50 62 25 2.5:1 0.75 Range of ratios (A:B) is from 20: 1 to 1: 1.6 1~
.
2~833~7 The synergistic activities of the compositions of the invention in most cases are applicable to bacteria, fungi, and a mixture of bacteria and fungi. Thus, the combinations not only lower the use-level of biocide but also broaden the spectrum of activity. This is especially useful in situations where either component alone does not achieve the best results due to weak activity against certain organisms.
Claims (13)
1. A microbicidal composition the first component of which is 2-methyl-3-isothiazolone and the second component of which is selected from one or more of the following: p-chloro-m-xylenol, sodium dichlorophene, bis-(2-hydroxy-5-chlorophenyl) sulfide, benzylbromoacetate, dolecylamine, 4-(2-nitrobutyl) morpholine and dipropylamino ether; wherein the weight ratio of first component to second component is in the range of from about 40:1 to about 1:32.
2. The composition of claim 1, wherein the ratio of the first component to the second component, p-chloro-m-xylenol, is in the range of from about 4:1 to about 1:32.
3. The composition of claim 1, wherein the ratio of the first component to the second component, sodium-dichlorophene, is in the range of from about 16:1 to about 1:16.
4. The composition of claim 1, wherein the ratio of the first component to the second component, bis-(2-hydroxy-5-chlorophenyl) sulfide is in the range of from about 8:1 to about 1:8.
5. The composition of claim 1, wherein the ratio of the first component to the second component, benzylbromoacetate is in the range of from about 40:1 to about 1:12.
6. The composition of claim 1, wherein the ratio of the first component to the second component, dodecylamine, is in the range of from about 40:1 to about 1:1.
7. The composition of claim 1, wherein the ratio of the first component to the second component, 4-(2-nitrobutyl)morpholine, is in the range of from about 16:1 to about 1:16.
8. The composition of claim 1, wherein the ratio of the first component to the second component, dipropylamine ether, is in the range of from about 20:1 to about 1:2.
9. A microbicidal product containing from about 0.01 to about 99.9% by weight of the composition of claim 1, and an organic solvent.
10. A microbiocidal product containing from about 5 to about 30% by weight of the composition of claim 1.
11. A microbicidal product accords to claim 14, additionally an emulsifier and water.
12. A method for inhibiting or preventing the growth of bacteria, fungi, or algae in a locus subject or susceptible to contamination thereby which comprises incorporating onto or into the locus, in an amount effective to adversely affect said growth, the composition of claim 1.
13. The method of claim 17 wherein the locus is an aqueous medium, and the composition additionally contains an organic solvent, an emulsiifer and water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79839891A | 1991-11-26 | 1991-11-26 | |
| US798,398 | 1991-11-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2083367A1 true CA2083367A1 (en) | 1993-05-27 |
Family
ID=25173302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002083367A Abandoned CA2083367A1 (en) | 1991-11-26 | 1992-11-19 | Synergistic microbicidal combinations containing 2-methyl-3-isothiazolone and certain commercial biocides |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5489588A (en) |
| EP (2) | EP0544418A3 (en) |
| JP (1) | JPH05246808A (en) |
| KR (1) | KR930009509A (en) |
| CA (1) | CA2083367A1 (en) |
| DK (1) | DK0645086T3 (en) |
| IL (1) | IL103668A (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69512452T2 (en) * | 1994-04-07 | 2000-05-18 | Rohm & Haas | Halogen free biocide |
| US5935518A (en) * | 1996-01-29 | 1999-08-10 | Bausch & Lomb Incorporated | Swimming pool treatment |
| US5902820A (en) * | 1997-03-21 | 1999-05-11 | Buckman Laboratories International Inc. | Microbicidal compositions and methods using combinations of propiconazole with dodecylamine or a dodecylamine salt |
| DE60336126D1 (en) | 2002-01-31 | 2011-04-07 | Rohm & Haas | Synergistic microbicidal combinations |
| KR100433207B1 (en) * | 2002-07-29 | 2004-05-28 | 에스케이케미칼주식회사 | 3-Isothiazolone solution |
| US9034905B2 (en) | 2003-02-05 | 2015-05-19 | Rohm And Haas Company | Synergistic microbicidal combinations |
| US20080063723A1 (en) * | 2006-09-08 | 2008-03-13 | Sungmee Choi | Isothiazolin-3-one-containing antimicrobial composition |
| JP5291292B2 (en) * | 2007-02-01 | 2013-09-18 | 協同油脂株式会社 | Metal working fluid and metal working method |
| US20100251602A1 (en) * | 2009-04-06 | 2010-10-07 | John Pohlman | Cold temperature stable biocidal composition |
| JP5210360B2 (en) * | 2009-07-30 | 2013-06-12 | ローム アンド ハース カンパニー | Synergistic microbicidal composition |
| DE102009048188A1 (en) | 2009-10-02 | 2011-04-07 | Schülke & Mayr GmbH | Antimicrobially effective use solutions containing combinations of isothiazolones and amines |
| DE102009048189A1 (en) * | 2009-10-02 | 2011-04-07 | Schülke & Mayr GmbH | Storage-stable microbicidal concentrates and their use as preservatives |
| ES2905266T3 (en) * | 2013-11-19 | 2022-04-07 | Arch Chem Inc | enhanced preservative |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3452034A (en) * | 1967-03-09 | 1969-06-24 | American Cyanamid Co | Substituted 2-(1,3,4-thiadiazol-2-yl)-4(5)-nitroimidazoles |
| US4325201A (en) * | 1967-03-09 | 1982-04-20 | Rohm And Haas Company | Seed treatment with 3-isothiazolones |
| US3929563A (en) * | 1975-03-03 | 1975-12-30 | Betz Laboratories | Synergistic compositions containing N (2 nitrobutyl) morpholine and their use |
| JPS6054281B2 (en) * | 1977-03-28 | 1985-11-29 | 株式会社パ−マケム・アジア | Fungicide |
| US4265899A (en) * | 1978-05-30 | 1981-05-05 | Rohm And Haas Company | Cosmetic formulation comprising 3-isothiazolones |
| JPS56113706A (en) * | 1980-02-09 | 1981-09-07 | Nissan Chem Ind Ltd | Mildewcide composition for industrial use |
| JPS59228247A (en) * | 1983-06-08 | 1984-12-21 | Konishiroku Photo Ind Co Ltd | Process for preventing hydrophilic colloid for silver halide photosensitive material from putrefaction |
| JPH0725645B2 (en) * | 1988-03-07 | 1995-03-22 | 栗田工業株式会社 | Antibacterial composition |
| US5028620A (en) * | 1988-09-15 | 1991-07-02 | Rohm And Haas Company | Biocide composition |
| US4906651A (en) * | 1988-12-22 | 1990-03-06 | Rohm And Haas Company | Synergistic microbicidal combinations containing 3-isothiazolone and commercial biocides |
| JPH0749362B2 (en) * | 1989-03-30 | 1995-05-31 | ソマール株式会社 | Antibacterial agent |
-
1992
- 1992-11-04 DK DK94119006T patent/DK0645086T3/en active
- 1992-11-04 EP EP19920310095 patent/EP0544418A3/en not_active Withdrawn
- 1992-11-04 EP EP94119006A patent/EP0645086A1/en not_active Withdrawn
- 1992-11-06 IL IL10366892A patent/IL103668A/en not_active IP Right Cessation
- 1992-11-19 CA CA002083367A patent/CA2083367A1/en not_active Abandoned
- 1992-11-24 KR KR1019920022167A patent/KR930009509A/en not_active Application Discontinuation
- 1992-11-26 JP JP4337776A patent/JPH05246808A/en not_active Withdrawn
-
1995
- 1995-03-16 US US08/405,573 patent/US5489588A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0544418A3 (en) | 1993-07-14 |
| EP0544418A2 (en) | 1993-06-02 |
| JPH05246808A (en) | 1993-09-24 |
| IL103668A (en) | 1996-06-18 |
| KR930009509A (en) | 1993-06-21 |
| US5489588A (en) | 1996-02-06 |
| IL103668A0 (en) | 1993-04-04 |
| DK0645086T3 (en) | 2003-09-29 |
| EP0645086A1 (en) | 1995-03-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |