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WO2008140469A2 - Compositions antimicrobiennes, procédés et systèmes - Google Patents

Compositions antimicrobiennes, procédés et systèmes Download PDF

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Publication number
WO2008140469A2
WO2008140469A2 PCT/US2007/021941 US2007021941W WO2008140469A2 WO 2008140469 A2 WO2008140469 A2 WO 2008140469A2 US 2007021941 W US2007021941 W US 2007021941W WO 2008140469 A2 WO2008140469 A2 WO 2008140469A2
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Prior art keywords
antimicrobial
composition
industrial preparation
undecenoic acid
formula
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PCT/US2007/021941
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WO2008140469A3 (fr
Inventor
Mervyn L. De Souza
Jill Louise Zullo
James C. Anderson
Richard L. Pederson
Yann Schrodi
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Elevance Renewable Sciences Inc
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Elevance Renewable Sciences Inc
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    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/06—Unsaturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/70—Esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/06—Groups 3 or 13
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/14—Group 7
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/16—Antiseptic; (micro) biocidal or bactericidal

Definitions

  • Materials that can benefit from protection against such microorganisms include, for example, materials such as paints and other coating formulations, surfactants, emulsions and resins, wood, adhesives, caulks, sealants, leather, textiles, and the like.
  • Other important commercial materials such as polymer dispersions or aqueous latex paints, clay and mineral suspensions and metalworking fluids (MWF), are also prone to degradation by the action of objectionable microorganisms that can spoil and significantly impair the usefulness of such compositions. Such degradation may produce, for example, changes in pH values, gas formation, discoloration, the formation of objectionable odors, and/or changes in rheological properties.
  • Antimicrobials can also be useful during the processing of materials.
  • animal skins are susceptible to attack by microorganisms both prior to and after the tanning process.
  • bactericides Prior to the tanning process, bactericides can be used in the brine solutions to prevent bacteria from damaging the hide grain.
  • wet blue hides After the tanning process, the so called wet blue hides can be subject to fungal attack during storage or transport, and fungicides can be used to inhibit this fungal growth.
  • Antimicrobials can also be used in the fat liquors and leather finishing products to prevent the growth of bacteria, fungi and yeast.
  • antimicrobial materials include halogenated compounds, organometallic compounds, quaternary ammonium compounds, phenolics, metallic salts, heterocyclic amines, formaldehyde adducts, organosulfur compounds, and the like.
  • Antimicrobial efficacy can be assessed in various ways, including spectrum of activity (e.g., effectiveness in controlling growth of bacteria, fungi and the like), rate of kill of microorganisms, residual antimicrobial effect, and the like.
  • spectrum of activity e.g., effectiveness in controlling growth of bacteria, fungi and the like
  • rate of kill of microorganisms e.g., rate of kill of microorganisms
  • residual antimicrobial effect e.g., antimicrobial effect
  • the specific requirements for antimicrobial agents can vary according to the intended application (e.g., sanitizer, disinfectant, sterilant, aseptic packaging treatment, etc.) and the applicable public health requirements.
  • antimicrobial agents such as iodophors, peracids, hypochlorites, chlorine dioxide, ozone, and the like
  • these agents sometimes have inadequate activity against fungi. Killing, inactivating, or otherwise reducing the active population of fungi on surfaces or within formulations can be particularly difficult.
  • the unique chemical composition of fungal cells, especially mold spores, makes them more resistant to chemical and physical agents than are other microorganisms. This resistance can be particularly troublesome when the spores or fungi are located on surfaces or in formulations that come in contact with food and/or beverages.
  • the invention provides antimicrobial compositions that comprise a combination of a first antimicrobial agent of Formula I and a second antimicrobial agent of Formula IV:
  • the first antimicrobial agent and second antimicrobial agent are present in a ratio of 1 : 1 by weight within the composition. In some embodiments, the first antimicrobial agent and second antimicrobial agent are present in the composition in a combined amount in the range of 0.01% to 0.1% by weight of said composition.
  • the antimicrobial composition can be provided with a pH in the range of 5 to 9. In accordance with aspects of the invention, the antimicrobial compositions can be formed by metathesis.
  • the antimicrobial compositions including a combination of antimicrobial agents of Formula (I) and Formula (IV) are effective as an antimicrobial agent with MIC levels of about 0.1% or less, against fungi selected from Aspergillus parasiticus, Trichoderma virens, Aureobasidium pullulans, Aspergillus flavus, Cladosporium cladosporiodes, Aspergillus flavus, Aspergillus oryzae, Aspergillus parasiticus, Ulocladium atrum, Candida albicans, Alternaria alternata, Stachybotrys chartarum, Aspergillus niger, and combinations thereof.
  • the invention provides antimicrobial products comprising the compositions described herein.
  • the antimicrobial products can include consumer products, industrial preparations, or a food or feed formulations.
  • the invention provides antimicrobial compositions comprising a combination of a first antimicrobial agent and a second antimicrobial agent.
  • the first antimicrobial agent can be selected from antimicrobial agents of Formula I, Formula II, Formula III, or a combination of any two or more of these.
  • the second antimicrobial agent can be selected from antimicrobial agents of Formula IV, Formula V, Formula VI, or a combination of any two or more of these. In other embodiments, the second antimicrobial agent can be selected from known antimicrobial agents.
  • the invention provides industrial preparations comprising an effective amount of an antimicrobial composition comprising 9- undecenoic acid, a salt of 9-undecenoic acid, an ester of 9-undecenoic acid, or a combination thereof.
  • the industrial preparations can be formed by metathesis.
  • certain embodiments of the invention can provide antimicrobial agents having efficacy against a broad spectrum of microorganisms, even at pH levels well above the neutral range, such as 8 and higher. This is significant, since many conventional antimicrobial agents lose efficacy at neutral pH levels and higher.
  • the invention provides methods for controlling bacterial growth in an environment, the method comprising contacting the environment with an effective amount of an antimicrobial composition that comprises a combination of a first antimicrobial agent of Formula I and a second antimicrobial agent of Formula IV.
  • the environment can be selected from consumer products, industrial preparations, and food or feed formulations.
  • the invention provides methods for controlling bacterial growth in an environment comprising contacting the environment with a composition comprising a first antimicrobial agent of Formula I and a second antimicrobial agent of Formula IV as active ingredients in a ratio of 1 : 1 by weight.
  • the bacterial growth comprises Gram positive bacteria and Gram negative bacteria.
  • the invention provides methods for controlling fungal growth in an environment comprising contacting the environment with a composition comprising a first antimicrobial agent of Formula I and a second antimicrobial agent of Formula IV as active ingredients in a ratio of 1 : 1 by weight.
  • FIGS. 1-13 are graphs illustrating antimicrobial properties for compositions in accordance with aspects of the invention, wherein composition identification and concentration (% by weight) are represented on the X-axis, and percentage fungal coverage (%) is represented on the Y-axis.
  • FIG. 14 is a graph illustrating antimicrobial properties for compositions in accordance with aspects of the invention, and compared to sodium benzoate, wherein time (days) is represented on the X-axis, and microbial reduction (Logi 0 ) is represented on the Y-axis.
  • the present invention relates to antimicrobial compositions, methods and systems that comprise one or more linear, monounsaturated fatty acids or derivatives thereof.
  • the antimicrobial compositions can be produced by metathesis of naturally occurring oils such as soybean or canola oils. More particularly, in one aspect, the invention relates to antimicrobial compositions comprising 9-undecenoic acid (also known as 9-hendecenoic acid, 9-undecylenic acid, and sometimes referred to herein as "9-UDA”), salts of 9-undecenoic acid, esters of 9-undecenoic acid, or a combination of any of these.
  • 9-undecenoic acid also known as 9-hendecenoic acid, 9-undecylenic acid, and sometimes referred to herein as "9-UDA”
  • the invention relates to antimicrobial compositions comprising a first antimicrobial agent selected from 9-undecenoic acid, a salt of 9- undecenoic acid, an ester of 9-undecenoic acid, or a combination of any two or more of these, and a second antimicrobial agent selected from 9-decenoic acid (also known as caproleic acid and sometimes referred to herein as 9-DA), a salt of 9- decenoic acid, an ester of 9-decenoic acid, or a combination of any two or more of these.
  • the antimicrobial composition can comprise 9- undecenoic acid and 9-decenoic acid.
  • the antimicrobial composition can comprise 9-undecenoic acid and 9-decenoic acid in a 1 : 1 ratio.
  • the antimicrobial agents can be formulated to provide a variety of antimicrobial compositions as end products.
  • the antimicrobial compositions can be in concentrated form or from a container, from an aerosol container, or from a container as a crystal, powdered or otherwise semi-solid or solid form, or as a liquid.
  • the antimicrobial compositions can be applied in various formulations such as, but not limited to, solutions, gels, creams, lotions, stick, balm, sprays, powders, granules, emulsions, and the like in either aqueous or nonaqueous vehicles.
  • the antimicrobial agents and compositions thus have utility in a wide variety of industrial and consumer applications.
  • the antimicrobial agent can be a monounsaturated fatty acid of 1 1 carbon atoms that can be provided as an acid, salt or ester.
  • the antimicrobial agent is 9-undecenoic acid having the structure shown in Formula (I):
  • 9-undecenoic acid also known as 9-hendecenoic acid or 9- undecylenic acid
  • 9-undecenoic acid has a molecular weight of approximately 184, and a boiling point of approximately 129°C/1 mm Hg.
  • 9-undecenoic acid has been found to be particularly effective as an antimicrobial agent, with a broad spectrum of efficacy.
  • 9-undecenoic acid exhibits low toxicity to humans and can be synthesized utilizing naturally-occurring starting materials.
  • the antimicrobial agent can be a salt of 9-undecenoic acid having the structure shown in Formula (II): ⁇ +n [Rr] n
  • Rl " is ; n is an integer, for example, ranging from 1 to 4; and K + " is a +n charged cation.
  • representative examples include group IA cations (such as Li + , Na + , K + , and Ag + ), and a variety of ammonium salts, such as those including ammonium (NH 4 + ) or quaternary ammonium (NR 4 + ) as cations.
  • group IA cations such as Li + , Na + , K + , and Ag +
  • ammonium salts such as those including ammonium (NH 4 + ) or quaternary ammonium (NR 4 + ) as cations.
  • representative examples include Ca 2+ , Mg 2+ , Zn 2+ , Cu 2+ , and Fe 2+ .
  • representative examples include Al 3+ , Fe 3+ and Ce 3+ .
  • representative examples include Ce 4+ .
  • the anion/cation pair (K +n [Rl " ] n ) can bind a known antimicrobial agent, such as those described elsewhere herein as useful for the second antimicrobial agent and/or known antimicrobial agent.
  • the anion/cation pair can serve a dual role, such as, for example, as antimicrobial agent and emulsifier or compatibility aid.
  • the antimicrobial agent can be an ester of 9- undecenoic acid having the structure shown in Formula (III):
  • organic group can be an aliphatic group, an alicyclic group, or an aromatic group.
  • Organic groups can include heteroatoms (such as O, N, or S atoms), as well as functional groups (such as carbonyl groups).
  • aliphatic group means a saturated or unsaturated, linear or branched, hydrocarbon group. This term is used to encompass alkyl, alkenyl, and alkynyl groups, for example.
  • alkyl group means a monovalent, saturated, linear or branched, hydrocarbon group.
  • alkenyl group means a monovalent, saturated, linear or branched, hydrocarbon group with one or more carbon-carbon double bonds.
  • alkynyl group means a monovalent, unsaturated, linear or branched, hydrocarbon group with one or more carbon-carbon triple bonds.
  • An alicyclic group is an aliphatic group arranged in one or more closed ring structures. The term is used to encompass saturated (such as cycloparaff ⁇ ns) or unsaturated (cycloolefins or cycloacetylenes) groups.
  • An aromatic group or aryl group is an unsaturated cyclic hydrocarbon having a conjugated ring structure. Included within aromatic or aryl groups are those possessing both an aromatic ring structure and an aliphatic group or an alicyclic group.
  • — R3 can be selected to serve a dual role as an antimicrobial agent and emulsifier or compatibility aid.
  • — R3 is a C 8 to C ]6 alkyl group may provide emulsification properties.
  • — R3 is an alkyl group, for example, a Ci to Ci 8 alkyl group or a Ci to C 6 alkyl group.
  • Representative examples include methyl, ethyl, propyl (n-propyl or i-propyl) butyl (n-butyl or t-butyl), heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, and the like.
  • — R3 can comprise a known antimicrobial agent, such as (but not limited to) antimicrobial agents described elsewhere herein as useful as first antimicrobial agents and/or known antimicrobial agents.
  • — R3 can be selected such that the structure of formula (III) is a monoglyceride, diglyceride, triglyceride, or a phospholipid.
  • — R3 is -CH 2 -CHOR'-CH 2 OR", where R' and R" are, independently, selected from fatty acids, phosphate groups, or hydrogen.
  • R' and R are, independently, selected from fatty acids, phosphate groups, or hydrogen.
  • the invention contemplates use of antimicrobial compositions composed of the agents of Formulae (I), (II) and/or (III) alone.
  • antimicrobial properties are provided primarily by the agent of Formulae (I), (II) and/or (III). To the extent any additional ingredients are included in the antimicrobial composition, such additional ingredient(s) do not contribute a significant antimicrobial property to the composition as a whole.
  • the inventive antimicrobial compositions can comprise a combination of a first antimicrobial agent and a second antimicrobial agent, wherein the first antimicrobial agent is selected from antimicrobial agents of Formulae (I), (II) and/or (III).
  • the second antimicrobial agent can be selected from 9-decenoic acid, salts of 9-decenoic acid, and/or esters of 9- decenoic acid.
  • antimicrobial compositions that comprise a combination of agents can include more than one of the first antimicrobial agents and/or second antimicrobial agents.
  • the second antimicrobial agent can be a monounsaturated fatty acid of 10 carbon atoms that can be provided as an acid, salt or ester.
  • the antimicrobial agent is 9-decenoic acid having the structure shown in Formula (IV):
  • 9-decenoic acid is a colorless liquid having a molecular weight of approximately 170, boiling point of approximately 269 0 C to 271°C/760 mm, specific gravity of 0.912 to 0.920 at 25 0 C, and refractive index of 1.44 to 1.45 at 2O 0 C.
  • 9-decenoic acid is soluble in water at biocidal levels, and soluble in alcohol.
  • the second antimicrobial agent is an ester of 9- decenoic acid having the structure shown in Formula V:
  • organic group can be an aliphatic group, an alicyclic group, or an aromatic group.
  • Organic groups can include heteroatoms (such as O, N, or S atoms), as well as functional groups (such as carbonyl groups).
  • aliphatic group means a saturated or unsaturated, linear or branched, hydrocarbon group. This term is used to encompass alkyl, alkenyl, and alkynyl groups, for example.
  • alkyl group means a monovalent, saturated, linear or branched, hydrocarbon group.
  • alkenyl group means a monovalent, saturated, linear or branched, hydrocarbon group with one or more carbon-carbon double bonds.
  • alkynyl group means a monovalent, unsaturated, linear or branched, hydrocarbon group with one or more carbon-carbon triple bonds.
  • An alicyclic group is an aliphatic group arranged in one or more closed ring structures. The term is used to encompass saturated (such as cycloparaffins) or unsaturated (cycloolefms or cycloacetylenes) groups.
  • An aromatic group or aryl group is an unsaturated cyclic hydrocarbon having a conjugated ring structure.
  • aromatic or aryl groups include those possessing both an aromatic ring structure and an aliphatic group or an alicyclic group.
  • — R can be selected to serve a dual role as an antimicrobial agent and emulsifier or compatibility aid.
  • — R is a C 8 to Ci 6 alkyl group may provide emulsification properties.
  • — R is an alkyl group, for example, a Ci to Ci 8 alkyl group or a Ci to C 6 alkyl group.
  • Representative examples include methyl, ethyl, propyl (n-propyl or i-propyl) butyl (n-butyl or t-butyl), heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, and the like.
  • — R can comprise a known antimicrobial agent, such as (but not limited to) antimicrobial agents described elsewhere herein as useful as first antimicrobial agents and/or known antimicrobial agents.
  • the second antimicrobial agent is a salt of 9-decenoic acid having the structure shown in Formula (VI):
  • n is an integer, for example, ranging from 1 to 4; and K + " is a +n charged cation.
  • representative examples include group IA cations (such as Li + , Na + , K + , and Ag + ), and a variety of ammonium salts, such as those including ammonium (NH 4 + ) or quaternary ammonium (NR 4 + ) as cations.
  • group IA cations such as Li + , Na + , K + , and Ag +
  • ammonium salts such as those including ammonium (NH 4 + ) or quaternary ammonium (NR 4 + ) as cations.
  • representative examples include Ca 2+ , Mg 2+ , Zn 2+ , Cu 2+ , and Fe 2+ .
  • representative examples include Al 3+ , Fe 3+ and Ce 3+ .
  • representative examples include Ce 4+ .
  • the anion/cation pair (K + " [R2 ⁇ ] n ) can bind a known antimicrobial agent, such as those described elsewhere herein as useful for the second antimicrobial agent.
  • the anion/cation pair can serve a dual role, such as, for example, as antimicrobial agent and emulsifier or compatibility aid.
  • utilization of a salt of 9-decenoic acid, as described in Formula (VI) can be advantageous, for example, by being more soluble in aqueous systems, less volatile, and/or easier to handle as compared to the acid or ester forms of 9-decenoic acid.
  • the choice of an antimicrobial agent from Formulae (IV), (V) and/or (VI) will depend upon the end use of the composition, including formulation considerations, target microorganisms, and the like.
  • 9-decenoic acid and salt can occur within a composition by virtue of the pH level of the composition.
  • a composition will be composed of approximately equal amounts of 9-decenoic acid and salt of 9-decenoic acid (50/50 9-deceonic acid/salt).
  • presence of 9-decenoic acid can be particularly advantageous.
  • antimicrobial compositions comprising a combination of a first antimicrobial agent of Formula (I), (II) and/or (III) and a second antimicrobial agent of Formulae (IV), (V) and/or (VI) provide antimicrobial compositions having superior activity against a wide range of microorganisms, including Gram-positive bacteria and fungi, as well as Gram-negative bacteria.
  • These antimicrobial compositions can, in some aspects, provide special value in a broad range of industrial and consumer applications due to their low oral, skin, eye and aquatic toxicity as well as low irritation properties. This ability to deliver efficacious antimicrobial activity while providing low toxicity and irritation properties can be particularly valuable in applications such as consumer products, where toxicity and environmental effects can be a concern.
  • the antimicrobial compositions can be synthesized by metathesis from natural products, thereby providing a synthesis route involving renewable resources as starting materials.
  • the invention can provide antimicrobial compositions comprising a combination of any one or more of the antimicrobial agents of Formula (I), (II) and/or (III), and a second antimicrobial agent that comprises one or more known antimicrobial agents.
  • the invention can provide commercial products with significantly lower toxicity than current products that include the known antimicrobial agent(s) alone.
  • toxicity is used in its broadest sense. It may mean toxicity to people per se, harm or damage to the environment, indirect harm to people via environmental damage, and/or simply skin or mucous membrane irritation.
  • the antimicrobial agents of Formula (I), (II) and/or (III) can replace at least a portion of the known antimicrobial agent, thus providing lower toxicity of the overall product. It is known that products such as KathonTM, TriclosanTM and others can have toxicity effects in current formulations. Thus, by replacing at least a portion of these substances with the antimicrobial agent of Formula (I), (II) and/or (III), an end product with lower overall toxicity can be achieved. In some aspects, this lower toxicity can be accomplished while maintaining efficacy of the antimicrobial agents as a whole.
  • any antimicrobial agent that is compatible with the antimicrobial agent of Formula I, II and/or III can be utilized as a known antimicrobial agent in accordance with these embodiments.
  • compatible is meant the antimicrobial agents can be mixed together without adversely affecting one or more useful properties of the individual antimicrobial agents, for example, the ability of the antimicrobial agents to be formulated into a stable composition, such that the individual antimicrobial agents remain in the composition without separating out over time (such as by precipitation).
  • the antimicrobial composition can provide one or more of the following benefits: broadened spectrum of activity; use of lower concentrations of individual antimicrobial agents, thus minimizing irritancy potential; reduced risk of the development of microbial resistance; synergistic effect, giving greater than the anticipated simple additive effect; potentiation, or activity of an antimicrobial agent ' is enhanced by combination with a microbiologically inactive or weakly active agent such as EDTA or Monolaurin; and/or improved long-term stability of product by combining a labile, strongly biocidal agent with a stable longer-acting agent.
  • formulating a composition that includes a reduced amount of the known antimicrobial agent can provide significant toxicity and/or environmental benefit.
  • Illustrative known antimicrobial agents include, but are not limited to: phenol derivatives (such as halogenated phenols, for example 3,5-dichlorophenol, 2,5-dichlorophenol, 3,5-dibromophenol, 2,5-dibromophenol, 2,5- or 3,5-dichloro-4- bromophenol, 3,4,5-trichlorophenol, 3,4,5-tribromophenol, phenylphenol, 4-chloro- 2-phenylphenol, 4-chloro-2-benzylphenol); dichlorophene, hexachlorophene; aldehydes (such as formaldehyde, glutaraldehyde, salicylaldehyde); alcohols (such as phenoxyethanol); antimicrobial carboxylic acids and derivatives thereof such as parabens, including methyl, propyl and benzyl parabens, and the like; organometallic compounds (such as tributyl tin derivatives); iodine compounds (
  • second antimicrobial agents include TriclosanTM (2,4,4'-trichloro-2'-hydroxydiphenyl ether, also known as 5- chloro-2-(2,4-dichlorophenoxy)phenol) and KathonTM (methyl chloroisothiazolinone and methyl isothiazolinone in various ratios).
  • an antimicrobial agent of Formula (I), (II) and/or (III) when combined with a known antimicrobial agent, the chemical reactivity of the ingredients is taken into consideration during formulation of the product.
  • the agent of Formula I can, in some instances (for example, 9-undecenoic acid) be incompatible with a certain known antimicrobial agent, but in other instances (for example, when formulated as a salt) will mix well.
  • the antimicrobial agent content is the total amount of antimicrobial agent (or agents), based on total weight of the composition, provided in the product. For example, when only one antimicrobial agent is selected from the agents defined in Formulae (I), (II) and/or (III), then the antimicrobial agent content is the amount of the agent included in the product, based on total weight of the product. In another example, if a combination of two antimicrobial agents (A and B) is provided in a composition, then the antimicrobial agent content is the total of A + B in the composition.
  • the invention provides antimicrobial compositions that include a combination of any two or more of the antimicrobial agents of Formulae (I), (II) and/or (III).
  • the relative amounts of each antimicrobial agent can be selected to provide an overall antimicrobial effect.
  • a combination of acid and salt can occur by virtue of the formulation parameters.
  • the antimicrobial composition comprises a combination of two antimicrobial agents, the antimicrobial agents can be provided in a 1 : 1 ratio.
  • the antimicrobial agents when the antimicrobial composition comprises a combination of two antimicrobial agents, can be provided in a ratio in the range of about 1 : 10 to about 10: 1, or in the range of about 1 :5 to about 5: 1, or in the range of about 1 : 1 to about 3: 1.
  • Embodiments of the antimicrobial agents of Formulae (I)-(VI) may be prepared, for example, by the cross-metathesis of propylene with a fatty acid, a fatty ester, a glyceride (e.g., triglyceride) or a mixture thereof.
  • the 9-undecenoic acid (or salt or ester thereof) and/or 9-decenoic acid (or salt or ester thereof) can be separated from the starting material and other components using known techniques for separation, including, for example, distillation or chromatography.
  • a useful synthetic route is reported, for example, in U.S. Provisional Patent Application 60/851,693, filed October 13, 2006, and entitled "SYNTHESIS OF TERMINAL ALKENES FROM INTERNAL ALKENES VIA OLEFIN METATHESIS",
  • the antimicrobial agents can be produced by cross metathesis of propylene with a naturally occurring oil such as soybean or canola oil.
  • the antimicrobial composition comprises 9-undecenoic acid (or salt or ester thereof) and 9-decenoic acid (or salt or ester thereof) in weight ratio of about 0.2: 1 to about 2: 1.
  • the antimicrobial composition comprises 9-undecenoic acid (or salt or ester thereof) and 9-decenoic acid (or salt or ester thereof) in a weight ratio of about 1 : 1.
  • the metathesis reaction product comprises a mixture of 9-undecenoic acid (or a salt thereof) and a second antimicrobial agent selected from 9-decenoic acid, a salt of 9-decenoic acid, an ester of 9-decenoic acid, or a mixture thereof. In these cases, separation of the product mixture is not required.
  • Non-metathesis routes to the production of 9-decenoic acid include, for example, the method reported by Black et al., in Unsaturated Fatty Acids. Part I. The Synthesis of Erythrogenic (Isantic) and Other Acetylenic Acids; Journal of the Chemical Society, Abstracts (1953) at pp. 1785-93. As reported by Black, a solution of chromium trioxide (19.0 g) in water (20 cc) was added over 1.5 hours with vigorous stirring to a solution of 1 : 1 diphenylundeca-l : 10-diene (25.0 g) in glacial acetic acid (250 cc) at 35°C.
  • 9-decenoic acid (8.5 g). 9-decenoic acid can also be obtained commercially, for example, from
  • 9-decenoic acid may be converted to its esters (see, formula V) and salts (see, formula VI) according to known synthetic techniques for converting carboxylic acid compounds into esters or salts, respectively.
  • Antimicrobial compositions in accordance with the invention can be formulated by mixing or dispersing the active ingredients in a selected proportion with a vehicle (e.g., liquid) for dissolving or suspending the active components.
  • vehicle e.g., liquid
  • the vehicle may contain a diluent, an emulsif ⁇ er, a wetting agent or the like, as typically used in formulation of antimicrobial compositions.
  • Illustrative uses of the antimicrobial compositions of the invention include the protection of paint, coatings, adhesives, aqueous industrial products, leather, wood products, inks, sealants, caulkings, metalworking fluids, petroleum applications, water treatments, textiles, polymer emulsions, and the like. Additional exemplary uses include personal care products (such as cosmetics and toiletries) and food or feed applications.
  • the compositions of the invention can be provided as wettable powders, liquid mixtures such as dispersions, emulsions, microemulsions or in any other suitable product form that is desirable or most useful for a particular application.
  • the composition also will likely be provided with adjuvants conventionally employed in compositions intended for such applications, such as organic binding agents, additional fungicides, auxiliary solvents, processing additives, fixatives, plasticizers, UV stabilizers or stability enhancers, water soluble or water insoluble dyes, color pigments, siccatives, corrosion inhibitors, antisettlement agents, anti-skinning agents, extenders, fillers, thickeners, driers, plasticizers, wetting agents, emulsifiers, free-thaw stabilizers, coalescents, dispersants, defoamers, and the like.
  • adjuvants can be included in the amounts ordinarily used for these purposes.
  • the invention provides methods for controlling bacterial and/or fungal growth in an environment, the method comprising contacting the environment with an effective amount of an antimicrobial comprising 9-undecenoic acid, a salt of 9-undecenoic acid, or a combination thereof.
  • the environment can comprise a consumer product, industrial preparation, and/or food or feed formulation.
  • the "effective amount" of antimicrobial composition that is desirable in a given consumer product, industrial preparation, or food or feed formulation can be determined by one of skill in the art using various known techniques and methods. Performance of a given antimicrobial composition in a product, preparation or formulation can be evaluated, for example, as described below.
  • the antimicrobial compositions of the invention can provide preservative, antiseptic, sanitizing, and/or disinfectant features to a wide variety of end products.
  • Some illustrative common applications that can benefit from the antimicrobial properties described herein include industrial and consumer applications, as well as food and feed (i.e., livestock feed) applications.
  • antimicrobial compositions including 9- undecenoic acid, a salt of 9-undecenoic acid, and/or an ester of 9-undecenoic acid are useful in controlling microbial growth.
  • control of microbial growth can involve preventing propagation of microbes within an environment, and/or elimination of many or all pathogenic microorganisms in an environment.
  • 9-undecenoic acid, salts of 9-undecenoic acid and/or esters of 9- undecenoic acid can be incorporated into compositions to protect the compositions themselves from microbial attack (i.e., as preservatives).
  • 9- undecenoic acid, salts of 9-undecenoic acid and/or esters of 9-undecenoic acid can be utilized as an auxiliary agent within the composition to be preserved and/or protected from microbial attack and/or spoilage.
  • 9-undecenoic acid, salts of 9-undecenoic acid and/or esters of 9-undecenoic acid can be employed as a disinfectant.
  • 9- undecenoic acid, salts of 9-undecenoic acid and/or esters of 9-undecenoic acid can be incorporated as an active ingredient in a variety of cleansing agent products for household and industrial use.
  • the term "disinfect" shall mean the elimination of many or all pathogenic microorganisms in an environment with the possible exception of bacterial endospores.
  • the term "sanitize” shall mean the reduction of contaminants in the inanimate environment to levels considered safe according to public health ordinance, or that reduces the bacterial population by significant numbers where public health requirements have not been established. An at least 99% reduction in bacterial population within a 24 hour time period is deemed "significant.”
  • the invention provides antimicrobial compositions having utility in industrial applications.
  • Some illustrative industrial applications include wood preservation (e.g., prevention or reduction in slime formation and/or wood rotting), preservation of polymer emulsions, surface coating applications (e.g., paints and coatings), metalworking fluids (MWF), petroleum production and preservation (oil well simulation, crude oil production, jet fuels), industrial water treatment systems (e.g., cooling water), pulp and paper production, leather production, and textile production and protection.
  • wood preservation e.g., prevention or reduction in slime formation and/or wood rotting
  • preservation of polymer emulsions e.g., surface coating applications
  • MMF metalworking fluids
  • petroleum production and preservation oil well simulation, crude oil production, jet fuels
  • industrial water treatment systems e.g., cooling water
  • pulp and paper production leather production, and textile production and protection.
  • the invention provides methods for protecting surface coating compositions (such as water-based paint or coating) from in-can spoilage or film degradation due to the action of microorganisms.
  • the method comprises incorporating into the surface coating composition an antimicrobial composition comprising 9-undecenoic acid, a salt of 9-undecenoic acid, an ester of 9-undecenoic acid, or a combination thereof.
  • the method comprises incorporating into the surface coating composition an antimicrobial composition comprising 9- undecenoic and, a salt of 9-undecenoic acid, an ester of 9-undecenoic acid, or a combination thereof, in combination with a second antimicrobial agent.
  • the second antimicrobial agent can comprise 9-decenoic acid, a salt of 9-decenoic acid, an ester of 9-decenoic acid, or a combination thereof, and/or a known antimicrobial agent.
  • the methods protect the surface coating composition from in-can spoilage from the action of microorganisms. In other embodiments, the methods protect the surface coating composition from film degradation due to the action of microorganisms. In an exemplary embodiment, the methods protect the surface coating composition from both in-can spoilage and film degradation from the action of microorganisms. Film degradation typically takes the form of discoloration, dulling, loss of integrity, increased dirt retention, and/or loss of adhesion of the film.
  • the amount of antimicrobial composition that is desirable in a given surface coating formulation can be determined by one of skill in the art using various known techniques and methods. Performance of a given antimicrobial composition in a composition may be evaluated, for example, as described below.
  • An antimicrobial for many coatings applications desirably provides protection against both fungal and algal growth.
  • An antimicrobial for many coatings applications desirably provides protection against both fungal and algal growth.
  • the fact that an antimicrobial composition is known to possess fungicidal activity, however, does not mean that it will necessarily be effective in inhibiting mold growth on exterior surfaces for long periods of time. For example, certain antimicrobial compositions may lose their fungicidal activity prior to being applied in a dried film.
  • antimicrobial compositions may prevent deterioration by anaerobic microorganisms in a sealed can, but may fail to prevent the formation of mold or mildew by aerobic microorganisms on a surface exposed to air.
  • the activity of the antimicrobial composition may be impaired by the weathering environment to which many exterior coatings are exposed.
  • the minimum inhibitory concentration (MIC) of the antimicrobial composition in a coating composition is determined.
  • MIC refers to the concentration of a given antimicrobial composition below which growth of microorganisms is not inhibited.
  • MIC may be determined using a dilution series to identify the amount of antimicrobial agent that is required to inhibit microbial growth under defined laboratory conditions. In this test, efficacy is determined against a selected grouping of fungal and/or algal species that are often found on coated surfaces.
  • Representative organisms include, for example, fungi, such as Alternaria alter nata, Aspergillus species, Aureobasidium pullulans, Cladosporium species, Penicillium species, Phoma violacea, Stachybotrys chararum; and algae, such as Oscillatoria spp., Chlorella spp., Trentepholia spp., Nostoc spp., and Pleurococcus spp.
  • MIC values are often presented in parts per million (ppm) required to inhibit the growth of a target organism or group of target organisms. A lower MIC value indicates increased efficacy.
  • Accelerated laboratory exposure may also be used to evaluate the desired amount of antimicrobial composition in a coating formulation.
  • This test typically involves placing panels painted with an antimicrobial composition-containing coating formulation into a test chamber having a humid atmosphere.
  • One or more test microorganisms are added directly to the coating or are introduced into the chamber.
  • the high humidity promotes rapid microbial growth and the painted samples are monitored over time to determine the effectiveness of the antimicrobial composition at the formulated level in inhibiting growth of the test organism(s).
  • a representative accelerated exposure protocol is reported in ASTM D3273 "Standard Test Method for Resistance to Growth of Mould on the Surface of Interior Coatings in an Environmental Chamber.”
  • field trials can be conducted in order to determine how an antimicrobial performs in a coating when exposed to outdoor conditions.
  • the coating containing antimicrobial composition is applied to a test panel and is exposed at a fixed orientation and angle.
  • the panels are monitored over time and are rated for the extent of microbial growth.
  • Performance of the antimicrobial composition is measured as the time (e.g., in months or years) that the antimicrobial composition prevents microbial growth form reaching a predetermined level.
  • a representative field trial protocol is reported in ASTM D3456 "Standard Practice for Determining by Exterior Exposure Tests the Susceptibility of Paint Films to Microbiological Attack.”
  • Performance of an antimicrobial composition for efficacy against in-can spoilage may be evaluated, for example, as described below.
  • the antimicrobial composition is evaluated to determine the MIC of the antimicrobial composition for in-can spoilage of a coating formulation.
  • the MlC may be determined using a dilution series to identify the amount of antimicrobial composition that is required to inhibit in-can microbial growth under defined laboratory conditions. Suitable MIC procedures are discussed elsewhere herein.
  • Another method for evaluating an antimicrobial composition for in-can preservation of a coating composition is a challenge test. In a challenge test, microorganisms are deliberately added to a sample of the coating formulation containing an antimicrobial composition. The survival of the microorganisms as a function of time is then monitored. In some test protocols, the sample is challenged several times. A representative protocol for evaluating antimicrobial composition efficacy is ASTM 2574 "Standard Test Method for Resistance of Emulsion Paints in the Container to Attack by Microorganisms.”
  • the antimicrobial composition can be incorporated into the surface coating formulations using conventional techniques.
  • two or more (for example, 2, 3, 4 or more) antimicrobial agents are used in a surface coating formulation in order to provide, for example, a broader spectrum of activity, lower toxicity, and/or lower cost.
  • two or more of: 9-undecenoic acid, salts of 9-undecenoic acid and/or esters of 9- undecenoic acid can be used together in a surface coating formulation in accordance with the invention.
  • one or more of 9-undecenoic acid, a salt of 9-undecenoic acid or an ester of 9-undecenoic acid can be used with one or more second antimicrobial agents.
  • the second antimicrobial agent(s) can comprise an antimicrobial agent having Formulae (IV), (V) and/or (VI)), and/or one or more known antimicrobial agents.
  • in-can preservatives include 4,4- dimethyloxazolidine; 3,4,4, -trimethyloxazolidine; l,2-dibromo-2,4-dicyanobutane; 2[(hydroxymethyl)-amino]ethanol; 2[(hydroxymethyl)-amino]propanol; 1 -(3- chlorallyl)-3,5,7-triaza-l-azoniaadamantane chloride; l,2-benzisothiazolin-3-one; 5- chloro-2-methyl-4-isothiazolin-3-one; 2-methyl-4-isothiazolin-3-one; 5- hydroxymethoxy-methyl-l-aza-Sjy-dioxa-bicyclo-p.S.OJoctane; 5-hydroxymethyl- l-aza-3
  • dry film preservatives include tetrachloroisophthalonitrile, 2-iodo-2-propynyl butyl carbamate, 2-n-octyl-4- isothiazolin-3-one, diiodomethyl-p-tolylsulphone, n-(trimethylthio)phthalimide, carbendazim, dichloro-octylisothiazolinone, zinc pyrithione, thiuram and barium meta-borate. Combinations may be used to gain broad-spectrum efficacy.
  • the first antimicrobial agent and the second antimicrobial agent are present in ratios ranging from about 1 : 10 to about 10: 1.
  • the first antimicrobial agent is added to the coating formulation in an amount ranging from about 0.01% weight to about 5% weight based on the total weight of the coating composition (e.g., about 0.1% to about 1% weight based on the total weight of the coating composition), and the second antimicrobial agent is added to the coating formulation in an amount ranging from about 0.01% weight to about 5% weight based on the total weight of the coating composition (e.g., about 0.1% to about 1% weight based on the total weight of the coating composition).
  • surface coatings of the invention comprise water- based latex paint compositions comprising a latex binder, water, and an antimicrobial agent comprising 9-undecenoic acid, an ester of 9-undecenoic acid, a salt of 9-undecenoic acid, or a combination thereof.
  • the surface coating compositions may contain various auxiliary materials, such as pigments, extenders, fillers, thickeners, driers, plasticizers, wetting agents, emulsifying agents, freeze- thaw stabilizers, coalescents, dispersants, anti-settling agents, defoamers, solvents, and the like in the amounts ordinarily used for these purposes.
  • a second in-can or dry film antimicrobial agent may be added.
  • the manufacture of a latex paint typically occurs in two steps, commonly referred to as the grind (step 1) and the letdown (step 2).
  • the liquid components e.g., water
  • the dry pigments are dispersed in the liquid components under high shear.
  • the letdown stage the latex binder and other ingredients are added, typically under low speed mixing to form the latex paint composition.
  • a biocidally effective amount of the antimicrobial agent(s) may be added at either the grind stage or the letdown stage, and may be preblended with a component of the composition or may be added directly.
  • the antimicrobial agent(s) is added in the letdown stage.
  • the invention provides methods for protecting metalworking fluids (MWF) from undesirable microbial growth.
  • the method comprises incorporating into the MWF an antimicrobial composition comprising 9- undecenoic acid, a salt of 9-undecenoic acid, an ester of 9-undecenoic acid, or a combination thereof.
  • the method comprises incorporating into the surface coating composition an antimicrobial composition comprising 9-undecenoic and, a salt of 9-undecenoic acid, an ester of 9-undecenoic acid, or a combination thereof, in combination with a second antimicrobial agent.
  • the second antimicrobial agent can comprise 9-decenoic acid, a salt of 9-decenoic acid, an ester of 9-decenoic acid, or a combination thereof, and/or a known antimicrobial agent.
  • the methods protect the MWF from spoilage from the action of microorganisms.
  • the antimicrobial composition can be added to the MWF during formulation, prior to storage and/or during storage.
  • the methods protect the MWF during use from degradation due to the action of microorganisms.
  • the methods protect the MWF from both spoilage and degradation during use from the action of microorganisms.
  • MWF degradation typically takes the form of loss of emulsion stability, pH changes, viscosity changes, loss of lubrication properties, discoloration, production of unpleasant odors and growth of slimes and other biomass deposits.
  • the growth of slimes and other biomass deposits can be particularly undesirable because they can clog up the pipes, filters and screens used in MWF handling systems.
  • Anaerobic bacteria, specifically the sulfate reducers may produce hydrogen sulfide and other disagreeable and toxic gases. More importantly, the microbial contaminants may result in adverse health effects in workers exposed to MWF aerosols.
  • the antimicrobial compositions are thermostable, to accommodate the elevated temperature ranges of the MWF.
  • MWF are used in metal processing operations such as cutting, drilling, tapping, grinding, milling, rolling, metal drawing, stamping and turning operations.
  • the primary function of the MWF is to provide cooling and lubrication to the metal and tools used in the processing operations.
  • MWF are also used to protect metals and metal working tools against corrosion and rust formation, as temporary surface coatings to protect newly machined articles such as coils and springs, as quenching fluids and as casting fluids.
  • MWF have a pH of about 3 to about 10, or about 7 to about 10, or about 6 to about 9 and are organized into four categories, namely, straight oils, soluble oils, semisynthetic fluids, and synthetic fluids.
  • the distinguishing feature among the fluids is the amount of highly refined oil. Straight oils are 60-100% oil and synthetic fluids contain no oil. The two largest classes, the soluble oils, and semisynthetic fluids, contain 5-85% oil. While these are often split into two categories, their only distinguishing feature is that semi-synthetic fluids contain less oil than the soluble oils.
  • inventive antimicrobial compositions can be utilized in straight oil MWF, soluble oil (emulsifiable oil) MWF, semi-synthetic MWF, synthetic MWF, quenching fluids, water-soluble corrosion products, casting fluids, and the like.
  • Antimicrobial agents can be incorporated as components in fo ⁇ nulated MWF or added to MWF before and during use to prevent microbial growth.
  • Illustrative commonly used biocides for MWF include nitroalcohols such as tris(hydroxymethyl) nitromethane (Tris NitroTM); s-triazines such as hexahydro- l,3,5-tris(2-hydroxyethyl)-S-triazine (GrotanTM, OnyxideTM 200, BusanTM 1060, BiobanTM GK, TriadineTM 3) and hexahydro-l,3,5-triethyl-S-triazine (Vancide TH); l-(3-chloroallyl)-3,5,7-triaza-l-azonia adamantane chloride (Dowicil 75); 4-(2- nitrobutyl)mo ⁇ holine-4,4-(2-ethyl-2-nitrotrimethylene) dimo ⁇ holine (BiobanTM P- 1487); o-phenyl phenol (DowicideTM -1); sodium 2-pyridinethiol-l -
  • antimicrobial agents for MWF include quaternary ammonium compounds; urea derivatives; antimicrobial amino compounds such as dodecylamine or 2-[(hydroxymethyl)-amino]ethanol; antimicrobial imidazole derivatives; antimicrobial nitrile compounds such as 2-bromo-2-bromomethyl-glutaronitrile; antimicrobial thiocyanate derivatives such as methylene(bis)thiocyanate; isothiazolin-3-ones such as 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4- isothiazolin-3-one, 4,5-dichloro-2-methylisothiazolin-3-one 2-n-octylisothiazolin-3- one, 4,5-trimethylene4-isothiazolin-3-one and 2-methyl-4,5-trimethylene-4- isothiazolin-3-one and mixtures thereof; thiazole derivatives; antimicrobial nitro compounds; iod
  • Some microbiocidal or microbiostatic activities of the known MWF antimicrobial agents occur through the release of formaldehyde.
  • Formaldehyde releasers are usually soluble in water rather than oil and are more effective against bacteria than fungi.
  • Tris(hydroxym ethyl) nitromethane and hexahydro-1,3,5, tris(2- hydroxyethyl)-s-triazine are examples of formaldehyde-releasing antimicrobial agents.
  • Formaldehyde is an airway irritant and recognized cause of occupational asthma. Further, studies have suggested that exposure to certain known antimicrobial agents can cause allergic or irritant contact dermatitis. Concerns have been raised about the potential carcogenicity of some of these known antimicrobial agents because of their formaldehyde-releasing action.
  • Non-formaldehyde-releasing antimicrobial agents are generally more effective against fungi than formaldehyde releasers but are also effective against bacteria.
  • the phenolic compounds are oil soluble, and the antimicrobial agent derivatives of morpholine and the dioxanes are partially soluble in oil and water.
  • Sodium 2-pyridinethiol-l -oxide and o-phenyl phenol are examples of non- formaldehyde-releasing biocides.
  • Nitrated antimicrobial agents such as Bronopol (2-bromo-2-nitro 1,3- propanediol), 2-methyl-2-nit.ro- 1,3 -propanediol, and 5-methyl-5-nitro-l ,3-dioxane, which have been shown to release nitrite, can act as nitrosating agents in MWF.
  • Bioban P- 1487 which is composed of 70% 4-(2-nitrobutyl) morpholine and 30% 4,4-(2-ethyl-2-nitrotrimethylene) dimorpholine, can dissociate to form nitrite ions.
  • Bioban P- 1487 added to metalworking fluid concentrate can directly form N- nitrosomorpholine (NMOR, an animal carcinogen), which can increase in concentration over time.
  • NMOR an animal carcinogen
  • known antimicrobial agents for use in MWF can have disadvantages, as noted above.
  • the inventive antimicrobial compositions can be used in substitution of these known metalworking fluid antimicrobial agents.
  • the inventive antimicrobial compositions can be used in combination with any one or more of these known metalworking fluid antimicrobial agents, thereby reducing the amount of the known antimicrobial agent required for preservative or biocidal effect. This, in turn, can reduce the potential hazards noted herein for these known metalworking fluid antimicrobial agents.
  • MWF can be prepared as a concentrate that is diluted with water prior to use.
  • the composition also will likely be provided with additives conventionally employed in compositions intended for such applications.
  • the MWF can include such additives as water, mineral oil, emulsifying agents, surfactants (which can be cationic, anionic or non-ionic), chelating agents, coupling agents, viscosity modifiers, detergent, plasticizer, anti-mist agents, anti-weld agents, oiliness agents, surfactant wetting agents, dispersants, passivators, anti-foam ing agents, alkaline reserves, dyes, odorants, corrosion inhibitors, oxidation inhibitors, and extreme pressure additives.
  • surfactants which can be cationic, anionic or non-ionic
  • chelating agents such additives as water, mineral oil, emulsifying agents, surfactants (which can be cationic, anionic or non-ionic), chelating agents, coupling agents, viscosity modifiers, detergent, plasticizer, anti-mist agents, anti-weld agents, oiliness agents, surfactant we
  • the inventive antimicrobial compositions can be added directly to the MWF, or the antimicrobial composition can be formulated with a carrier for ease of handling and dosing.
  • the carrier can be a solid or a liquid medium (thereby forming a solution, suspension, emulsion or micro- emulsion).
  • the carrier is a liquid, it is generally selected so that the formulation is compatible with the MWF to be protected.
  • the carrier is preferably a solvent, especially a non-polar solvent.
  • the carrier is preferably water or a water-miscible organic solvent or mixture thereof.
  • the antimicrobial composition formulation is in the form of a suspension or emulsion, it preferably also contains a surface active agent to produce a stable dispersion or to maintain the discontinuous phase uniformly distributed throughout the continuous phase.
  • a surface active agent to produce a stable dispersion or to maintain the discontinuous phase uniformly distributed throughout the continuous phase.
  • Any surface active agent that does not have a significant adverse effect on the antimicrobial activity of the antimicrobial agent can be utilized.
  • Suitable surface active agents include emulsifiers, surfactants, and mixtures thereof.
  • the emulsifiers/surfactants may be non-ionic, anionic, or a mixture thereof.
  • Suitable anionic emulsifiers and surfactants include alkylarylsulfonates (e.g., calcium dodecylbenzensulfonate), alkylsulfates (e.g., sodium dodecyl sulfate), sulfosuccinates (e.g., sodium dioctylsulfosuccinate), alkyletheresulfates, alkylaryletheresulfates, alkylether carboxylates, alkylaryletherecarboxylates, lignin sulfonates or phosphate esters.
  • alkylarylsulfonates e.g., calcium dodecylbenzensulfonate
  • alkylsulfates e.g., sodium dodecyl sulfate
  • sulfosuccinates e.g., sodium dioctylsulfosuccinate
  • alkyletheresulfates
  • Suitable non-ionic emulsifiers and surfactants include fatty acid ethoxylates, ester ethoxylates, glyceride ethoxylates (e.g., castor oil ethoxylate), alkylaryl polygylcol ethers (e.g., nonylphenol ethoxylates), alcohol ethoxylates, propylene oxide-ethylene oxide condensation products, amine ethoxylates, amide ethoxylates, amine oxides, alkyl polyglucosides, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylenesorbitol esters or alcohol ethoxy carboxylates (e.g., those obtainable from Ci 2 - I4 alcohols).
  • the amount of antimicrobial composition that is desirable in a given MWF formulation can be determined by one of skill in the art using various known techniques and methods. Performance of a given antimicrobial composition in a composition may be
  • performance of an antimicrobial composition for efficacy against spoilage of MWF is evaluated, for example, as described in ASTM E2169- 01 "Standard Practice for Selecting Antimicrobial Pesticides Use in Water-Miscible Metalworking Fluids.”
  • Another method for assessment of performance of an antimicrobial composition for efficacy against microorganisms can be based on ASTM E686-91 : “Standard Test Method for Evaluation of Antimicrobial Agents in Aqueous Metal Working Fluids.”
  • the MWF is selected, and the test microorganisms (bacteria, fungi) are gradually acclimatised to the MWF.
  • the organisms are grown in biocide-free MWF (containing 50% (v/v) minimal broth) with aeration at 25 0 C until microbial count reaches 10 9 cfu/ml. Every seven (7) days each microorganism is subcultured into 90 ml (10 ml inoculum) and re-incubated. Subculturing can be done for three cycles before use.
  • Bacteria and fungi are enumerated by streaking an aliquot onto nutrient or malt agar as appropriate.
  • the mixtures are aerated using capillary tubing to bubble air into the bottom of the bottle (introduced by means of a multi-valve air manifold).
  • Antifoam is also added.
  • the aeration is stopped and volume replaced with sterile distilled water.
  • the mixture is allowed to sit for 64 hours and then mixed. 10 ml of inoculum is used to re-inoculate and all losses are replaced with antimicrobial composition containing MWF.
  • the pH of the MWF is measured at the start of the test and every 7 days.
  • the physical condition of the MWF is also noted at the start of the test and every 7 days. Aeration is resumed and the regime repeated for a minimum of 6 weeks or until failure.
  • MlC is the lowest treatment dose that will prevent a laboratory test culture population from proliferating, or otherwise contributing to biodeteri oration.
  • a kill dose is about two to six times greater than the MIC dose.
  • the invention provides methods for protecting consumer products.
  • Illustrative consumer products include cleansing agents and personal care products (such as cosmetics and toiletries).
  • the invention provides methods for protecting personal care products from spoilage or degradation during use due to the action of microorganisms.
  • the method comprises incorporating into the personal care product an antimicrobial composition comprising 9-undecenoic acid, a salt of 9- undecenoic acid, an ester of 9-undecenoic acid, or a combination thereof.
  • the method comprises incorporating into the personal care product an antimicrobial composition comprising 9-undecenoic and, a salt of 9-undecenoic acid, an ester of 9-undecenoic acid, or a combination thereof, in combination with a second antimicrobial agent.
  • the second antimicrobial agent can comprise 9- decenoic acid, a salt of 9-decenoic acid, an ester of 9-decenoic acid, or a combination thereof, and/or a known antimicrobial agent.
  • the amount of antimicrobial composition added to a given personal care product can be determined by one of skill in the art using various known techniques and methods.
  • two or more (for example, 2, 3, 4 or more) antimicrobial agents are used in a personal care product, in similar manner to that described above for surface coating formulations.
  • Illustrative second antimicrobial agents that are known personal care antimicrobial agents include: phenol derivatives (such as halogenated phenols, for example 3,5-dichlorophenol, 2,5-dichlorophenol, 3,5-dibromophenol, 2,5- dibromophenol, 2,5- or 3,5-dichloro-4-bromophenol, 3,4,5-trichlorophenol, 3,4,5- tribromophenol, phenylphenol, 4-chloro-2-phenylphenol, 4-chloro-2-benzylphenol); dichlorophene, hexachlorophene; aldehydes (such as formaldehyde, glutaraldehyde, salicylaldehyde); alcohols (such as phenoxyethanol); antimicrobial carboxylic acids and derivatives thereof such as parabens, including methyl, propyl and benzyl parabens, and the like; organometallic compounds (such as tributyl tin derivatives); iodine
  • second antimicrobial agents include TriclosanTM (2,4,4'-trichloro-2'-hydroxydiphenyl ether, also known as 5-chloro-2-(2,4-dichlorophenoxy)phenol) and KathonTM (methyl chloroisothiazolinone and methyl isothiazolinone in various ratios).
  • the phenol derivatives suitable as second antimicrobial agent do not include phenolic compounds having antioxidant properties.
  • examples of such compounds include BHT, BHA, TBHQ and natural analogues with similar anti-oxidant properties such as tocopherols, cinnamic acid compounds and compounds described as flavins or flavinoids.
  • the antimicrobial carboxylic acids suitable as second antimicrobial agents do not include short chain organic acids that are water soluble, such as lactic, acetic, citric, malic, succinic, natural amino acids, formic, propionic, butyric, and the like.
  • Illustrative short chain organic acids of this type have four or fewer carbon atoms in the carbon backbone and can also contain other substituent groups such as -OH, NH 2 , and the like.
  • alcohols suitable as second antimicrobial agents do not include short chain alcohols, such as Ci-C 4 alcohols such as methanol, ethanol, propanol, butanol.
  • the antimicrobial agents of Formulae (I), (II) and (III) can be effective in low concentrations without combining with these particular second antimicrobial agents.
  • Illustrative household cleansing agents include dishwashing cleaners, detergents, hard surface cleaners, glass cleaner, appliance cleaner, floor cleaner, bath and kitchen cleaners, auto cleaning and polishing products, water treatment (including cleaners for humidifiers and water softeners), and the like.
  • hard surface includes, but is not limited to, bathroom surfaces (e.g., floor, tub, shower, mirror, toilet, bidet, bathroom fixtures), kitchen surfaces (e.g., counter tops, stove, oven, range, sink, refrigerator, microwave, appliances, tables, chairs, cabinets, drawers, floor), furniture surfaces (e.g., tables, chairs, entertainment centers, libraries, cabinets, desks, doors, shelves, couches, beds, television, stereo, pool table, ping pong table), windows, window ledges, tools, utility devices (e.g., telephones, radios, CD players, digital sound devices, palm computers, laptop computers), toys, writing implements, watches, framed picture or paintings, books).
  • bathroom surfaces e.g., floor, tub, shower, mirror, toilet, bidet, bathroom fixtures
  • kitchen surfaces e.g., counter tops, stove, oven, range, sink, refrigerator, microwave, appliances, tables, chairs, cabinets, drawers, floor
  • furniture surfaces e.g., tables, chairs, entertainment centers, libraries, cabinets, desks
  • antimicrobial compositions can be utilized in connection with personal care cleansing agents.
  • personal care cleansing agents in accordance with these aspects include, but are not limited to, skin lotions and creams, soap bars, liquid hand and body lotions, liquid hand soaps, bath salts, ointments, face lotions, hair shampoo and conditioning products, hair tonics, skin oils, powders, sunscreen creams, contact lens storage and/or cleansing solution, and the like.
  • the antimicrobial compositions can also find utility in connection with cosmetics.
  • inventive antimicrobial compositions have utility in food or feed formulations, as well as potable water-contacting applications.
  • Illustrative water-contacting applications include water treatment systems.
  • the inventive antimicrobial compositions possess a broad spectrum of efficacy against Gram negative bacteria, fungi, and even Gram positive bacteria.
  • the antimicrobial compositions in accordance with the invention can find wide application in industrial products, consumer products, and food/feed applications.
  • Table 1 summarizes some relevant microorganisms and applications that relate to some of these microorganisms.
  • the antimicrobial compositions in accordance with the invention provide a broad spectrum of antimicrobial efficacy.
  • This broad spectrum encompasses Gram positive bacteria, fungi, and even Gram negative bacteria.
  • embodiments of the antimicrobial compositions can exhibit antimicrobial efficacy even at pH levels about neutral. This expanded efficacy can provide significant benefits and broaden the applications of these antimicrobial agents significantly over known antimicrobial agents.
  • the efficacy of antimicrobial compositions in accordance with aspects of the invention against the following organisms was determined as follows. The following organisms were incubated in the presence of varying concentrations of 9- decenoic acid (9-DA), 9-undecenoic acid (9-UDA), or a combination of 9-decenoic acid and 9-undecenoic acid (9-DA/9-UDA) on an agar surface: Aspergillus parasiticus (ATCC 56857), Trichoderma virens (ATCC 9645;, Aureobasidium pullulans (ATCC 12536), Aspergillus flavus (ATCC 96045), Cladosporium cladosporiodes (ATCC 16022), Aspergillus flavus (ATCC 5917), Aspergillus oryzae (ATCC 10124), Aspergillus parasiticus (ATCC 13539), Ulocladium atrum (ATCC 52426), Candida albicans (ATCC 1
  • the minimum inhibitory concentration (MIC) was defined as the least concentration tested that completely inhibited growth of the organism.
  • Antimicrobial compositions (9-DA, 9-UDA or 9-DA/9-UDA) were added by percent weight to molten autoclaved PDA media, with consideration of specific gravity (0.915g/mL for 9-DA and 0.9179g/mL for 9-UDA) and purity (98% for 9- DA and 97% for 9-UDA).
  • specific gravity 915g/mL for 9-DA and 0.9179g/mL for 9-UDA
  • purity 98% for 9- DA and 97% for 9-UDA
  • the antimicrobial agents were added in equal proportion.
  • a 1.0% 9-DA/9-UDA solution would contain 0.5% 9-DA and 0.5% 9-UDA.
  • the agar was thoroughly mixed and poured into sterile petri plates and allowed to solidify.
  • the agar plates were inoculated with the spore solution to achieve 10 2 spores/plate.
  • the plates were incubated at 25-30°C in Ziploc bags with a wet paper towel to keep the moisture level high.
  • the plates were examined for growth at 1, 2, 3, 4, 8, 1 1, 15, 17, 23, 29 and 31 days. The percent coverage of growth on the agar surface was recorded at each sample point.
  • both 9-DA and 9-UDA were observed to be effective antimicrobial agents with MICs in the ranges of 0.01% to 0.05% and 0.01% to 0.1% respectively.
  • MICs in the ranges of 0.01% to 0.05% and 0.01% to 0.1% respectively.
  • Aspergillus parasiticus ATCC 56857 Trichoderma virens ATCC 9645, Aspergillus parasiticus ATCC 13539, Candida albicans ATCC 1 1651, Alternaria alternata ATCC 52170, Stachybotr ⁇ s chartarum ATCC 16026, and Aspergillus niger ATCC 1 1414
  • a synergistic effect was observed when using a 9-DA/9-UDA (50:50) mixture.
  • the MIC when using the 9-DA/9-UDA (50:50) mixture was lower than would be expected for a comparable amount of either 9DA or 9UDA by itself.
  • Results are illustrated in Figures 1-13, wherein antimicrobial composition is represented on the X-axis, and percentage fungal coverage is represented on the Y- axis.
  • Example 2
  • Efficacy of 9-UDA against several microorganisms was measured based on percent reduction in comparison to growth of the controls.
  • the growth inhibition due to 9-UDA was determined for the following organisms: Enterobacter aerogenes (ATCC 13048), Escherichia coli (ATCC 1 1229), Escherichia coli (ATCC 8739), Bacillus subtilis (ATCC 6051), Bacillus cereus (ATCC 14579), Pediococcus acidolactici (ATCC 8042), and Lactobacillus casei (ATCC 334).
  • MRS medium (Difco 288130) was purchased from Becton, Dickinson and Company, Sparks, MD.
  • the efficacy of 0.25% and 0.5% 9-UDA (free acid) to inhibit the growth of various microorganisms of interest indicated above was tested as follows.
  • the pH of MRS media with various concentrations of 9-UDA was measured to ensure that there were not significant variations in pH due to addition of the 9-UDA.
  • the selected organisms were incubated overnight in 5 ml of MRS medium at 35°C and 250 rpm.
  • a 0.25 and 0.50% 9-UDA in MRS medium were prepared, along with a control of straight media (no 9-UDA).
  • the concentrated 9-UDA was diluted with the appropriate media required for the respective microorganisms, to reach the required concentrations for the studies as indicated below.
  • the antimicrobial (9-UDA) was added by weight / volume percent to the media.
  • the specific gravity (0.9179g/mL) and purity (97%) of the compounds were taken into account.
  • the pH of the medium was not adjusted.
  • the target for initial cell density was 10 5 to 10 6 cfu/ml.
  • 0.01 OD OOO is equivalent to approximately 10 cfu/ml.
  • 30 ⁇ l of overnight culture diluted to 0.01 OD 6O0 was added to the 3 ml of media in each tube. The tubes were incubated at 35 0 C. Treatments were all done in duplicate. All strains were shaken at 250 rpm, with the exception of Lactobacillus (because it is anaerobic). OD 600 readings were taken at 0, 24, and 48 hours.
  • both 0.25% and 0.5% 9-UDA resulted in a complete reduction when compared with the control culture that was grown in MRS medium the absence of any antimicrobial agent.
  • 9-UDA resulted in a complete reduction when compared with the control culture that was grown in the absence of any antimicrobial compound for E. coli 8739, Bacillus subtilis 6051, Bacillus cereus 14579, Pediococcus acidolactici 8042, and Lactobacillus casei 334. It is worthwhile to note that 0.5% 9-UDA resulted in a complete inhibition of E.coli 8739.
  • Efficacy of potassium salts of 9-DA and 9-UDA were determined through incubation of the following organisms in the presence of varying concentrations of the potassium salt: Serratia marcescens A TCC 990, Pseudomonas straminea A TCC 33636, Bacillus subtilis ATCC 6051, Bacillus licheniformis ATCC 14580, Bacillus cereus ATCC 14579, Pediococcus acidilactici ATCC 8042, and Lactobacillus casei ATCC 334 .
  • MRS medium (Difco 288130) was purchased from Becton, Dickinson and Company, Sparks, MD.
  • K-9- DA and K-9-UDA The efficacy of different levels of potassium salts of 9-DA and 9-UDA (K-9- DA and K-9-UDA) were tested depending on the organism to inhibit the growth of various microorganisms indicated above. The selected organisms were incubated overnight in 5 ml of MRS medium at
  • MRS media with K-9-DA or K-9-UDA were prepared, along with a control of straight media (no antimicrobial added).
  • the concentrated antimicrobial agents were diluted with the appropriate media required for the respective microorganisms, to reach the required concentrations for the studies as indicated below.
  • the antimicrobial agents were added by weight / volume percent on an 'as 9-DA' or 'as 9-UDA' basis to the media.
  • the purity of the antimicrobial agent (99% for K-9-DA and 96% for K-9-UDA) was taken into account.
  • the pH of the medium was not adjusted.
  • the target for initial cell density was 10 5 to 10 6 cfu/ml.
  • 0.01 OD 600 is equivalent to approximately 10 cfu/ml.
  • 30 ⁇ l of overnight culture diluted to 0.01 OD 600 was added to the 3 ml of media in each tube. The tubes were incubated at 35°C. Treatments were all done in duplicate. All strains were shaken at 250 rpm, with the exception of Lactobacillus (because it is anaerobic). OD 6O0 readings were taken at 0, 4, 17, 23 and 47 hours.
  • MRS medium is considered to be a rich medium by those skilled in the art and one would expect the potassium salts of 9-DA and 9- UDA to be even more effective in sub-optimal culture conditions for the various microorganisms tested. Thus it is expected that even greater reductions in growth when compared with growth could be observed with even lower concentrations of the antimicrobial compounds that those listed above.
  • Example 4 Efficacy of potassium salts of 9-DA and 9-UDA was tested at various pH levels against the following: E.coli ATCC 8739, Serratia marcescens ATCC 990, Bacillus cereus ATCC 14579, Bacillus licheniformis ATCC 14580, Bacillus subtilis ATCC 6051, Pediococcus acidolactici ATCC 8042, Pseudomonas straminea ATCC 33636, Pseudomonas stutzeri ATCC 17588, Pseudomonas oleovorans ATCC 8062 and Lactobacillus casei ATCC 334. Stock cultures of each organism were transferred into MRS liquid medium. MRS medium (Difco 288130) was purchased from Becton, Dickinson and Company, Sparks, MD.
  • MRS medium (Difco 288130) was purchased from Becton, Dickinson and Company, Sparks, MD.
  • MRS media with K-9-DA or K-9-UDA were prepared, along with a control of straight media (no antimicrobial added).
  • the efficacy of potassium salts of 9-DA and 9-UDA in food applications was determined through the comparison at equimolar equivalence to 1000 to 500 concentrations (ppm) of potassium sorbate (control). Efficacy was determined against the following microorganisms: Lactobacillus plantarwn-WMtype from Dressing, Listeria innocua ATCC 32293, Pseudomonas putida ATCC 12633, Bacillus cereus F3802A184, E. coli ATCC 1 1229, and Saccharomyces cerevisiae ATCC 32167.
  • Each organism was grown in 10 ml APT broth at a pH of 6.5 and was incubated at 21 0 C for 3 days, except for yeast and mold at 5 days.
  • a 1,000-ppm (0.1%) and 500-ppm (0.05%) concentration for Potassium 9-Decenoic Acid Salt (K9DA), Potassium 9-Undecenoic Acid Salt (K9UDA) and Potassium Sorbate (K Sorbate) were made as indicated below.
  • a 1000-ppm K Sorbate, purity 99%, solution was made using 1.0 Ig salt into 50ml-distilled water; filter sterilized and added to sterile 950 ml APT broth.
  • Each solution was checked for a final pH (6.5 +/- 0.05) and dispensed into properly numbered tubes necessary for 5 testing periods in duplicate.
  • Each tube was inoculated with about 100-1000 microbes per ml.
  • the inoculum was plated on APT agar and incubated at 2O 0 C for 3 days, with the exception of yeast and mold at 5 days to act as a positive control.
  • sets of non- inoculated tubes were used as negative controls.
  • results indicate that the potassium salts of 9-UDA and 9-DA have antimicrobial activity against several potential spoilage microorganisms and were very effective against Saccharomyces cerevisiae ATCC 32167. While the potassium salts of 9-DA were not effective antimicrobial agents, at the concentrations used, against Listeria innocua ATCC 32293, the potassium salts of 9-UDA were very effective antimicrobial agents. Results indicate that the potassium salt of 9-UDA was very effective at concentrations equimolar with 1 OOOppm and 500 ppm potassium sorbate.
  • Alicyclobacillus cocktail consisting of four different species. Alicyclobacillus is a common juice spoilage organism. Potassium salts of 9-DA and 9-UDA at equimolar equivalence respectively to 500 ppm and 100 ppm sodium benzoate were found to be more effective than the control sodium benzoate. Other concentrations of the potassium salts of 9-DA and 9-UDA were found to be as effective as the equimolar amount of sodium benzoate.
  • Alicyclobacillus acidoterrestris ATCC 49025 and wildtype A. acidoterrestris from orange juice, Alicyclobacillus acidocaldarius ATCC 27009 and wildtype A. acidocaldarius from orange juice were enriched on 5 Yeast, Starch, and Glucose (YSG) spread plates for each culture. Plated cultures were incubated at 46 0 C for 7 days to produce spores. Plates were incubated in a plastic bag to avoid moisture loss.
  • potassium 9-DA and potassium 9-UDA concentrations of potassium 9-DA and potassium 9-UDA were prepared: 500-ppm (0.05%) and 100-ppm (0.01%) concentration solutions for Potassium 9-Decenoic Acid Salt (K9DA), Potassium 9-Undecenoic Acid Salt (K9UDA) and Sodium Benzoate.
  • K9DA Potassium 9-Decenoic Acid Salt
  • K9UDA Potassium 9-Undecenoic Acid Salt
  • Sodium Benzoate concentration solutions for Potassium 9-Decenoic Acid Salt
  • K9UDA Potassium 9-Undecenoic Acid Salt
  • Sodium Benzoate concentration solutions for Potassium 9-Decenoic Acid Salt (K9DA), Potassium 9-Undecenoic Acid Salt (K9UDA) and Sodium Benzoate.
  • the antimicrobial agents were tested at two temperatures points (46 0 C and 32 0 C).
  • 500-ppm Sodium Benzoate purity 99%
  • 9-DA or 9-UDA were tested at equimolar levels to 500 ppm or 100 ppm sodium benzoate as indicated in the table below.
  • Table 17 Molar equivalent for 50-1000 ppm Sodium benzoate (144.11 MW)
  • Each solution was checked for a final pH (3.7 +/- 0.1) and dispensed into properly numbered tubes necessary for 5 testing periods in triplicate. After 7 days incubation, cultures were examined under a microscope using a wet mount for spores. If spores were present, sterile distilled water was used to produce inoculum. The samples were heat shocked at 80 0 C for 10 minutes. Time was not counted until solutions reached 80 0 C. Each YSG tube was inoculated with approximately 100-1000 microbes per ml. Then the inoculum was plated on YSG agar and incubated at 46 0 C for 5 days for a positive control. Plates were incubated in a plastic bag to avoid moisture loss, hi addition, 5 non-inoculated YSG tubes per condition were included to act as negative controls. Samples were tested in triplicate except for the negative controls.
  • n 3 for all treatments -0.30 equals ⁇ lcfu/g 0.70 equals ⁇ 10cfu/g
  • Alicyclobacillus sp. are bacterial spore formers that are sometimes called ⁇ acidophilic thermophilic bacteria (ATB). These bacteria cause spoilage of many shelf-stable juice products, resulting in off-flavor and off-odor in these products.
  • ATB acidophilic thermophilic bacteria
  • Bleaching clay (Pure Flow B80 CG, 5 wt% to product) is added to the crude reaction mixture, which is then stirred overnight under argon at 70 0 C.
  • the crude product mixture containing the clay is subsequently filtered through a packed bed of sand (10 g), celite (5 g), bleaching clay (12.5 g), and sand (10 g).
  • the filtered oil is analyzed by GC analysis.
  • Vacuum Distillation A glass 2.0 L 3-necked round bottom flask with a magnetic stirrer, packed column, distillation head, and temperature controller was charged with methyl ester products and placed in a heating mantle. The flask was attached to a 2-inch x 36-inch glass distillation packed column contain 0.16" Pro- PakTM stainless steel saddles. The distillation column was adapted to a fractional distilling head, which was connected to a vacuum line. A 500 mL pre-weighed round bottom flask was used for collecting the fractions. Vacuum on this system was ⁇ 1 mmHg.
  • Oven temperature Starting temperature: 100°C, hold time: 1 minute. Ramp rate 10°C/min to 25O 0 C, hold time: 12 minutes.
  • Carrier gas Helium Mean gas velocity: 31.3 ⁇ 3.5% cm/sec (calculated)
  • Methyl soyate (source: Chemol) was reacted according to the general metathesis procedure provided above. Catalyst 827 and propene (130 psi, unless specified otherwise) were used, and the reaction was performed at 60 0 C. The results are provided in Table 21.
  • Percentages correspond to GC area. 2 Reaction performed with 100 psi propene.
  • Fatty acid methyl esters were reacted according to the general metathesis procedure provided above.
  • Canola FAME source: Cognis, Lot # MF-CNF6C27
  • SBO FAME source: Chemol, Lot # IF-24298
  • Sun FAME source: Nu Chek, Lot # "Special”
  • Catalyst 827 (5 ppm) and propene (130 psi) were used, and the reaction was performed at 60 0 C. The results are provided in Table 22.
  • Fatty acid methyl esters were reacted according to the general metathesis procedure provided above.
  • Canola FAME source: Cognis
  • SBO FAME source: Cognis
  • Sun FAME source: Nu Chek
  • Propene 130 psi was used as the terminal olefin, and the reaction was performed at 60 0 C for 4 hours. The results are provided in Table 23.

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Abstract

La présente invention concerne des compositions antimicrobiennes comprenant une combinaison d'un premier agent antimicrobien de Formule I et d'un second agent antimicrobien de Formule IV. Les compositions antimicrobiennes comprenant une combinaison d'agents antimicrobiens de Formule (I) et de Formule (IV) offrent l'efficacité d'un agent antimicrobien présentant des niveaux de concentration inhibitrice minimale d'environ 0,1 % ou moins contre certains champignons. L'invention se rapporte en outre à des produits antimicrobiens tels que des produits de consommation, des préparations industrielles et des formules alimentaires.
PCT/US2007/021941 2006-10-13 2007-10-15 Compositions antimicrobiennes, procédés et systèmes Ceased WO2008140469A2 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7951232B2 (en) 2006-02-09 2011-05-31 Elevance Renewable Sciences, Inc. Surface coating compositions and methods
JP2013194010A (ja) * 2012-03-21 2013-09-30 Kitakyushu Foundation For The Advancement Of Industry Science & Technology 防カビ剤及びそれを用いたい草の防カビ方法並びに防カビ処理されたい草製品
WO2015076830A1 (fr) * 2013-11-22 2015-05-28 General Electric Company Dispersant biologique d'acide gras, et procédés d'utilisation
US9193937B2 (en) 2011-02-17 2015-11-24 The Procter & Gamble Company Mixtures of C10-C13 alkylphenyl sulfonates
EP3007691A1 (fr) * 2013-06-10 2016-04-20 Justus-Liebig- Universitat Giessen Ester d'acides gras permettant le traitement d'états associés au malassezia
WO2019155178A1 (fr) * 2018-02-12 2019-08-15 Societe Commerciale Industrielle Et Maritime Socomari Procédé de protection de conduites de circulation d'eau
US20220049111A1 (en) * 2018-12-19 2022-02-17 Corning Incorporated Biocidal coatings

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DE2447627C3 (de) * 1974-10-05 1980-06-26 Dr. Rudolf Kuerner Chemische Spezialprodukte Inh. Dr. Rudolf Kuerner, 6380 Bad Homburg Antimikrobielles Präparat
US4442125A (en) * 1978-06-26 1984-04-10 Oxford Hill, Ltd. Process for detaching or preventing attachment of microorganisms to a surface
US4224028A (en) * 1978-11-20 1980-09-23 Thiele Geraldine H Retardation of the putrefaction of hides and skins
GB9209238D0 (en) * 1992-04-29 1992-06-17 Unilever Plc Cosmetic conditioner
KR20010004177A (ko) * 1999-06-28 2001-01-15 김영환 반도체소자 제조방법

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7951232B2 (en) 2006-02-09 2011-05-31 Elevance Renewable Sciences, Inc. Surface coating compositions and methods
US9193937B2 (en) 2011-02-17 2015-11-24 The Procter & Gamble Company Mixtures of C10-C13 alkylphenyl sulfonates
JP2013194010A (ja) * 2012-03-21 2013-09-30 Kitakyushu Foundation For The Advancement Of Industry Science & Technology 防カビ剤及びそれを用いたい草の防カビ方法並びに防カビ処理されたい草製品
EP3007691A1 (fr) * 2013-06-10 2016-04-20 Justus-Liebig- Universitat Giessen Ester d'acides gras permettant le traitement d'états associés au malassezia
WO2015076830A1 (fr) * 2013-11-22 2015-05-28 General Electric Company Dispersant biologique d'acide gras, et procédés d'utilisation
US10597314B2 (en) 2013-11-22 2020-03-24 General Electric Company Fatty acid biodispersant and methods of use
WO2019155178A1 (fr) * 2018-02-12 2019-08-15 Societe Commerciale Industrielle Et Maritime Socomari Procédé de protection de conduites de circulation d'eau
FR3077816A1 (fr) * 2018-02-12 2019-08-16 Societe Commerciale Industrielle Et Maritime Socomari Procede de protection de conduites de circulation d'eau
US20220049111A1 (en) * 2018-12-19 2022-02-17 Corning Incorporated Biocidal coatings

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