WO2015031874A1 - Synergistic combination of a lenacil compound and carbendazim for dry film protection - Google Patents

Synergistic combination of a lenacil compound and carbendazim for dry film protection Download PDF

Info

Publication number
WO2015031874A1
WO2015031874A1 PCT/US2014/053618 US2014053618W WO2015031874A1 WO 2015031874 A1 WO2015031874 A1 WO 2015031874A1 US 2014053618 W US2014053618 W US 2014053618W WO 2015031874 A1 WO2015031874 A1 WO 2015031874A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbendazim
lenacil
antimicrobial
dry film
coating composition
Prior art date
Application number
PCT/US2014/053618
Other languages
French (fr)
Inventor
Kenneth M. Donnelly
Pierre Marie Lenoir
Lukas L. VILLIGER
Original Assignee
Rohm And Haas Company
Dow Global Technologies Llc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rohm And Haas Company, Dow Global Technologies Llc filed Critical Rohm And Haas Company
Priority to KR1020167007163A priority Critical patent/KR20160051792A/en
Priority to CN201480045868.1A priority patent/CN105517438B/en
Priority to AU2014311985A priority patent/AU2014311985B2/en
Priority to US14/913,033 priority patent/US9408388B2/en
Priority to MX2016002107A priority patent/MX360553B/en
Priority to JP2016537928A priority patent/JP6411507B2/en
Priority to EP14766316.5A priority patent/EP3010342A1/en
Priority to RU2016110840A priority patent/RU2650521C2/en
Publication of WO2015031874A1 publication Critical patent/WO2015031874A1/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • 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
    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides

Definitions

  • This invention relates to combinations of antimicrobial compounds and their uses in dry film protection applications, the combinations having unexpectedly greater activity than would be expected for the use of both of the individual antimicrobial compounds.
  • Antimicrobial compounds are sometimes included in liquid coating compositions that are applied to a substrate and that become dry films. It is desirable that such dry films control surface fungi and algae and that such dry films also present as little adverse effect as possible on health and the environment.
  • synergistic antimicrobial composition comprising lenacil and carbendazim (CAS registry number is 10605-21-7 ).
  • the invention further provides a method of inhibiting the growth of or controlling the growth of microorganisms in a building material, the method comprising the step of adding a synergistic antimicrobial composition comprising lenacil and carbendazim; wherein the weight ratio of the carbendazim to lenacil is from 1:10 to 10:1.
  • the present invention further comprises a coating composition comprising a synergistic antimicrobial composition comprising lenacil and carbendazim.
  • the coating composition of the present invention may also comprise a synergistic antimicrobial composition comprising lenacil and carbendazim; wherein the weight ratio of the
  • carbendazim to lenacil is from 1:10 to 10:1.
  • the present invention provides a dry film made by a process comprising applying a layer of the coating composition comprising a synergistic antimicrobial composition comprising lenacil and carbendazim; wherein the weight ratio of the
  • carbendazim to lenacil is from 1 : 10 to 10: 1 to a substrate and drying the coating composition or allowing the coating composition to dry.
  • antimicrobial compound refers to a compound capable of inhibiting the growth of or controlling the growth of microorganisms; antimicrobial compounds include bactericides, bacteriostats, fungicides, fungistats, algaecides, algistats, and herbicides depending on the dose level applied, system conditions and the level of microbial control desired.
  • antimicrobial compound as used herein is synonymous with the term “biocide”.
  • microorganism includes, for example, fungi (such as yeast and mold), bacteria and algae.
  • temperatures are in degrees centigrade (°C), and references to percentages are by weight (wt ).
  • Percentages of antimicrobial compounds in the composition of this invention are based on the total weight of active ingredients in the composition, i.e., the antimicrobial compounds themselves, exclusive of any amounts of solvents, carriers, dispersants, stabilizers or other materials which may be present.
  • carbendazim is methyl benzimidazol-2-ylcarbamate (CAS registry number 10605-21-7).
  • ratios are the herein to be "X: l or higher,” it is meant that the ratio is Y: l, where Y is X or greater, and when a ratio is the herein to be “X: 1 or lower,” it is meant that the ratio is Z: 1, where Z is X or less.
  • X: l or higher it is meant that the ratio is Y: l, where Y is X or greater
  • X: 1 or lower it is meant that the ratio is Z: 1, where Z is X or less.
  • Lenacil belongs to the class of uracil herbicides, 3-cyclohexyl-l, 5,6,7- tetrahydrocyclopentapyrimidine-2,4(3H)-dione (C1 3 H1 8 N2O2 ) (CAS registry number 2164-08- 1).
  • Lenacil is a known herbicide that is approved in many jurisdictions as a soil-acting herbicide for the control of grass and broad-leaved weeds in beet and other crops.
  • Lenacil has relatively low solubility in water. This relatively low solubility in water is preferred for an antimicrobial material that may be included in a coating composition or other building material, because dried coatings and building materials are exposed to water, which could tend to remove a highly soluble compound from the dried coating or the building material.
  • the present invention involves a composition that contains both lenacil and carbendazim. It has been surprisingly found that such a composition is synergistically effective as a biocide. It has been especially surprisingly found that compositions that contain both lenacil and carbendazim are synergistically effective as biocides.
  • the weight ratio of carbendazim to lenacil compound is preferably 1: 10 to 10:1.
  • the mixture of lenacil and carbendazim may be included in a coating composition.
  • Lenacil and carbendazim may be added to the coating composition separately or as a mixture or any combination thereof.
  • Preferred coating compositions are liquid.
  • compositions may be aqueous or non-aqueous.
  • Aqueous coating compositions generally contain 30% or more water by weight of the mixture, based on the weight of the coating composition.
  • preferred coating compositions are liquid compositions, especially compositions that contain dispersions of polymers in aqueous media.
  • the antimicrobial compound combinations of the present invention are particularly useful in preservation of building materials, e.g., adhesives, caulk, joint compound, sealant, wallboard, etc., polymers, plastics, synthetic and natural rubber, paper products, fiberglass sheets, insulation, exterior insulating finishing systems, roofing and flooring felts, building plasters, bricks, mortar, gypsum board, wood products and wood-plastic composites.
  • building materials e.g., adhesives, caulk, joint compound, sealant, wallboard, etc., polymers, plastics, synthetic and natural rubber, paper products, fiberglass sheets, insulation, exterior insulating finishing systems, roofing and flooring felts, building plasters, bricks, mortar, gypsum board, wood products and wood-plastic composites.
  • Coating compositions are designed so that a layer of the coating composition can readily be applied to a substrate and then dried or allowed to dry to form a dry film.
  • Coating compositions contain a binder. Binders contain one or more of the following: one or more polymer, one or more oligomer, and/or one or more monomer. Oligomers and monomers in binders are designed to polymerize and/or crosslink during or after the formation of the dry film. Polymers in a binder may or may not be designed to crosslink during or after the formation of the dry film.
  • Coating compositions optionally contain one or more pigment.
  • a pigment is a mineral or an organic substance in the form of small solid particles. Pigments provide full or partial opacity to the dry film.
  • the antimicrobial compound combinations are useful for preservation of the dry film coating resulting after application of paint or other liquid coating composition.
  • the antimicrobial composition is an aqueous latex paint comprising one or more of the antimicrobial compound combinations disclosed herein, or the dry film coating resulting from application of the paint to a surface.
  • An aqueous latex paint is an aqueous liquid coating composition in which the binder is a polymer in the form of a latex (i.e., in the form of polymer particles dispersed throughout the water). More preferred are aqueous latex paints in which the binder contains one or more acrylic polymer.
  • the amount of the antimicrobial compound combinations of the present invention to control the growth of microorganisms is from 100 ppm to 40,000 ppm active ingredient.
  • lenacil plus carbendazim is present in an amount from 100 ppm to 10,000 ppm.
  • the antimicrobial combinations of the composition are present in an amount of at least 100 ppm and no more than 8,000 ppm, preferably no more than 6,000 ppm, preferably no more than 5,000 ppm, preferably no more than 4,000 ppm, preferably no more than 3,000 ppm, preferably no more than 2500 ppm, and preferably no more than 2,000 ppm. Concentrations mentioned above are in a liquid coating
  • composition containing the antimicrobial compound combinations; antimicrobial compound combination levels in the dry film coating will be higher.
  • the present invention also encompasses a method for preventing microbial growth in building materials, especially in dry film coatings, by incorporating any of the claimed antimicrobial compound combinations into the materials.
  • the antimicrobial compositions are used to inhibit growth of algae and/or fungi.
  • the composition of the present invention contains lenacil and carbendazim. It is contemplated that some embodiments may contain one or more additional antimicrobial compound.
  • the paints were mixed 90 seconds with the horse power shaker (AXEL 75M3372/ Agitateur SO-10MI) until uniformity was achieved. Paints containing different antimicrobial compounds at the same levels were mixed together in order to obtain the desired ratio of antimicrobial compounds. After one day, the paints were applied to Schleicher & Schuell filter paper at 280 ⁇ wet film thickness and dried for 3 days at room temperature avoiding direct exposure to sunlight. Square discs (1.6 cm x 1.6 cm) were cut out from each panel and were used as the substrate for algal efficacy tests. This sample size allowed for an agar border when the sample disc was placed into the well of the test plate.
  • Algal efficacy was tested according to modified ASTM 5589 which is a standard accelerated test method for determining resistance of various coatings (including paints) to algal defacement. To accommodate for high-throughput screening, this method was scaled down from petri dishes to 6-well plates. Bold Modified Basal Freshwater Nutrient Solution was used as growth medium. A single coated filter paper coupon was placed with a pair of sterile forceps at the center of the agar plug (on top) with the painted surface facing upwards. Algal inoculums were prepared by mixing equal concentrations (lx 10 6 cfu/ml) and equal volumes of exponentially growing algae cultures. [0036] Algal inoculums:
  • Each well that contains a tested coupon was inoculated with 1750 ⁇ of algal suspensions (lx 10 6 cfu/ml) making sure that the whole surface (paint film as well as the agar surrounding it) was evenly covered.
  • the plates were incubated at room temp (21°C - 25 °C) with cyclic exposure to light and dark phases, for a period of four weeks.
  • SI is calculated based on F.C.Kull et. Al. method (Applied Microbiology, Vol. 9 (1961). In this study, SI was calculated based on the following formula with the minimum inhibitory concentration chosen based on the percent inhibitory exhibited by the individual antimicrobial against each microorganisms tested.
  • SI value of ⁇ 1 in the formula indicates a synergism of the blended biocides exists.
  • compositions listed below that contain both lenacil and carbendazim are examples of the present invention.
  • Test Results for carbendazim with lenacil at 4 weeks were as follows:
  • Carbendazim + Lenacil at ratio 1: 10 to 10:1 exhibited a synergy.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Dentistry (AREA)
  • Zoology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Architecture (AREA)
  • Paints Or Removers (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

A synergistic antimicrobial composition containing lenacil and carbendazim is provided. Also provided is a method of inhibiting the growth of or controlling the growth of microorganisms in a building material by adding such a synergistic antimicrobial composition. Also provided is a coating composition containing such a synergistic antimicrobial composition, and a dry film made from such a coating composition.

Description

SYNERGISTIC COMBINATION OF A
LENACIL COMPOUND AND CARBENDAZIM FOR DRY FILM PROTECTION
[0001] This invention relates to combinations of antimicrobial compounds and their uses in dry film protection applications, the combinations having unexpectedly greater activity than would be expected for the use of both of the individual antimicrobial compounds.
[0002] Use of combinations of at least two antimicrobial compounds can broaden potential markets, reduce use concentrations and costs, and reduce waste. In some cases, commercial antimicrobial compounds cannot provide effective control of microorganisms, even at high use concentrations, due to weak activity against certain types of microorganisms, e.g., those resistant to some antimicrobial compounds. Combinations of different antimicrobial compounds are sometimes used to provide overall control of microorganisms in a particular end user environment. For example, WO 1998/121962 discloses combinations of 3-iodo-2-propynyl-butylcarbamate and pyrithione, but this reference does not suggest any of the combinations claimed herein. Moreover, there is a need for additional combinations of antimicrobial compounds with relatively low impact on health and/or the environment. The problem addressed by this invention is to provide such additional combinations of antimicrobial compounds.
[0003] Antimicrobial compounds are sometimes included in liquid coating compositions that are applied to a substrate and that become dry films. It is desirable that such dry films control surface fungi and algae and that such dry films also present as little adverse effect as possible on health and the environment.
[0004] In the present invention there is provided a synergistic antimicrobial composition comprising lenacil and carbendazim (CAS registry number is 10605-21-7 ).
[0005] The invention further provides a method of inhibiting the growth of or controlling the growth of microorganisms in a building material, the method comprising the step of adding a synergistic antimicrobial composition comprising lenacil and carbendazim; wherein the weight ratio of the carbendazim to lenacil is from 1:10 to 10:1.
[0006] The present invention further comprises a coating composition comprising a synergistic antimicrobial composition comprising lenacil and carbendazim. The coating composition of the present invention may also comprise a synergistic antimicrobial composition comprising lenacil and carbendazim; wherein the weight ratio of the
carbendazim to lenacil is from 1:10 to 10:1. [0007] Lastly, the present invention provides a dry film made by a process comprising applying a layer of the coating composition comprising a synergistic antimicrobial composition comprising lenacil and carbendazim; wherein the weight ratio of the
carbendazim to lenacil is from 1 : 10 to 10: 1 to a substrate and drying the coating composition or allowing the coating composition to dry.
[0008] The following is a detailed description of the invention.
[0009] As used herein, the following terms have the designated definitions, unless the context clearly indicates otherwise.
[0010] The term "antimicrobial compound" refers to a compound capable of inhibiting the growth of or controlling the growth of microorganisms; antimicrobial compounds include bactericides, bacteriostats, fungicides, fungistats, algaecides, algistats, and herbicides depending on the dose level applied, system conditions and the level of microbial control desired. Such term "antimicrobial compound" as used herein is synonymous with the term "biocide".
[0011] The term "microorganism" includes, for example, fungi (such as yeast and mold), bacteria and algae.
[0012] The following abbreviations are used throughout the specification: ppm = parts per million by weight (weight/ weight), mL = milliliter, ATCC = American Type Culture
Collection, SAG = Culture Collection of Algae at Goettingen University, CCAP = Culture Collection of Algae and Protozoa and MIC = minimum inhibitory concentration.
[0013] Unless otherwise specified, temperatures are in degrees centigrade (°C), and references to percentages are by weight (wt ). Percentages of antimicrobial compounds in the composition of this invention are based on the total weight of active ingredients in the composition, i.e., the antimicrobial compounds themselves, exclusive of any amounts of solvents, carriers, dispersants, stabilizers or other materials which may be present.
[0014] As used herein, "carbendazim" is methyl benzimidazol-2-ylcarbamate (CAS registry number 10605-21-7).
[0015] When a ratio is the herein to be "X: l or higher," it is meant that the ratio is Y: l, where Y is X or greater, and when a ratio is the herein to be "X: 1 or lower," it is meant that the ratio is Z: 1, where Z is X or less. The same logic follows for ratios that are "1 :X or higher" and " 1:X or lower".
[0016] Lenacil belongs to the class of uracil herbicides, 3-cyclohexyl-l, 5,6,7- tetrahydrocyclopentapyrimidine-2,4(3H)-dione (C13H18N2O2) (CAS registry number 2164-08- 1). Lenacil is a known herbicide that is approved in many jurisdictions as a soil-acting herbicide for the control of grass and broad-leaved weeds in beet and other crops.
[0017] Lenacil has relatively low solubility in water. This relatively low solubility in water is preferred for an antimicrobial material that may be included in a coating composition or other building material, because dried coatings and building materials are exposed to water, which could tend to remove a highly soluble compound from the dried coating or the building material.
[0018] The present invention involves a composition that contains both lenacil and carbendazim. It has been surprisingly found that such a composition is synergistically effective as a biocide. It has been especially surprisingly found that compositions that contain both lenacil and carbendazim are synergistically effective as biocides.
[0019] When carbendazim is present, preferably the weight ratio of carbendazim to lenacil compound is preferably 1: 10 to 10:1.
[0020] The mixture of lenacil and carbendazim may be included in a coating composition. Lenacil and carbendazim may be added to the coating composition separately or as a mixture or any combination thereof. Preferred coating compositions are liquid. Coating
compositions may be aqueous or non-aqueous. Aqueous coating compositions generally contain 30% or more water by weight of the mixture, based on the weight of the coating composition.
[0021] Among embodiments in which lenacil and carbendazim are included in paint or other coating composition, preferred coating compositions are liquid compositions, especially compositions that contain dispersions of polymers in aqueous media.
[0022] In addition to paints and other coating compositions such as marine anti-fouling, the antimicrobial compound combinations of the present invention are particularly useful in preservation of building materials, e.g., adhesives, caulk, joint compound, sealant, wallboard, etc., polymers, plastics, synthetic and natural rubber, paper products, fiberglass sheets, insulation, exterior insulating finishing systems, roofing and flooring felts, building plasters, bricks, mortar, gypsum board, wood products and wood-plastic composites. When an antimicrobial compound combination of the present invention is present in a building material, it is preferred that some or all of the antimicrobial compound combination is present at the surface of the building material or near enough to the surface of the building material to inhibit microbial growth on that surface.
[0023] In some embodiments, latex paints or other liquid coating compositions are used that contain the antimicrobial compound combinations disclosed herein. [0024] Coating compositions are designed so that a layer of the coating composition can readily be applied to a substrate and then dried or allowed to dry to form a dry film. Coating compositions contain a binder. Binders contain one or more of the following: one or more polymer, one or more oligomer, and/or one or more monomer. Oligomers and monomers in binders are designed to polymerize and/or crosslink during or after the formation of the dry film. Polymers in a binder may or may not be designed to crosslink during or after the formation of the dry film.
[0025] Coating compositions optionally contain one or more pigment. A pigment is a mineral or an organic substance in the form of small solid particles. Pigments provide full or partial opacity to the dry film.
[0026] The antimicrobial compound combinations are useful for preservation of the dry film coating resulting after application of paint or other liquid coating composition. Preferably, the antimicrobial composition is an aqueous latex paint comprising one or more of the antimicrobial compound combinations disclosed herein, or the dry film coating resulting from application of the paint to a surface. An aqueous latex paint is an aqueous liquid coating composition in which the binder is a polymer in the form of a latex (i.e., in the form of polymer particles dispersed throughout the water). More preferred are aqueous latex paints in which the binder contains one or more acrylic polymer.
[0027] Typically, the amount of the antimicrobial compound combinations of the present invention to control the growth of microorganisms is from 100 ppm to 40,000 ppm active ingredient. For example, in the present invention, lenacil plus carbendazim is present in an amount from 100 ppm to 10,000 ppm. The antimicrobial combinations of the composition are present in an amount of at least 100 ppm and no more than 8,000 ppm, preferably no more than 6,000 ppm, preferably no more than 5,000 ppm, preferably no more than 4,000 ppm, preferably no more than 3,000 ppm, preferably no more than 2500 ppm, and preferably no more than 2,000 ppm. Concentrations mentioned above are in a liquid coating
composition containing the antimicrobial compound combinations; antimicrobial compound combination levels in the dry film coating will be higher.
[0028] The present invention also encompasses a method for preventing microbial growth in building materials, especially in dry film coatings, by incorporating any of the claimed antimicrobial compound combinations into the materials.
[0029] Typically, the antimicrobial compositions are used to inhibit growth of algae and/or fungi. [0030] The composition of the present invention contains lenacil and carbendazim. It is contemplated that some embodiments may contain one or more additional antimicrobial compound.
[0031] The following are examples of the present invention.
[0032] Sample preparation for antimicrobial testing was performed as follows:
[0033] Slurries containing 33% antimicrobial active ingredient (Lenacil) were post added to a white, acrylic/silicone based outdoor paint free of biocides to give a total active ingredient concentration of 10000 and 1000 ppm respectively. Slurries containing 34.3% carbendazim were post added to a white, acrylic/silicone based outdoor paint free of biocides to give a total active ingredient concentration of 10000 and 1000 ppm respectively. These paints were then diluted with an antimicrobial free acrylic/silicone based paint and mixed to prepare targeted concentrations of antimicrobial compounds for the testing. The total biocides concentrations tested were 125, 250, 500, 1000, 2000 and 5000 ppm. After biocides addition or dilution, the paints were mixed 90 seconds with the horse power shaker (AXEL 75M3372/ Agitateur SO-10MI) until uniformity was achieved. Paints containing different antimicrobial compounds at the same levels were mixed together in order to obtain the desired ratio of antimicrobial compounds. After one day, the paints were applied to Schleicher & Schuell filter paper at 280μιη wet film thickness and dried for 3 days at room temperature avoiding direct exposure to sunlight. Square discs (1.6 cm x 1.6 cm) were cut out from each panel and were used as the substrate for algal efficacy tests. This sample size allowed for an agar border when the sample disc was placed into the well of the test plate.
[0034] Algal Efficacy Testing:
[0035] Algal efficacy was tested according to modified ASTM 5589 which is a standard accelerated test method for determining resistance of various coatings (including paints) to algal defacement. To accommodate for high-throughput screening, this method was scaled down from petri dishes to 6-well plates. Bold Modified Basal Freshwater Nutrient Solution was used as growth medium. A single coated filter paper coupon was placed with a pair of sterile forceps at the center of the agar plug (on top) with the painted surface facing upwards. Algal inoculums were prepared by mixing equal concentrations (lx 106 cfu/ml) and equal volumes of exponentially growing algae cultures. [0036] Algal inoculums:
Figure imgf000007_0001
[0037] Each well that contains a tested coupon was inoculated with 1750 μΐ of algal suspensions (lx 106 cfu/ml) making sure that the whole surface (paint film as well as the agar surrounding it) was evenly covered. The plates were incubated at room temp (21°C - 25 °C) with cyclic exposure to light and dark phases, for a period of four weeks.
[0038] At the end of the four week incubation period, the samples were scored for percent inhibition regarding visible algal growth compared to the blank sample (0% inhibition).
[0039] The Synergy Index calculation was performed as follows.
[0040] The SI is calculated based on F.C.Kull et. Al. method (Applied Microbiology, Vol. 9 (1961). In this study, SI was calculated based on the following formula with the minimum inhibitory concentration chosen based on the percent inhibitory exhibited by the individual antimicrobial against each microorganisms tested.
SI= Qa/QA+Qb/QB
Qa = the concentration of Antimicrobial A in the blend
QA = the concentration of Antimicrobial A as the only biocide
Qb = the concentration of Antimicrobial B in the blend
QB = the concentration of Antimicrobial B as the only antimicrobial
[0041] SI value of < 1 in the formula indicates a synergism of the blended biocides exists.
[0042] Note: If any of the active with maximum concentration tested did not exhibit some inhibition, this maximum concentration is used to calculate the estimated SI and a sign of less than (<) is included to take into account that higher concentration of the active (Lenacil) is needed to achieve the targeted inhibition. The minimal targeted inhibition was set at 75%, meaning a coupon with at least 75% algal growth inhibition was considered as a pass.
[0043] Compositions listed below that contain both lenacil and carbendazim are examples of the present invention. [0044] Test Results for carbendazim with lenacil at 4 weeks were as follows:
[0045] Pass level >75 inhibition
Figure imgf000008_0001
[0046] Carbendazim + Lenacil at ratio 1: 10 to 10:1 exhibited a synergy.

Claims

1. A synergistic antimicrobial composition comprising lenacil and
carbendazim.
2. The synergistic antimicrobial composition of claim 1, wherein the weight ratio of the carbendazim to lenacil is from 1:10 to 10:1.
3. A method of inhibiting the growth of or controlling the growth of microorganisms in a building material, the method comprising the step of adding the synergistic antimicrobial composition of claim 1 to the building material.
4 A method of inhibiting the growth of or controlling the growth of microorganisms in a building material, the method comprising the step of adding the synergistic antimicrobial composition of claim 2 to the building material.
5. A coating composition comprising the synergistic antimicrobial composition of claim 1.
A coating composition comprising the synergistic antimicrobial composition of claim 2.
A dry film made by a process comprising applying a layer of the coating composition of claim 5 to a substrate and drying the coating composition or allowing the coating composition to dry.
8. A dry film made by a process comprising applying a layer of the coating composition of claim 6 to a substrate and drying the coating composition or allowing the coating composition to dry.
PCT/US2014/053618 2013-08-30 2014-08-30 Synergistic combination of a lenacil compound and carbendazim for dry film protection WO2015031874A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
KR1020167007163A KR20160051792A (en) 2013-08-30 2014-08-30 Synergistic combination of a lenacil compound and carbendazim for dry film protection
CN201480045868.1A CN105517438B (en) 2013-08-30 2014-08-30 For the lenacil compound of dry film protection and the synergistic combination of carbendazim
AU2014311985A AU2014311985B2 (en) 2013-08-30 2014-08-30 Synergistic combination of a lenacil compound and carbendazim for dry film protection
US14/913,033 US9408388B2 (en) 2013-08-30 2014-08-30 Synergistic combination of a lenacil compound and carbendazim for dry film protection
MX2016002107A MX360553B (en) 2013-08-30 2014-08-30 Synergistic combination of a lenacil compound and carbendazim for dry film protection.
JP2016537928A JP6411507B2 (en) 2013-08-30 2014-08-30 Synergistic combination of lenacyl compound and carbendazim for dry film protection
EP14766316.5A EP3010342A1 (en) 2013-08-30 2014-08-30 Synergistic combination of a lenacil compound and carbendazim for dry film protection
RU2016110840A RU2650521C2 (en) 2013-08-30 2014-08-30 Synergistic combination of lenacil compound and carbendazim for dry film protection

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201361871989P 2013-08-30 2013-08-30
US61/871,989 2013-08-30

Publications (1)

Publication Number Publication Date
WO2015031874A1 true WO2015031874A1 (en) 2015-03-05

Family

ID=51541345

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2014/053618 WO2015031874A1 (en) 2013-08-30 2014-08-30 Synergistic combination of a lenacil compound and carbendazim for dry film protection

Country Status (9)

Country Link
US (1) US9408388B2 (en)
EP (1) EP3010342A1 (en)
JP (1) JP6411507B2 (en)
KR (1) KR20160051792A (en)
CN (1) CN105517438B (en)
AU (1) AU2014311985B2 (en)
MX (1) MX360553B (en)
RU (1) RU2650521C2 (en)
WO (1) WO2015031874A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017176544A1 (en) * 2016-04-04 2017-10-12 Dow Global Technologies Llc Synergistic combination of a lenacil compound and fludioxonil for dry film protection
WO2017210048A1 (en) * 2016-05-31 2017-12-07 Dow Global Technologies Llc Synergistic combination of lenacil and thiabendazole for dry film protection
WO2017210051A1 (en) * 2016-05-31 2017-12-07 Dow Global Technologies Llc Synergistic combination of a lenacil compound and chlorothalonil for dry film protection

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3836332A1 (en) * 1988-10-25 1990-04-26 Richter Gedeon Vegyeszet Use of 3-cyclohexyl-5,6-(trimethylene)uracil and/or 3-tert-butyl-5-chloro-6-methyluracil to change the biological water quality of open waters
US5756500A (en) * 1992-12-08 1998-05-26 Schulke & Mayr Gmbh Aqueous dispersion having a fungicidal and algicidal effect
WO1998021962A1 (en) 1996-11-20 1998-05-28 Troy Corporation Synergistic algaecide
WO1998033380A1 (en) * 1997-01-30 1998-08-06 Air Liquide Sante (International) Algicidal and fungicidal preservative with alternaria-activity
JPH1135409A (en) * 1997-05-20 1999-02-09 Takeda Chem Ind Ltd Algecidal and mildencidal composition
US6197805B1 (en) * 1999-05-27 2001-03-06 Troy Technology Corporation, Inc. Broad spectrum antimicrobial mixtures

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4650808A (en) * 1984-03-28 1987-03-17 Buckman Laboratories, Inc. Synergistic compositions containing hydroxypropyl methanethiolsulfonate and methods of using same
GB8629360D0 (en) * 1986-12-09 1987-01-21 Sandoz Ltd Fungicides
DE10040814A1 (en) * 2000-08-21 2002-03-07 Thor Gmbh Synergistic biocide composition
CN1274776C (en) * 2000-12-26 2006-09-13 李昌柱 Water-thinned finishing latex paint
PL214973B1 (en) * 2002-03-21 2013-10-31 Basf Ag Fungicide mixture, method for fighting harmful fungi and fungicide
UA80368C2 (en) * 2003-10-29 2007-09-10 Basf Ag Fungicidal mixture, agent, method for control, seed and use of compounds
CN101473835B (en) * 2008-01-03 2013-11-06 上海生农生化制品有限公司 Composition with function for killing sigatoka pathogen and other harmful fungi
BRPI1010111A2 (en) * 2009-06-18 2015-08-25 Basf Se Fungicidal mixture, fungicide, triazole compound, use of a fungicidal mixture, agrochemical composition, seed and method for controlling pathogenic fungi

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3836332A1 (en) * 1988-10-25 1990-04-26 Richter Gedeon Vegyeszet Use of 3-cyclohexyl-5,6-(trimethylene)uracil and/or 3-tert-butyl-5-chloro-6-methyluracil to change the biological water quality of open waters
US5756500A (en) * 1992-12-08 1998-05-26 Schulke & Mayr Gmbh Aqueous dispersion having a fungicidal and algicidal effect
WO1998021962A1 (en) 1996-11-20 1998-05-28 Troy Corporation Synergistic algaecide
WO1998033380A1 (en) * 1997-01-30 1998-08-06 Air Liquide Sante (International) Algicidal and fungicidal preservative with alternaria-activity
JPH1135409A (en) * 1997-05-20 1999-02-09 Takeda Chem Ind Ltd Algecidal and mildencidal composition
US6197805B1 (en) * 1999-05-27 2001-03-06 Troy Technology Corporation, Inc. Broad spectrum antimicrobial mixtures

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
APPLIED MICROBIOLOGY, vol. 9, 1961

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017176544A1 (en) * 2016-04-04 2017-10-12 Dow Global Technologies Llc Synergistic combination of a lenacil compound and fludioxonil for dry film protection
CN108882707A (en) * 2016-04-04 2018-11-23 陶氏环球技术有限责任公司 For the lenacil compound of dry film protection and the synergistic combination of fludioxonil
WO2017210048A1 (en) * 2016-05-31 2017-12-07 Dow Global Technologies Llc Synergistic combination of lenacil and thiabendazole for dry film protection
WO2017210051A1 (en) * 2016-05-31 2017-12-07 Dow Global Technologies Llc Synergistic combination of a lenacil compound and chlorothalonil for dry film protection

Also Published As

Publication number Publication date
JP6411507B2 (en) 2018-10-24
CN105517438B (en) 2018-03-27
AU2014311985A1 (en) 2016-03-24
US9408388B2 (en) 2016-08-09
MX2016002107A (en) 2016-06-28
US20160198709A1 (en) 2016-07-14
JP2016534126A (en) 2016-11-04
CN105517438A (en) 2016-04-20
RU2016110840A (en) 2017-10-05
AU2014311985B2 (en) 2017-09-21
RU2650521C2 (en) 2018-04-16
MX360553B (en) 2018-11-07
EP3010342A1 (en) 2016-04-27
KR20160051792A (en) 2016-05-11

Similar Documents

Publication Publication Date Title
AU2013352023B8 (en) Synergistic combination of lenacil and one of DCOIT or OIT for dry film protection
AU2017201379B2 (en) Synergistic combination of a lenacil compound and zinc pyrithione for dry film protection
AU2013352024B2 (en) Synergistic combination of lenacil and IPBC for dry film protection
AU2014311985B2 (en) Synergistic combination of a lenacil compound and carbendazim for dry film protection
AU2014311984B2 (en) Synergistic combination of a lenacil compound and flurochloridone for dry film protection
AU2013352026B2 (en) Synergistic combination of lenacil and terbutryn for dry film protection
EP3010343A1 (en) Synergistic combination of a lenacil compound and phenylurea herbicides for dry film protection
EP2953459A1 (en) Synergistic combination of a flurochloridone compound and ipbc for dry film protection
WO2017210048A1 (en) Synergistic combination of lenacil and thiabendazole for dry film protection
WO2017176543A1 (en) Synergistic combination of a lenacil compound and n-butyl-1,2-benzisothiazolin-3-one for dry film protection
WO2014085745A1 (en) Synergistic combination of a zoxamide compound and terbutryn for dry film protection
EP2914110A1 (en) Synergistic combination of zoxamide and one of dcoit or oit for dry film protection
WO2017210051A1 (en) Synergistic combination of a lenacil compound and chlorothalonil for dry film protection
WO2017176544A1 (en) Synergistic combination of a lenacil compound and fludioxonil for dry film protection
WO2014160957A1 (en) Synergistic combination of a chlorotoluron compound and terbutryn for dry film protection

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14766316

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2014766316

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: MX/A/2016/002107

Country of ref document: MX

ENP Entry into the national phase

Ref document number: 2016537928

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 14913033

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112016003447

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 20167007163

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2014311985

Country of ref document: AU

Date of ref document: 20140830

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2016110840

Country of ref document: RU

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 112016003447

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20160218