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WO2007019237A2 - Compositions d'enduction pour la lutte contre des organismes nuisibles - Google Patents

Compositions d'enduction pour la lutte contre des organismes nuisibles Download PDF

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Publication number
WO2007019237A2
WO2007019237A2 PCT/US2006/030306 US2006030306W WO2007019237A2 WO 2007019237 A2 WO2007019237 A2 WO 2007019237A2 US 2006030306 W US2006030306 W US 2006030306W WO 2007019237 A2 WO2007019237 A2 WO 2007019237A2
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WO
WIPO (PCT)
Prior art keywords
composition
composition according
polyol
microencapsulated pesticide
microencapsulated
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Application number
PCT/US2006/030306
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English (en)
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WO2007019237A3 (fr
Inventor
Jacqueline Behles
Nelson Johnson
Patrick Mulqeen
John Silverthorne
Ian Tovey
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Syngenta Participations Ag
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Application filed by Syngenta Participations Ag filed Critical Syngenta Participations Ag
Publication of WO2007019237A2 publication Critical patent/WO2007019237A2/fr
Publication of WO2007019237A3 publication Critical patent/WO2007019237A3/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N25/08—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 containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds

Definitions

  • the field of the invention relates to polyurethane coating compositions, methods for coating substrates with the compositions and methods for using such compositions to control pests.
  • Baiting is another method to control termites. Bait stations are installed underground around the perimeter of the house, for example, every 10 to 20 feet and 2 feet out from the house. This method takes considerable time to eliminate a colony of up to one year. It relies upon individual termites feeding on the bait which contains a non-repellant termiticide (e.g. hexaflumuron, sulfluramid), and returning to the colony to pass the poison on to other members, killing a portion of the exposed colony. However, termites that are not attracted to the bait may seek out wood in the building to feed on.
  • a non-repellant termiticide e.g. hexaflumuron, sulfluramid
  • the present invention is directed to a curable polyurethane composition containing a microencapsulated pesticide, non-foam coatings prepared there from, and methods of making the same.
  • the coating compositions of the invention containing microencapsulated pesticides are usually significantly lower in their acute toxicities to non-targets (e.g. humans) than are non-encapsulated pesticide products thereby allowing easier safe handling of the compositions and incorporation of pesticides without significant operator health concerns.
  • the controlled release characteristics of such coatings containing microencapsulated pesticides allow for greater flexibility in overall product design and polymer selection to achieve the desired release characteristics.
  • the curable polyurethane composition of the invention is a mixture of one or more components that react to form a non-foam polyurethane coating and at least one microencapsulated pesticide, which composition is suitable for coating various substrates or loci by applying a layer or layers of such composition thereto.
  • Suitable components that react to form a polyurethane include at least one polyisocyanate material and at least one active hydrogen-containing material.
  • the present invention provides a curable, two- part non-foaming polyurethane coating composition adapted to cure under ambient conditions comprising a mixture of (A) at least one polyisocyanate, (B) at least one polyol and (C) at least one microencapsulated pesticide.
  • the microencapsulated pesticides can be premixed with the polyisocyanate or with the polyol component or they can be added separately to the reaction mixture as it is being applied to a target substrate or locus.
  • the coating composition is a high-solids composition which is substantially free of water and blowing agents.
  • the inventive coating composition may also contain polymerization catalysts, antimicrobial agents, non-encapsulated pesticides, or other additives such as rheology control agents, plasticizers, thickeners, surfactants, pigments, fillers, dispersants, freeze-thaw stabilizers, flame retardants and coalescents.
  • compositions of the invention are particularly suitable for use in a method for reducing or preventing pest attack or pest infiltration of substrates or loci that are susceptible or vulnerable to such attack or infiltration, which method comprises (I) providing a curable, non-foaming reaction mixture of at least one microencapsulated pesticide and one or more components that react to form a polyurethane (such as at least one polyisocyanate and at least one polyol), (II) applying the mixture to the susceptible substrate or locus; and (III) curing the mixture under ambient conditions to form a polyurethane coating on the substrate or in the locus.
  • a curable, non-foaming reaction mixture of at least one microencapsulated pesticide and one or more components that react to form a polyurethane (such as at least one polyisocyanate and at least one polyol)
  • a polyurethane such as at least one polyisocyanate and at least one polyol
  • a coating is formed on a target substrate such as a construction material (e.g., concrete), a plastic vapor barrier or a utility penetration such as a pipe or conduit.
  • a coating is formed in a pest susceptible locus such as a wall void or bath trap.
  • the coating compositions of the invention can be applied to target substrates and loci by professionals or non-professionals by spraying, painting, rolling, or brushing, before, during, or after construction and may be formulated to provide coatings having effectiveness against fungi, wood destroying microorganisms, insects and representatives of the order acarina, including, for example, arthropods such as termites, wood-boring ants, wood-boring insects and spiders.
  • ambient temperature shall be understood to mean a temperature of from about 0 degrees Celsius to about 50 degrees Celsius; or particularly from about 15 degrees Celsius to about 32 degrees Celsius; or more particularly from about 20 degrees Celsius to about 25 degrees Celsius.
  • curing under ambient conditions shall be understood to mean a curing reaction that takes place at ambient temperatures without the addition of external heat. As the curing reaction itself is exothermic, it will be understood that the temperature of the reaction mixture per se may temporarily exceed ambient temperatures during curing due to the exothermic nature of the chemical reaction occasioned by the formation of the urethane coating.
  • high-solids shall be understood to mean coating systems with a solids content exceeding 85 wt %.
  • microencapsulated insecticide is understood to refer to small solid particles or liquid droplets of a compound which has a lethal effect on insects of a type to be controlled (namely that the application of an appropriate amount of such compound results in death of a substantial portion of the insects being treated) coated with a thin film of a polymer coating or shell material.
  • microencapsulated insecticide is used to describe particles with diameters between 0.05 and 1000 ⁇ m.
  • suitable microencapsulated insecticides have and average particle size of from about 1 to 50 ⁇ m.
  • the term "monomer” means a polymerizable molecule that forms a basic repeating unit in a polymer chain.
  • Oligomer refers to a polyfunctional polymerized compound whose backbone is formed from 2 to 10 monomers.
  • Prepolymer refers to a polyfunctional polymerized compound whose backbone is formed from more than 10 monomers, but has a viscosity or can be made to have a viscosity at ambient temperatures that is suitable for coating.
  • non-foam or “non-foaming” in relation to the coating composition of the invention means a composition which cures to a substantially non-cellular polyurethane film.
  • substantially non-foaming in this context means that such a film may contain small amounts of foam such that the density of the coating will be at least equivalent to 90% of that of the polymer phase of the film.
  • pests includes fungi and other wood decaying microorganisms, insects and representatives of the order acarina, including termites, ants, other wood boring insects and spiders. Specific species of such pests are defined in more detail below.
  • pesticide product refers to the combination of active and inert constituents associated with a microencapsulated pesticide that is used alone or in combination with one or more non-encapsulated pesticides.
  • compositions of the invention relate to compositions having at least two parts including (A) a polyisocyante material in a first part, (B) a polyol in a second part and (C) the above-described microencapsulated pesticide in said first or said second part, or optionally in one or more additional parts as desired (such as a separate pesticide containing part, for example), the two (or more) parts being intended to be mixed together prior to use.
  • polyurethane coatings containing microencapsulated pesticides have improved pesticide retention and a concomitant resistance to wood pests such as termites, wood-boring ants, wood-boring insects, spiders, fungi and wood destroying microorganisms.
  • the pest resistant polyurethane coatings are prepared from a curable polyurethane reaction system comprising (i) a mixture of one or more components that react to form a polyurethane and (ii) at least one microencapsulated pesticide.
  • the system is suitable for use in coating various substrates or loci by applying a layer or layers of such system thereto.
  • Suitable components that react to form a polyurethane include at least one polyisocyanate material and at least one active hydrogen-containing material.
  • a two-part, non-foaming polyurethane coating composition adapted to cure under ambient conditions which comprises: (A) at least one polyisocyanate, (B) at least one polyol and (C) at least one microencapsulated pesticide.
  • compositions are high-solids and substantially free of water and blowing agents.
  • the release rate of pesticides from coated substrates and loci can be better controlled by applying to a target substrate or locus a non-foaming coating composition comprising a mixture of at least one polyisocyanate, at least one polyol and at least one microencapsulated pesticide, which mixture is curable under ambient conditions to form a microencapsulated pesticide containing polyurethane coating on the substrate or in the locus.
  • the present invention provides a high-solids, non- foaming pesticidal coating composition
  • a high-solids, non- foaming pesticidal coating composition comprising a reactive mixture of: (A) at least one polyisocyanate, (B) at least one polyol, and (C) a pesticidally effective amount of at least one microencapsulated pesticide, which composition is curable under ambient conditions and wherein the microencapsulated pesticide within coatings prepared therefrom is effective to reduce or prevent pest attack or pest infiltration of the coated substrate.
  • any known system for producing non-foaming polyurethane coatings and films may be used as a starting point for the pesticidal coating compositions of the invention, such as those set forth in the chapter on Coatings by Zeno W. Wicks Jr. (section 8.3. Urethane Systems) of the Kirk-Othmer Encyclopedia of Chemical Technology Copyright ⁇ 2002 by John Wiley & Sons, Inc.
  • base formulations will be modified to include a pesticidally effective amount of a microencapsulated pesticide.
  • each of the components are mixed together in a mixing chamber.
  • each of the components is separately introduced into the mixing chamber.
  • each of the components can be introduced as a separate stream into the mixing chambers.
  • any means which is recognized in the art, such as a variable speed pump, can be employed to separately control the flow of each of the components into the mixing chamber in order to provide the desired product.
  • one or more of the components can be premixed prior to introduction into the mixing chamber.
  • the polyols (or polyisocyanates) and a microencapsulated pesticide can be premixed and introduced to the mixing chamber as one component. It is possible to combine all of the ingredients other than the diisocyanate (or polyol) and introduce just two components to the mixing stream. It also is possible to pre- react the diisocyanate with at least a portion of the polyol. The pre-polymer is then introduced to the mixing chamber along with the other components, either singularly or premixed, to produce a polyurethane coating. Since an extra step is involved, the resulting coating is usually more expensive.
  • the components can be adjusted so that the final polyurethane film coating may contain small amounts of foam such that the density of the coating will be at least equivalent to 90% of that of the polymer phase of the film.
  • foam such that the density of the coating will be at least equivalent to 90% of that of the polymer phase of the film.
  • the polyurethane coating system is mixed with a pesticidally effective amount of a suitable microencapsulated pesticide.
  • the microencapsulated pesticide is selected to impart pest resistive properties to the final coating and coated substrate or target locus as required under the prevailing circumstances.
  • a pre-mix of the microencapsulated pesticide with the polyol, catalyst (if used) and other ingredients (except the polyisocyanate) is prepared which is suitable to package, sell and ship and is suitable for use in a multi-component (e.g., two-part) polyurethane coating system.
  • microencapsulated pesticide with the active hydrogen (polyol) component and, optionally, other additives such as a catalyst or reaction accelerator in a composition which is substantially free of isocyanate functional compounds.
  • a pre-mix of the microencapsulated pesticide with the polyisocyanate and other ingredients is also within the scope of the invention.
  • microencapsulated products will be produced via an aqueous interfacial process, resulting in a dispersion of microcapsules in water. Water will then need to be removed from such a system. This can be achieved by separation of the capsules from the aqueous phase by some separation technique (e.g. centrifugation) to lower to water content, or the capsule product may be dried by any suitable technique (such as spray drying). Dry product may then be added directly to the film components (in either phase). Such methods are well known in the art. All possible combinations are thus anticipated and incorporated into this teaching.
  • Suitable spray-drying adjuvants include water-soluble salts such as ammonium sulfate or sodium, potassium or calcium chlorides.
  • the adjuvants may also include surfactants, water soluble polymers, higher alcohols and other water-soluble or water-dispersible components such as gums, clays and silica's.
  • chemistries are well known to those skilled in the art but include polymer stabilisers such as polyacrylic acids, polyvinyl alcohols (and their copolymers), polyvinylpyrrolidones (and their copolymers), surface active agents such as ethylene oxide-propylene oxide copolymers, naphthalene sulphonic acid-formaldehyde condensates and alkylbenzene sulphonates.
  • polymer stabilisers such as polyacrylic acids, polyvinyl alcohols (and their copolymers), polyvinylpyrrolidones (and their copolymers), surface active agents such as ethylene oxide-propylene oxide copolymers, naphthalene sulphonic acid-formaldehyde condensates and alkylbenzene sulphonates.
  • polymer stabilisers such as polyacrylic acids, polyvinyl alcohols (and their copolymers), polyvinylpyrrolidones (and their copo
  • a two part system as a co-package or in a dispenser having a static mixer or the like that is suitable for shipping and/or selling which comprises a f ⁇ rst pre-mix (A) containing at least one polyisocyanate material which is substantially free of active hydrogen compounds, a second pre-mix (B) containing at least one polyol which is substantially free of isocyanate functional compounds, and wherein at least one of the first or the second pre-mixes contain (C) at least one microencapsulated pesticide.
  • a pesticidally effective amount of the microencapsulated pesticide is present in only one of the pre-mixtures.
  • both pre-mixes in the co-pack contain a portion of the total pesticidally effective amount of the microencapsulated pesticide.
  • the polyisocyanate, polyol and microencapsulated pesticide are provided in separate premixes in a tri-pack configuration.
  • the two pre-mixes are mixed together immediately prior to application (such as by spraying or brushing) to prevent the clogging of the application equipment.
  • the two parts are combined within the nozzle of a pressurized spraying device.
  • suitable spraying devices are suitable for the practice of the present invention. These devices are well understood by those having skill in the art.
  • one spray configuration employs a dispensing gun and associated container pumps actuated by compressed air (e.g., 110 psi).
  • Each container (such as a 55 gal. drum) contains one part of the two-part system, with at least one part containing a microencapsulated pesticide.
  • the dispensing gun cartridge assembly contains a mixing chamber, where the two parts are combined under pressure.
  • the parts are mixed in substantially stochiometric amounts and, in particular, at a 1:1 ratio.
  • the polyisocyanate and polyol parts are placed in separate receptacles, usually pressurizable containers, within an outer container such as a metal aerosol can, and the can is sealed with an aerosol valve.
  • a dispenser is attached to the can for dispensing the polyurethane coating composition into a curable state.
  • suitable spraying devices allow the pre-mixes to be combined within the nozzle by directing at least two liquid feed streams into the spraying nozzle. It will be understood that three liquid feed streams will be provided in systems having a tri-pack configuration.
  • the present invention contemplates a two (or more) part system wherein a first part comprising at least one active hydrogen-containing material is combined with a second part comprising at least one polyisocyanate material to form the pest resistant polyurethane coating, wherein either one or both of the parts contains a microencapsulated pesticide.
  • This may be accomplished simply by applying the two (or more) parts to the substrate or locus to be protected sequentially; first with the active hydrogen-containing material mixture and then with the second part containing the polyisocyanate material.
  • the combined parts are curable under ambient conditions to form a polyurethane coating containing a pesticidally effective amount of a microencapsulated pesticide.
  • suitable polyurethane formulations will have a viscosity that is acceptable for coating.
  • the viscosity at ambient temperature be within the range of 100 to 10,000 cP, particularly 500 to 1,000 cP, to provide a coating composition which penetrates and spreads adequately over the surface of a substrate being coated.
  • More viscous compositions may be made less viscous by the addition of compatible solvents (both inert and reactive).
  • suitable inert solvents include the fully etherif ⁇ ed or esterified glycol ethers, the acetates, xylene, toluene and methyl isobutyl ketone.
  • Suitable reactive solvents include the lower molecular weight diols such as ethylene glycol, diethylene glycol, 1 ,4-butane diol, 1 ,6-hexane diol, and 1,10- decane diol and the lower molecular weight oligomers of ethylene, propylene and butylene glycol, for example, polyethylene glycol 400 or polypropylene glycol 425.
  • the solvents may be present in an amount of up to about 15% by weight and more particularly from about 10 to 15% by weight of the entire composition.
  • the compositions are substantially free of added volatile organic solvents.
  • microencapsulated pesticides used in the coating compositions of the invention may contain some organic solvent and that this is considered to not be a constituent of added solvent).
  • suitable polyisocyanates include aromatic, aliphatic, and cycloaliphatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate (“MDI”), toluene diisocyanate (“TDI”), xylylene diisocyanate, tetramethylxylene diisocyanate, naphthalene diisocyanate, para-phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, mixtures thereof, and the like.
  • MDI 4,4'-diphenylmethane diisocyanate
  • TDI toluene diisocyanate
  • xylylene diisocyanate tetramethylxylene diisocyanate
  • naphthalene diisocyanate para-phenylene diisocyanate
  • tetramethylene diisocyanate hexamethylene
  • the polyol component comprises more than one polymerizable OH (hydroxyl) functional compounds, suitably comprising two or more hydroxyl groups, per molecule on average.
  • the polymerizable, hydroxyl functional compounds may be aliphatic and/or aromatic.
  • the polymerizable, hydroxyl functional compounds may be straight, cyclical, fused, and/or branched.
  • polymerizable hydroxyl functional compounds include at least one diol, at least one triol, and/or at least one tetrol. Any of these polyol compounds may be monomelic, oligomeric, and/or polymeric as desired. If oligomeric and/or polymeric, the polyol(s) may be selected from one or more hydroxyl functional polyethers, polyesters, polyurethanes, polyacrylics, epoxy resins, polyamides, polyamines, polyureas, polysulfones, castor oil, combinations of these, or the like. Polyether polyols such as the polyalkylene ether and polyester polyols may be mentioned as these are commercially available at relatively low cost and are hydrolytically stable.
  • Suitable polyalkylene ether polyols include the poly(alkylene oxide) polymers such as poly(ethylene oxide) and poly(propylene oxide) polymers and copolymers with terminal hydroxyl groups derived from polyhydric compounds, including diols and triols; for example, ethylene glycol, propylene glycol, 1,3-butane diol, 1 ,4-butane diol, 1 ,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylol propane and similar low molecular weight polyols.
  • Suitable commercially available polyether polyols include those sold under the trade name Voranol* (The Dow Chemical Company).
  • the polyester polyols which are suitable in accordance with the invention include the known polycondensates of organic dihydroxy and optionally polyhydroxy (trihydroxy, tetrahydroxy) compounds and dicarboxylic and also optionally polycarboxylic (tricarboxylic, tetracarboxylic) acids or hydroxycarboxylic acids or lactones.
  • polycondensates of organic dihydroxy and optionally polyhydroxy (trihydroxy, tetrahydroxy) compounds and dicarboxylic and also optionally polycarboxylic (tricarboxylic, tetracarboxylic) acids or hydroxycarboxylic acids or lactones instead of the free polycarboxylic acids it is also possible to use the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols to prepare the polyesters such as, for example, phthalic anhydride.
  • diols examples include ethylene glycol, 1,2-butanediol, diethylene glycol, Methylene glycol, polyalkylene glycols, such as polyethylene glycol, and also 1,2- and 1,3-propanediol, 1 ,4-butanediol, 1 ,6-hexanediol, neopentyl glycol or neopentyl glycol hydroxypivalate.
  • polyols having 3 or more hydroxyl groups in the molecule which may be used additionally, if desired, include trimethylolpropane, trimethylolethane, glycerol, erythritol, pentaerythritol, di- trimethylolpropane, dipentaerythritol, trimethylol-benzene or trishydroxyethyl isocyanurate.
  • a particularly suitable class of polyols useful in the compositions, coatings and methods of the invention are the phthalic anhydride based polyester-ether polyols which are described, for example, in U.S. patent 6,855,844 which is incorporated by reference herein. Suitable commercially available phthalic anhydride based polyester-ether polyols include the "Stepanpols" (Stepan Company).
  • suitable polyols are those having a viscosity at 25 degrees C of from about 500 to 15,000 cP and a hydroxyl number of from about 25 to 400.
  • the amount of polyisocyanate material employed in the invention should be sufficient to provide at least about 0.7 NCO group per reactive hydrogen present in the total reaction system.
  • a stoichiometric excess of polyol compound may be conveniently employed. Stoichiometric excess generally means that the ratio of OH groups of the polyol component to the NCO groups of the polyisocyanate component is greater than 1 , specifically from greater than about 1.5 to about 20, more specifically from greater than about 2 to about 10, most specifically from greater than about 2.2 to about 10.
  • an OH/NCO molar ratio of about 2.5 to about 6 would be especially suitable to provide compositions that cure at a desirable rate without substantial foaming, if any, to form coatings with excellent pesticide retention characteristics, hi one embodiment, the materials are employed in a 1:1 OH/NCO ratio.
  • levels may be specified within the scope of the invention.
  • compositions of the invention may include an effective amount of a catalyst or reaction accelerator such as tertiary amines, metal-organic compounds, co- curatives, and the like.
  • a catalyst is, for example, from about 0.005 to 2 percent by weight of the reactive polyol and polyisocyanate components.
  • the catalyst is present at a level of about 0.01 to about 1.0 percent, based on the total weight of the polyisocyanate material and active hydrogen-containing material employed in the composition.
  • An exact amount can be readily determined by statistical analysis under the reaction conditions, including the actual polyol and polyisocyanate component reactivity, the anticipated reaction conditions, the equipment available, and the like, without undue experimentation.
  • Suitable catalysts include tertiary amines, organometallic tin compounds, triethylene diamine, dibutyl tin dilaurate, dibutylbis(laurylthio)stannate, dibutyltinbis(isooctylmercapto acetate), dibutyltinbis(isooctyl maleate), dimethylcyclohexylamine, and l,8-diazabiscyclo[5,4,0]undec-7-ene (DBU).
  • tertiary amines organometallic tin compounds
  • triethylene diamine dibutyl tin dilaurate
  • dibutylbis(laurylthio)stannate dibutyltinbis(isooctylmercapto acetate)
  • dibutyltinbis(isooctyl maleate) dimethylcyclohexylamine
  • DBU l,8-diazabiscyclo
  • the polyurethane coating compositions will be formulated to produce a coating that is optimized for the environment in which it is to be applied such as suitable open time to allow for uniform application and penetration, proper adhesion of the coating to the target substrate, resistance of the coating to chemical degradation in basic or acidic environments, UV stability, etc., as the case may be.
  • suitable open time to allow for uniform application and penetration
  • proper adhesion of the coating to the target substrate resistance of the coating to chemical degradation in basic or acidic environments, UV stability, etc., as the case may be.
  • coatings that are provided beneath concrete slabs are often exposed to a more alkaline environments that coatings that are provided above a slab.
  • a polyurethane such as, for example, a sterically hindered polyol (such as a phthalic anhydride based polyester polyol) which can better resist base catalyzed hydrolysis.
  • a sterically hindered polyol such as a phthalic anhydride based polyester polyol
  • compositions of the invention may be employed with other ingredients or adjuvants to impart to or modify particular characteristics of the composition.
  • the adjuvants should be added only at a level that does not materially adversely interfere with the stability of the microencapsulated pesticide or the adhesion of coatings prepared from the composition.
  • the adjuvants may comprise up to 50 weight percent of the polyol/microencapsulated pesticide composition either individually or in combination.
  • chain-extension agents e.g., short chain polyols such as ethylene glycol or butanediol
  • fillers e.g., carbon black; glass, ceramic, metal or plastic bubbles; metal oxides such as zinc oxide; and minerals such as talc, clays, silica, silicates, and the like
  • thermoplastic resins plasticizers; antioxidants; pigments; U.V.
  • absorbers such as silanes, and the like may be included to modify set time, open time, green strength build-up, tack, flexibility, adhesion, ductility, adhesive strength, gloss; elongation, pliability, buckling strength, crease resistance; as well as increased resistance to solvents, acids, bases, light, heat, cold, and sudden temperature changes, etc.
  • adhesion promoters such as silanes, and the like may be included to modify set time, open time, green strength build-up, tack, flexibility, adhesion, ductility, adhesive strength, gloss; elongation, pliability, buckling strength, crease resistance; as well as increased resistance to solvents, acids, bases, light, heat, cold, and sudden temperature changes, etc.
  • adhesion promoters such as silanes, and the like may be included to modify set time, open time, green strength build-up, tack, flexibility, adhesion, ductility, adhesive strength, gloss; elongation, pliability, buckling strength
  • flame retardants can be incorporated.
  • Useful flame retardants include, without limitation, any compound with flame suppression properties that can be dissolved or dispersed in the polyurethane coating. These include compounds such as chlorinated or brominated phosphates, phosphonates, inorganic oxides and chlorides.
  • the flame retardant is a soluble liquid such as triethyl phosphonate, pentabromodiphenyl oxide, and in ⁇ ⁇
  • the flame retardants are employed in an amount of from 5 to 15 parts by weight.
  • composition mixture may be formulated such that the polyurethane coating may be made to cure to any useful color or shade as would be readily apparent to one skilled in the field of polyurethane coatings.
  • colorants may be used to create films with color.
  • the ratio of polyurethane to pesticidal product in the cured coating at the time that a film of the composition cures is at least 70:30 polymer: pesticide product, particularly 80:20 polyme ⁇ pesticide product and more particularly 85:15 polymer: pesticide product.
  • a filler such as fiber may be added to improve cohesion and flow characteristics of the coating composition.
  • suitable fibers there may be mentioned glass fibers.
  • the fibers help to prevent the liquid surface coating from sagging on pitched or vertical surfaces of target substrates during cure and to improve robustness and structural integrity of the cured film or coating.
  • Other solid fillers such as clay, calcium carbonate, and titanium dioxide are also contemplated.
  • polyols and polyisocyanates that can be used are those that are capable of fo ⁇ ning a substantially water-impermeable polyurethane coating upon curing.
  • the coating is substantially water-impermeable, it is best tested by an appropriate water resistance test (for example, ASTM Method D 870-2).
  • ASTM Method D 870-2 ASTM Method D 870-2
  • the resultant polyurethane is one that is compatible with the polymer in the wall of the microcapsule employed in the composition.
  • polyurethane coatings having a thickness of from 0.1 to 10 mm are formed on a target substrate.
  • the coating thickness can be greater, indeed it can be employed to fill substantially completely the void space.
  • Those skilled in the art will adapt the coating thickness as appropriate under the prevailing circumstances such as by allowing a small amount of foaming to occur to increase the volume of the film.
  • the polyurethane coatings of the invention may be provided with a protective overcoat such as a latex or a polyurethane composition without a microencapsulated pesticide.
  • Latexes suitable as overcoats of the cured polyurethane coatings are derived from a wide variety of polymers and co-polymers and combinations thereof.
  • Suitable latexes for use as overcoats comprise polymers and copolymers of styrene, alkyl styrenes, isoprene, butadiene, acrylonitrile lower alkyl acrylates, vinyl chloride, vinylidene chloride, vinyl esters of lower carboxylic acids and alpha, beta-ethylenically unsaturated carboxylic acids, including polymers containing three or more different monomer species copolymerized therein, as well as post-dispersed suspensions of silicones or polyurethanes.
  • the latex overcoats can be compounded with, or have mixed therein, other known ingredients such as plasticizers, emulsifiers, stabilizers, curing agents, fillers, antioxidants, antifoaming agents, dying adjuvants, levelling agents, pigments, or other compounding aids.
  • plasticizers emulsifiers
  • stabilizers emulsifiers
  • curing agents fillers
  • antioxidants antifoaming agents
  • dying adjuvants e.g., levelling agents, pigments, or other compounding aids.
  • thickeners or bodying agents may be added to the polymer latexes so as to control the viscosity of the latexes and thereby achieve the proper flow properties for the particular application desired.
  • thickeners or bodying agents may be added to the polymer latexes so as to control the viscosity of the latexes and thereby achieve the proper flow properties for the particular application desired.
  • Such materials are well known in the art.
  • the non-curable ingredients of the coating composition and cured coating herein further comprise at least one pesticide product comprising at least one microencapsulated pesticide and, optionally, one or more non-microencapsulated pesticides.
  • the microencapsulated pesticide portion of the pesticide product is present in an amount of at least 1% by weight of the cured coating.
  • the amount of any non-microencapsulated pesticides that are present in the composition are utilized in an amount of from 0 to about 99% by weight of the entire pesticide product present in the cured composition. Mixtures of pesticides and mixtures of microencapsulated products are also possible.
  • the pesticide products in the coating composition and cured polyurethane film coating including insecticides, acaricides and fungicides are employed in pesticidally effective amounts which will correspond to rates dependent on their activity levels for the desired end use.
  • suitable rates for the pesticide products are the existing rates given on the current product labels for such pesticide products.
  • Microencapsulated pesticide active ingredients suitable for use in the coating compositions and cured coatings according to the invention are prepared with any suitable technique known in the art.
  • various processes for microencapsulating material have been previously developed. These processes can be divided into three categories- physical methods, phase separation and interfacial reaction.
  • microcapsule wall material and core particles are physically brought together and the wall material flows around the core particle to form the microcapsule.
  • phase separation category microcapsules are formed by emulsifying or dispersing the core material in an immiscible continuous phase in which the wall material is dissolved and caused to physically separate from the continuous phase, such as by coacervation, and deposit around the core particles.
  • microcapsules are formed by emulsifying or dispersing the core material in an immiscible continuous phase and then an interfacial polymerization reaction is caused to take place at the surface of the core particles.
  • concentration of the pesticidal active ingredient present in the microcapsules can vary from 0.1 to 60% by weight of the microcapsule.
  • Suitable microcapsules for use in the polyurethane coating compositions and cured coatings of the invention include microcapsules of both the relatively thin-walled quick- release type and the relatively thicker-walled controlled-release type or combinations thereof.
  • suitable microcapsule wall materials are selected from the polyureas, aminoplasts, polyurethanes and polyamidesand mixtures thereof.
  • polyurea microcapsules containing a suitable termiticide are prepared as exemplified in U.S. Pat. No. 4,285,720, which involves the use of at least one polyisocyanate such as polymethylene polyphenylisocyanate (PMPPI) and/or tolylene diisocyanate (TDI) as the prepolymer.
  • PMPPI polymethylene polyphenylisocyanate
  • TDI tolylene diisocyanate
  • the wall- forming reaction is initiated by heating the emulsion to an elevated temperature at which point the isocyanate polymers are hydrolyzed at the interface to form amines, which in turn react with unhydrolyzed polymers to form the polyurea microcapsule wall.
  • microencapsulated pesticides suitable for use in the invention will be produced via an aqueous interfacial process, resulting in a dispersion of microcapsules in water.
  • the water may be decreased or removed from such systems by freeze drying, spray drying and other drying techniques known in the art prior to adding to the polyol or polyisocyanate component of the curable composition.
  • Processes for production of relatively dry water-dispersible compositions of microencapsulated pesticides are described, for example, in U.S. Pat. Nos. 5,354,742 and 6,555,122 which are incorporated by reference herein.
  • the spray drying of the microcapsule is carried out under typical spray-drying conditions and with the use of typical spray-drying equipment in which the inlet temperatures generally range from about 105 to about 200' C. and output temperatures range from about 45 to about 95 0 C.
  • suitable insecticidal, termiticidal or acaricidal active ingredients for use in the polyurethane coating composition and cured coatings include, but are not limited to, pyrethrins and synthetic pyrethroids; azoles, bisamides, oxadizine derivatives; chloronicotinyls; nitroguanidine derivatives; triazoles; organophosphates; pyrrols; pyrazoles; phenyl pyrazoles; diacylhydrazines; biological/fermentation products; carbamates and combinations of these types of compounds.
  • suitable insecticides, termiticides or acaricides for use in the inventive polyurethane compositions and cured coatings include tefluthrin, permethrin, the cyhalothrins including lambda cyhalothrin and gamma cyhalothrin, resmethrin, deltamethrin, cypermethrin, cyphenothrin, cyfluthrin, deltamethrin, chlorpyrifos, fenoxycarb, diazinon, dichlorophen, methyl isothiocyanate, pentachlorophenol, tralomethrin, chlorfenapyr, f ⁇ pronil, neonicotinoids and combinations of these compounds.
  • suitable neonicotinoids include, but are not limited to, thiamethoxam, nitenpyram, imidacloprid, clothianidin, . o
  • acetamiprid and thiacloprid.
  • One specific class of pesticides for use in the microcapsules are the class of cyhalothrins including lambda cyhalothrin and gamma cyhalothrin.
  • suitable rates for the insecticide are the existing rates given on the current product labels for pesticide products containing such pesticide.
  • suitable fungicides for use in the polyurethane coating composition and cured coatings include, but are not limited to, the azoles such as cyproconazole, propiconazole, tebuconazole and difenoconazole; the strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifJoxystrobin; chlorothalonil; and thiabendazole.
  • suitable rates for the fungicide are the existing rates given on the current product labels for pesticide products containing such fungicide.
  • microencapsulated insecticides (optionally including at least one non-microencapsulated pesticide such as an insecticide or fungicide) are present in the coating composition in an amount to provide an effective barrier to insect pests such as arthropods which contact or come into the vicinity of coatings prepared from the compositions.
  • insect pests such as arthropods which contact or come into the vicinity of coatings prepared from the compositions.
  • the exact amount will vary depending upon factors including the type of microcapsule employed, the substrate or locus to be coated as well as the thickness and orientation (horizontal or vertical) of the coating.
  • the insecticide of the coating must not prematurely dissipate and should be efficacious during that time in the target insects' life cycle which may cause potential damage to wood portions of a building or other construction.
  • the barrier coating of the present invention will contain an amount of insecticide that is insecticidally effective.
  • An insecticidally effective amount a used herein means that amount of insecticide that will kill insect pests or will consistently reduce or retard the amount of damage produced by insect pests.
  • target pests include insects and representatives of the order acarina such as termites, ants (such as carpenter ants) and spiders. More specifically, termites that may be controlled by the composition and method of the invention include, for example, Reticutitermes spp. such as R. ⁇ avipes, R. hesperus, R. tibialis, R. virginicus, R.santonensis and R. hageni and Coptotermes spp. such as C.formosanus.
  • the application methods such as spraying, misting, atomising, broadcasting, brushing, caulking, spreading, dipping or pouring, and the nature of the composition are adapted to suit the intended aims and the prevailing circumstances.
  • Optimum rates of application of the inventive composition, for a particular target substrate or locus and set of insect pressure conditions, can be determined easily and without undue experimentation by simple ranging studies carried out in wood such as in wooden building construction and wood which is in contact with soil for example fence posts, utility poles, railroad cross-ties and wooden supports, that can be structurally degraded by the action of one or more fungal or wood pests including, but not limited to, wood destructive fungi, termites, ants and other boring insects or arthropods.
  • the compositions of the invention are applied to substrates or loci such as clean, dry surfaces, typically concrete and cement including in and around concrete slab joins such as construction joints, key joints, tool joints and saw joints.
  • suitable targets include substrates such as plastic surfaces and substrates such as a DPM (Damp-proof membrane), vapor or moisture barriers or retarders and loci in or around structures, such as, homes, buildings, utility penetrations, bath traps, wall voids, wooden structures and other construction materials or construction substrates.
  • DPM Digital-proof membrane
  • vapor or moisture barriers or retarders in or around structures, such as, homes, buildings, utility penetrations, bath traps, wall voids, wooden structures and other construction materials or construction substrates.
  • DPM's can be a simple polyethylene membrane, a chemically etched polyethylene (such as Corona treated polyethylene for greater wetting, substantivity of the polymer film to the polyethylene sheet) or re-in forced, structured multilayer polyethylene sheets such as the product range sold under the Tradename GRIFFOLYN® sold by Reef Industries, Inc. (Houston, TX).
  • the coating compositions are also applied to self-amalgamating tapes and films such as those composed of bitumous materials, butyl rubber, polyisobutene and the like, such as those sold under the Tradename Jiffy Seal® either prior to or after application of such self- amagamating materials to a target substrate such as a construction substrate, material or utility penetration such as a PVC or copper pipe or the like.
  • the coating composition After the coating composition has been applied to the target substrate or locus, it is cured to form the polymer coating.
  • the coating is “cured”, or when “curing” the coating is referred to, what is meant is that a solid coating of components is formed from the polyol(s) and polyisocyanate(s) in the composition. Curing is often the result of a chemical reaction, adsorption, sequestration, or other forms of polymer curing that are known in the art.
  • the polyurethane coating composition when coated onto substrates or loci exhibits resistance to pests including termites such that if termites do attempt to feed or tunnel through the coating, they find it not palatable or it causes mortality.
  • the main component used in the coating composition that either causes mortality or makes it not palatable is a microencapsulated pesticide.
  • the cured physical polyurethane coating also contributes synergistically to this protection against insects such as arthropods including termites and wood-boring ants by inhibition of feeding.
  • Demand CS microencapsulated lambda cyhalothrin, Syngenta Crop Protection, Inc., Greensboro, NC
  • a surfactant solution prepared from 300g of water, 6.Og of Morwet** D425 (sodium sulfonate of naphthalene formaldehyde condensate/ Witco) and 0.7g of HiSiI 233 (silica filler/ PPG).
  • the components are thoroughly mixed until a stable mixture is formed.
  • Sprayed-dried Demand CS is obtained by pumping the mixture at 21-22 ml/min into a spray drier having an inlet temperature of 105 C and an outlet temperature of 74-75 C.
  • EXAMPLE 7 Polyurethane Film (above concrete) 1.48 g Air Products Dabco T-12 catalyst (dibutyl tin dilaureate) and 198.52 g Stepan Company's Stepanpol PS-2002 were mixed together to form a homogeneous solution at room temperature. Using 1O g of this polyol solution, 0.30 g of spray-dried Demand IOCS was mixed in thoroughly and then 5.36 g of Rubinate M was added. These components were quickly stirred together and spread the top of a dry block of dry concrete following the procedure of example 3.
  • EXAMPLE 8 Polyurethane Film (above concrete) 1752 + PC 1.45 g Air Products Dabco T-12 catalyst (dibutyl tin dilaureate), 198.55 g Stepan Company's Stepanpol PS-1752, and 22.22 g of Jeffsol ® AG 1555 were mixed together to form a homogeneous solution at room temperature. Using 11.11 g of this polyol solution, 0.31 g of spray-dried Demand IOCS was mixed in thoroughly and then 4.47 g of Rubinate M was added. These components were quickly stirred together and spread the top of a dry block of dry concrete following the procedure of example 3.
  • a sample of about 1 gram of each film prepared and in accordance with examples 1 - 11 each containing a given % by weight of microencapsulated pesticide is transferred to a 2 oz bottle. 20 ml of tetrahydrofuran (THF) solvent is added to the bottle and sonicated in a water bath for about 30 minutes. Each sample is filtered through a 0.45 micron filter and analyzed for lambda cyhalothrin by HPLC. The results (% retention based on initial assay) are reported in the table below for both 1 and 2 months after treatment (MAT).
  • THF tetrahydrofuran
  • This slurry was spray dried with an inlet tempearture of 170 0 C and an outlet temperature of 66°C to yield a solid product containing 22.5% Lambda-cyhalothrin.
  • a portion of the capsules were formulated into a polyurethane film and illustrates the use of a system with more than two feedstock streams in the film preparation::
  • this invention provides a new curable polyurethane composition containing a microencapsulated pesticide, non-foam coatings prepared therefrom, and methods of making the same. Variations may be made in proportions, procedures and materials without departing from the scope of the invention as defined by the following claims.

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne une composition de polyuréthanne pouvant être durcie contenant un pesticide microencapsulé, des matériaux d'enduction sensiblement non moussants préparés à partir de cette composition ainsi que des procédés de fabrication de cette composition.
PCT/US2006/030306 2005-08-04 2006-08-01 Compositions d'enduction pour la lutte contre des organismes nuisibles WO2007019237A2 (fr)

Applications Claiming Priority (2)

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US60/705,675 2005-08-04

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2913308A1 (fr) * 2007-03-05 2008-09-12 Julien Boutiron Procede pour la protection contre les insectes, notamment les termites des surfaces a batir
FR2932509A1 (fr) * 2008-06-13 2009-12-18 Julien Boutiron Film de protection des surfaces a batir contre les insectes ainsi que procede d'obtention d'un tel film de protection
FR2952085A1 (fr) * 2009-11-03 2011-05-06 Antoine Boutiron Procede de protection des habitations contre les insectes, en particulier les termites
WO2020068749A1 (fr) * 2018-09-28 2020-04-02 Rohm And Haas Company Agents de conservation du bois
US12059000B1 (en) 2020-09-03 2024-08-13 Drexel University Use of erythritol compositions as mammal-safe insecticides
US12082583B2 (en) 2017-03-31 2024-09-10 Nutrition & Biosciences Usa 2, Llc Wood preservatives
US12168307B2 (en) 2018-09-28 2024-12-17 Nutrition & Biosciences Usa 2, Llc Wood preservatives

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US5063059A (en) * 1987-12-25 1991-11-05 Sumitomo Chemical Co., Ltd. Microencapsulated cockroach-controlling composition
US6322803B1 (en) * 1999-07-03 2001-11-27 Bioguard Technologies, Inc. Method for applying pesticides and repellents
US6803051B1 (en) * 1998-02-25 2004-10-12 Battelle Memorial Institute K1-53 Multi-layer barrier preventing wood pest access to wooden structures

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3803303A (en) * 1972-01-27 1974-04-09 Kibben G Mc Polymeric compositions for attracting cotton boll weevils
US4670246A (en) * 1984-11-05 1987-06-02 Pennwalt Corporation Microencapsulated pyrethroids
US5063059A (en) * 1987-12-25 1991-11-05 Sumitomo Chemical Co., Ltd. Microencapsulated cockroach-controlling composition
US6803051B1 (en) * 1998-02-25 2004-10-12 Battelle Memorial Institute K1-53 Multi-layer barrier preventing wood pest access to wooden structures
US6322803B1 (en) * 1999-07-03 2001-11-27 Bioguard Technologies, Inc. Method for applying pesticides and repellents

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2913308A1 (fr) * 2007-03-05 2008-09-12 Julien Boutiron Procede pour la protection contre les insectes, notamment les termites des surfaces a batir
FR2913310A1 (fr) * 2007-03-05 2008-09-12 Boutiron Julien Marie Christia Protection antitermites des batiments au moment de leur construction
FR2913309A1 (fr) * 2007-03-05 2008-09-12 Julien Boutiron Procede pour la protection contre les insectes, notamment les termites des surfaces a batir
WO2008119916A2 (fr) * 2007-03-05 2008-10-09 Julien Boutiron Procédé pour la protection contre les insectes, notamment les termites des surfaces a bâtir
WO2008119916A3 (fr) * 2007-03-05 2009-01-22 Julien Boutiron Procédé pour la protection contre les insectes, notamment les termites des surfaces a bâtir
FR2932509A1 (fr) * 2008-06-13 2009-12-18 Julien Boutiron Film de protection des surfaces a batir contre les insectes ainsi que procede d'obtention d'un tel film de protection
FR2952085A1 (fr) * 2009-11-03 2011-05-06 Antoine Boutiron Procede de protection des habitations contre les insectes, en particulier les termites
US12082583B2 (en) 2017-03-31 2024-09-10 Nutrition & Biosciences Usa 2, Llc Wood preservatives
WO2020068749A1 (fr) * 2018-09-28 2020-04-02 Rohm And Haas Company Agents de conservation du bois
CN114845547A (zh) * 2018-09-28 2022-08-02 营养与生物科技美国第二有限公司 木材防腐剂
CN114845547B (zh) * 2018-09-28 2024-04-02 营养与生物科技美国第二有限公司 木材防腐剂
US12168307B2 (en) 2018-09-28 2024-12-17 Nutrition & Biosciences Usa 2, Llc Wood preservatives
US12059000B1 (en) 2020-09-03 2024-08-13 Drexel University Use of erythritol compositions as mammal-safe insecticides

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