PROTECTING PLANTS FROM PESTS CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U. S. Provisional Patent Application No. 62/482,794 filed April 7, 2017, which is hereby incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

A. Field of the Invention

[0002] The present invention relates generally to the field of insecticidal coatings. More particularly, it concerns protective coating compositions and methods of their use for protecting a variety of plants from pests.

B. Description of Related Art

[0003] Attempts to protect plants from pests typically include the use of systemic pesticides, insecticidal coatings, pheromone traps placed near the plant, cutting and/or burning of infected plants, and curing infected plants, especially at the early stages of infestation. However, there are many drawbacks to these treatments, including the requirement to repeatedly treat the plants, the need to use a large amount of pesticides, and negative impacts to the environment.

[0004] For example, systemic pesticide application includes applying insecticide through a hole in the trunk or stem of the plant above an infested area or spraying an insecticide on the ground surrounding the plant. The systemic insecticides enter the vascular system of the plant and are transported throughout the plant, with sometimes the undesirable effect of having fruit or other edible portions of the plant exposed to pesticides. Systemic pesticide application typically requires a relatively large amount of insecticide for effectiveness and much of the pesticide can be lost to the environment, including undesirable seepage into ground water.

[0005] Insecticidal coatings have been used on plants and seeds to remedy some of the problems with systemic application and the other typical plant protection methods. The coatings typically contain a pesticide and an adhesive/glue, such as a polymeric adhesive. For example, International Patent Application Publication No. WO 2016/009279 to Rettori et al. discloses a plant treatment coating layer that contains an insecticide and a polymeric adhesive. Llacer et al. {J Econ Entomol. 2010; 103(2):402-8) discloses an insecticidal paint based on chlorpyrifos and pyriproxyfen in a microencapsulated formulation. However, current insecticidal coatings are not without their own problems. The coatings can require re- application due to degradation of the active insecticide or wearing away of the coating. Further, the coatings can potentially hinder the free flow of seeds and/or retain foreign unwanted material if the coatings do not completely dry or lose their tackiness in a short period of time. Attempts to remedy these problems have been made. For example, U.S. Patent Application Publication No. 2008/0167374 to Stickler et al., U.S. Patent No. 9,204,630 to Shirly et al., and European Patent No. EP 0 250 908 to Rheaume et al. each disclose insecticidal compositions that can contain UV protectants to help prevent degradation of the insecticide. U.S. Patent Application Publication Nos. 2008/0167374 to Stickler et al. and 2010/0297259 to Wilson et al. each disclose insecticidal compositions that can contain antioxidants to also help protect the insecticide.

[0006] Some of the issues concerning current insecticidal coatings are that they still do not sufficiently protect the insecticide from degradation and/or are not sufficiently durable, especially when exposed to inclement weather conditions. The lack of durability can lead to breakdown of the coating and ultimately loss of efficacy in protecting the plants from pests.

SUMMARY OF THE INVENTION

[0007] A solution has been discovered to at least some of the aforementioned problems associated with insecticidal coatings. The solution is premised on the development of durable non-tacky protective coatings that reduce or eliminate the amount of pesticide that enters the vascular system of a plant. The protective coatings of the present invention can be an insecticidal coating layer designed to be in direct contact with the plant and/or can be a non- tacky overcoating layered over an insecticidal coating. In the context of the present invention, the insecticidal coating and the overcoating can both generally be referred to as "protective coating(s)." The overcoating can being capable of reducing degradation of the insecticide or the insecticidal coating during use. The protective coatings can form a hardened surface that can reduce the need to reapply the coatings. The protective coatings of the present invention can contain an insecticide, a photoprotectant, an antioxidant, a hydrolysis resistant additive, a surface hardening additive, and/or an aqueous dispersed polymeric adhesive material. Further, and as illustrated in a non-limiting manner in the Examples, protective coating compositions that include carbon black as a photoprotectant exhibit strong protection of the insecticide {e.g., chlorpyrifos) and good durability when subjected to accelerated weathering conditions. This is especially true when an insecticidal coating composition is protected with an overcoating composition of the present invention.

[0008] It has also been discovered that the insecticide, chlorpyrifos, and/or degradation products of chlorpyrifos can have surface hardening properties. Thus, the use of this insecticide in the protective coatings of the present invention can allow for a reduction of or removal of traditional surface hardening additives from the coatings. The resulting protective coating compositions can be more cost efficient to produce while retaining their desired durability. Alternatively, additional hardening additives can be added to further increase the durability of the chlorpyrifos containing protective coating compositions.

[0009] In one aspect of the present invention, there is disclosed a durable insecticidal coating composition capable of protecting plants from pests. The insecticidal coating composition can be configured to be in direct contact with an exterior surface of a plant. The insecticidal coating composition can contain an insecticide, a photoprotectant and/or a surface hardening additive, and an aqueous dispersed polymeric adhesive material, or any combination thereof.

[0010] In another aspect of the present invention, there is disclosed an overcoat/overcoating composition that is capable of protecting the insecticide in an insecticidal coating during use. The insecticidal coating can be any insecticidal coating, including but not limited to the insecticidal coating compositions of the present invention. In some aspects, the overcoating composition can contain a photoprotectant and/or a surface hardening additive and an aqueous dispersed polymeric adhesive material. The overcoating composition can be capable of reducing degradation of an insecticidal coating composition and/or an insecticide contained in the insecticidal coating composition. In some instances, the overcoating composition reduces the degradation of the insecticidal coating composition while the insecticidal coating composition is protecting plants from pests.

[0011] The aqueous dispersed polymeric adhesive material that can be used in the protective coatings of the present invention can include a continuous aqueous phase and a dispersed polymer phase. The insecticide and the photoprotectant, if present, can be dispersed in the aqueous phase. The surface hardening additive, antioxidant, and/or hydrolysis resistant additive, if present, can either be solubilized in the aqueous phase or dispersed in a polymer phase of the aqueous dispersed polymeric adhesive material. In some instances, the polymeric material can be aqueous-dispersed polyvinyl acetate. However, other polymeric materials can be used in the context of the present invention, including those disclosed throughout this specification and claims. Without wishing to be bound by theory, it is believed that the aqueous dispersed polymeric adhesive material can provide a structure by acting as a binder that allows for the other ingredients in the insecticidal coating or overcoating compositions (e.g., an insecticide, a photoprotectant, an antioxidant, a hydrolysis resistant additive, and/or a surface hardening additive) to remain stable prior to, during application of, and/or drying of the compositions. The resulting compositions, whether formulated as an insecticidal coating or as an overcoat, can be durable in challenging weather conditions (e.g., heat, sand storms, arid conditions, etc.) and/or can limit leaching of the insecticide into the vascular system of the plants and the surrounding environment.

[0012] In one aspect of the invention, 44 embodiments are described. Embodiment 1 is a durable insecticidal coating composition capable of protecting plants from pests, the insecticidal coating composition comprising: an insecticide; a photoprotectant and/or a surface hardening additive; and an aqueous dispersed polymeric adhesive material that includes a continuous aqueous phase and a dispersed polymer phase, wherein the insecticide and the photoprotectant, if present, are dispersed in the aqueous phase. Embodiment 2 is the durable insecticidal coating composition of embodiment 1, wherein the composition comprises a surface hardening additive that is either solubilized in the aqueous phase or dispersed in a polymer phase. Embodiment 3 is the insecticidal coating composition of any of embodiments 1 to 2, comprising: at least 80 wt. %, preferably at least 90 wt. %, of the aqueous dispersed polymeric adhesive material; 1 wt. % to 5 wt. %, preferably 2 wt. % to 3 wt. %, of the insecticide; 0.1 wt. % to 3 wt. %, preferably 0.5 wt. % to 2 wt. %, of the photoprotectant; and 0.01 wt. % to 2 wt. %, preferably 0.1 wt. % to 1 wt. %, of the surface hardening additive. Embodiment 4 is the insecticidal coating composition of any one of embodiments 1 to 3, wherein the dispersed polymer phase comprises polyvinyl acetate, methyl cellulose, polyvinyl alcohol, polyvinylidene chloride, polyacrylic, cellulose, polyvinylpyrrolidone, polysaccharide, natural latex, or synthetic latex, or any combination thereof. Embodiment 5 is the insecticidal coating composition of embodiment 4, wherein the aqueous-dispersed polymeric adhesive material is aqueous-dispersed polyvinyl acetate. Embodiment 6 is the insecticidal coating composition of any one of embodiments 1 to 5, wherein the insecticide comprises tefluthrin and/or chlorpyrifos. Embodiment 7 is the composition of embodiment 5, wherein the insecticide comprises chlorpyrifos mixed into the coating and/or chemically bonded to an insecticide carrier. Embodiment 8 is the composition of embodiment 7, wherein the chlorpyrifos is chemically bonded to an insecticide carrier and the insecticide carrier is a particulate having an average particle size of less than about 20 to 500 microns, preferably about 50 to 120 microns. Embodiment 9 is the insecticidal coating composition of any one of embodiments 1 to 8, wherein the insecticidal coating composition comprises a photoprotectant, preferably carbon black. Embodiment 10 is the insecticidal coating composition of any one of embodiments 1 to 9, wherein the insecticidal coating composition comprises a surface hardening additive, preferably sulfuric acid and/or derivatives thereof. Embodiment 11 is the insecticidal coating composition of embodiment 10, wherein the surface hardening additive is chlorpyrifos. Embodiment 12 is the insecticidal coating composition of embodiment 11, wherein no acid-based surface hardening additive is added to the insecticidal coating. Embodiment 13 is the insecticidal coating composition of embodiment 1, comprising: at least 90 wt. % of the aqueous-dispersed polymeric adhesive material, wherein the aqueous-dispersed polymeric adhesive material is aqueous-dispersed polyvinyl acetate; 2 wt. % to 3 wt. % of the insecticide, wherein the insecticide is chlorpyrifos; and 0.5 wt. % to 2 wt. %, of the photoprotectant, wherein the photoprotectant is carbon black. Embodiment 14 is the insecticidal coating composition of embodiment 1, comprising: at least 90 wt. % of the aqueous-dispersed polymeric adhesive material, wherein the aqueous-dispersed polymeric adhesive material is aqueous-dispersed polyvinyl acetate; 2 wt. % to 3 wt. % of the insecticide, wherein the insecticide is chlorpyrifos; and 0. wt. % to 1 wt. %, of the surface hardening additive, wherein the surface hardening additive is sulfuric acid, derivatives of sulfuric acid, chlorpyrifos, and/or byproducts of chlorpyrifos. Embodiment 15 is the insecticidal coating composition of any of embodiments 1 to 14, wherein the aqueous dispersed polymeric adhesive material further comprises a surfactant. Embodiment 16 is the insecticidal coating composition of any one of embodiments 1 to 15, further comprising an antioxidant and/or a hydrolysis resistant additive to protect the insecticide from degradation, wherein the antioxidant and/or hydrolysis resistant additive is optionally present in the composition in an amount of 0.01 wt. % to 2 wt. %, preferably 0.5 wt. % to 1 wt. %. Embodiment 17 is the insecticidal coating composition of embodiment 16, wherein the antioxidant and/or hydrolysis resistant additive is selected from citric acid, phosphoric acid, benzoic acid, a combination of citric acid and phosphoric acid, or any combination thereof. Embodiment 18 is the insecticidal coating composition of any one of embodiments 1 to 17, wherein the insecticidal coating composition is in direct contact with an exterior surface of a plant, preferably a palm tree selected from Phoenix dactylifera or Phoenix canariensis, and wherein the insecticide is active against red palm weevil.

[0013] Embodiment 19 is a method of treating or preventing infestation of a plant by a pest, the method comprising: applying the insecticidal coating composition of any one of embodiments 1 to 18 to an exterior surface of the plant to form an insecticide-containing layer that is in direct contact with the surface of the plant, wherein the insecticide-containing layer is effective for treating or preventing infestation of the plant by a pest without the insecticide entering the vascular system of the plant. Embodiment 20 is the method of embodiment 19, wherein the pest is a red palm weevil and the plant is a palm tree, preferably Phoenix dactylifera or Phoenix canariensis. Embodiment 21 is the method of any one of embodiments 19 to 20, wherein the insecticidal coating composition is applied to severed and/or live leaf bases and/or petiole bases of the plant.

[0014] Embodiment 22 is an overcoating composition for an insecticidal coating composition capable of protecting plants from pests, the overcoating composition comprising: a photoprotectant and/or a surface hardening additive; and an aqueous dispersed polymeric adhesive material that includes a continuous aqueous phase and a dispersed polymer phase, wherein the photoprotectant, if present, is dispersed in the aqueous phase and the surface hardening additive, if present, is solubilized in the aqueous phase, and wherein the overcoating composition is capable of reducing degradation of the insecticidal coating composition and/or insecticide contained in the insecticidal coating composition during use. Embodiment 23 is the overcoating composition of embodiment 22, comprising: at least 80 wt. % to 99.99 wt. %, preferably at least 90 wt. % to 99.9 wt. %, of the polymeric adhesive material; and 0.1 wt. % to 3 wt. %, preferably 0.5 wt. % to 2 wt. %, of the photoprotectant and/or 0.01 wt. % to 2 wt. %, preferably 0.1 wt. % to 1 wt. %, of the surface hardening additive. Embodiment 24 is the overcoating coating composition of any one of embodiments 22 to 23, wherein the dispersed polymer phase comprises polyvinyl acetate, methyl cellulose, polyvinyl alcohol, polyvinylidene chloride, polyacrylic, cellulose, polyvinylpyrrolidone, polysaccharide, natural latex, or synthetic latex, or any combination thereof. Embodiment 25 is the overcoating composition of embodiment 24, wherein the aqueous-dispersed polymeric adhesive material is aqueous-dispersed polyvinyl acetate. Embodiment 26 is the overcoating composition of any one of embodiments 22 to 25, wherein the insecticide comprises tefluthrin and/or chlorpyrifos. Embodiment 27 is the composition of embodiment 26, wherein the insecticide comprises chlorpyrifos mixed into the coating and/or chemically bonded to an insecticide carrier. Embodiment 28 is the composition of embodiment 27, wherein the chlorpyrifos is chemically bonded to an insecticide carrier and the insecticide carrier is a particulate having an average particle size of less than about 50 to 120 microns. Embodiment 29 is the overcoating composition of any one of embodiments 22 to 28, wherein the overcoating composition comprises a photoprotectant, preferably carbon black. Embodiment 30 is the overcoating composition of any one of embodiments 22 to 29, wherein the overcoating composition comprises a surface hardening additive, preferably sulfuric acid and/or derivatives thereof. Embodiment 31 is the overcoating composition of embodiment 30, wherein the surface hardening additive is chlorpyrifos and/or byproducts of chlorpyrifos. Embodiment 32 is the insecticidal coating composition of embodiment 31, wherein no acid-based surface hardening additive is added to the insecticidal coating. Embodiment 33 is the overcoating composition of embodiment 22, comprising: at least 80 wt. % to 99.99 wt. %, preferably at least 90 wt. % to 99.9 wt. %, of the aqueous-dispersed polymeric adhesive material, wherein the aqueous- dispersed polymeric adhesive material is aqueous-dispersed polyvinyl acetate; and 0.5 wt. % to 2 wt. %, of the photoprotectant, wherein the photoprotectant is carbon black. Embodiment 34 is the overcoating composition of embodiment 22, comprising: at least 90 wt. % of the aqueous-dispersed polymeric adhesive material, wherein the aqueous-dispersed polymeric adhesive material is aqueous-dispersed polyvinyl acetate; and 0.01 wt. % to 2 wt. %, preferably 0.1 to 1 wt. % of the surface hardening additive, wherein the surface hardening additive is sulfuric acid or derivatives of sulfuric acid. Embodiment 35 is the overcoating composition of any one of embodiments 22 to 34, wherein the aqueous dispersed polymeric adhesive material further comprises a surfactant. Embodiment 36 is the overcoating composition of any one of embodiments 22 to 35, wherein the overcoating composition forms a protective overcoat layer on the insecticidal coating composition. Embodiment 37 is the overcoating composition of embodiment 36, wherein the insecticidal coating composition is the composition of any one of embodiments 1 to 17 that has been dried. Embodiment 38 is the overcoating composition of embodiment 37, wherein the dried insecticidal coating composition comprises an insecticide and a polymeric adhesive layer, wherein the insecticide is dispersed in the polymeric layer. Embodiment 39 is the overcoating composition of embodiment 38, wherein the dried insecticidal coating composition comprises: at least 80 wt. %, preferably at least 95 wt. %, of the polymeric adhesive layer; and 1 wt. % to 5 wt. %, preferably 2 wt. % to 3 wt. % of the insecticide. Embodiment 40 is the overcoating composition of any one of embodiments 38 to 39, wherein the polymeric adhesive layer comprises polyvinyl acetate, methyl cellulose, polyvinyl alcohol, polyvinylidene chloride, polyacrylic, cellulose, polyvinylpyrrolidone, polysaccharide, natural latex, or synthetic latex, or any combination thereof, preferably aqueous dispersed polyvinyl acetate. Embodiment 41 is the overcoating composition of any one of embodiments 36 to 40, wherein the insecticidal coating composition is in direct contact with an exterior surface of the plant, preferably a palm tree selected from Phoenix dactylifera or Phoenix canariensis, and wherein the insecticide is active against red palm weevil.

[0015] Embodiment 42 is a method of treating or preventing infestation of a plant by a pest, the method comprising: applying an insecticidal containing coating composition to an exterior surface of the plant to form an insecticide-containing polymeric adhesive layer that is in direct contact with the surface of the plant, wherein the insecticide-containing polymeric adhesive layer is effective for treating or preventing infestation of the plant by a pest without the insecticide entering the vascular system of the plant; and applying the overcoating composition of any one of embodiments 22 to 35 to a surface of the insecticide-containing polymeric adhesive layer, wherein the overcoating composition forms a second polymeric adhesive layer that is in direct contact with the surface of the insecticide-containing polymeric adhesive layer, and wherein the second polymeric adhesive layer protects the insecticide and/or the insecticide- containing polymeric adhesive layer from degradation. Embodiment 43 is the method of embodiment 42, wherein the pest is a red palm weevil and the plant is a palm tree, preferably Phoenix dactylifera or Phoenix canariensis. Embodiment 44 is the method of any one of embodiments 42 to 43, wherein the insecticidal coating composition is applied to severed and/or live leaf bases and/or petiole bases of the plant.

[0016] The following includes definitions of various terms and phrases used throughout this specification.

[0017] "Chemically bonded" and "chemical bond" includes covalent bonds, ionic bonds, metallic bonds, hydrogen bonds, and London dispersion forces.

[0018] The terms "directly contact" or "direct contact" are defined as a physical contact between the materials in contact. In some instances, direct contact can include a physical mixing of the materials.

[0019] The use of the words "a" or "an" when used in conjunction with the term "comprising," "including," "containing," or "having" in the claims or the specification may mean "one," but it is also consistent with the meaning of "one or more," "at least one," and "one or more than one."

[0020] The terms "about" or "approximately" are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0021] The term "substantially" and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.

[0022] The terms "wt.%", "vol.%", or "mol.%" refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component. In a non-limiting example, 10 moles of component in 100 moles of the material is 10 mol.% of component.

[0023] The terms "inhibiting" or "reducing" or "preventing" or "avoiding" or any variation of these terms, when used in the claims and/or the specification includes any measurable decrease or complete inhibition to achieve a desired result. [0024] The term "effective," as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.

[0025] The words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "includes" and "include") or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0026] The compositions and methods of the present invention can "comprise," "consist essentially of," or "consist of particular steps, components, compositions, etc., disclosed throughout the specification. With respect to the transitional phase "consisting essentially of," in one non-limiting aspect, a basic and novel characteristic of the insecticidal coating and overcoating compositions of the present invention are their durability, which is especially advantageous when used in inclement weather conditions.

[0027] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The following drawings form part of the present specification and are included to further demonstrate certain non-limiting aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments presented herein.

[0029] FIG. 1A-D: Effect of accelerated weathering at 70% relative humidity (RH) on glue coating: A) glue without chlorpyrifos at 0 h exposure; B) glue without chlorpyrifos at 200 h exposure; C) glue with chlorpyrifos at 0 h exposure; D) glue with chlorpyrifos at 200 h exposure.

[0030] FIG. 2A-D: Effect of accelerated weathering with water spray and 30% RH on glue coating: A) glue without chlorpyrifos at 0 h exposure; B) glue without chlorpyrifos at 200 h exposure; C) glue with chlorpyrifos at 0 h exposure; D) glue with chlorpyrifos at 200 h exposure.

[0031] FIG. 3A-B: Effect of accelerated weathering on polyvinyl acetate (PVAc) from 0 to 648 h of accelerated weathering for films with or without chlorpyrifos.

[0032] FIG. 4: Effect of accelerated weathering on the polydispersity of PVAc from 0 to 350 h of accelerated weathering for the films with or without pesticides.

[0033] FIG. 5: Possible chemical events taking place upon weathering of a pesticide.

[0034] FIG. 6: Degradation profile of chlorpyrifos in glue formulation. C = Chlorpyrifos blank; PI = Carbon black; P2 = CHIMASSORB® 944.

[0035] FIG. 7: Degradation profile of chlorpyrifos in glue formulation. C = Chlorpyrifos blank; Al = Citric acid; A2 = Phosphoric acid; A3 = Benzoic acid.

[0036] FIG. 8: Effect of an overcoating composition of the present invention on degradation of chlorpyrifos during accelerated weathering observed at higher concentration for chlorpyrifos.

[0037] FIG. 9: Effect of an overcoating composition of the present invention on degradation of chlorpyrifos during accelerated weathering observed at lower concentration for chlorpyrifos.

[0038] FIG. 10: Effect of an overcoating composition of the present invention on the chlorpyrifos retention on exposure until 150 h using accelerated weathering.

[0039] FIG. 11: Effect of an overcoating composition of the present invention on the tefluthrin retention on exposure until 150 h using accelerated weathering.

[0040] FIG. 12A-B: Image collected for the insecticidal coating with (A) and without (B) an overcoating composition of the present invention in scatter mode using a two camera imaging system.

[0041] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and may herein be described in detail. The drawings may not be to scale.

DETAILED DESCRIPTION OF THE INVENTION

[0042] As discussed above, current coating compositions that are used to protect plants from pests suffer from a range of problems that can include lack of durability, the need for multiple applications, instability of the insecticides, and/or the leaching of insecticides into the plant vascular system or into the surrounding environment (e.g., ground, atmosphere, etc.). The present invention offers a solution to at least one, some, or all of these problems. The solution is premised on the development of insecticidal coating compositions and/or overcoating compositions (both compositions can be generally referred to as "protective coating(s)") that are structured in a manner that provides increased stability to the ingredients within the compositions. By way of example, the protective coating(s) can be structured as aqueous dispersions of polymeric adhesive material that include a continuous aqueous phase and a dispersed polymer phase. Additional ingredients such as insecticide(s), photoprotectant(s), and/or surface hardening additive(s) can be incorporated into either the aqueous phase or the dispersed polymeric phase. Notably, this structure can result in durable and stable protective coating(s) that can withstand all types of weather conditions ranging from hot and arid environments, humid environments, temperate environments, and/or cold environments. Stated another way, the protective coating(s) can be used in all types of climate zones (e.g., polar, zones, temperate zones, and tropical zones). Even further, the protective coating(s) can be used on all type of plants in all of the aforementioned environments and climate zones. For example, while plants located in hot arid environments may be preferred plants in the context of the present invention (e.g., palm trees), other types of plants are contemplated in the context of the present invention, a non-limiting list of which is provided below.

[0043] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections with reference to the figures.

A. Protective Coating(s) of the Present Invention

[0044] The protective coating(s) of the present invention can be formed as a single or multilayered structure. The protective coating(s) can be an insecticidal coating and/or an overcoating. The insecticidal coating and/or an overcoating can contain an insecticide, a photoprotectant, an antioxidant, a hydrolysis resistant additive, a surface hardening additive, and/or an aqueous dispersed polymeric adhesive material. The insecticidal coating that contacts the surface of the plant can contain an insecticide, a photoprotectant and/or a surface hardening additive, and an aqueous dispersed polymeric adhesive material. The overcoating can contain a photoprotectant and/or a surface hardening additive and an aqueous dispersed polymeric adhesive material. Still further, both protective coatings can also include an antioxidant and/or a hydrolysis resistant additive.

i. Polymer

[0045] A polymer can be used in the protective coating(s) to retain the insecticide, a photoprotectant, an antioxidant, a surface hardening additive, an antioxidant, and/or a hydrolysis resistant additive, in the protective coating(s). The polymer can also assist in retaining the protective coating(s) on the plant. The polymer can be a polymer dispersed in an aqueous solution (e.g., water). The dispersed polymer can contain polyvinyl acetate, methyl cellulose, polyvinyl alcohol, polyvinylidene chloride, polyacrylics, cellulose, polyvinylpyrrolidone, polysaccharide, natural latex, or synthetic latex, or any combination thereof. The dispersed polymer can be an adhesive material. In a preferred embodiment, the aqueous-dispersed polymeric adhesive material is aqueous-dispersed polyvinyl acetate,

ii. Insecticide

[0046] The protective coating(s) can protect a plant from pests by containing an insecticide. The protective coating(s) can reduce or eliminate the amount of insecticide entering the vascular system of the plant and/or entering the environment around the protective coating(s). The layer which is in direct contact with the surface of the tree can contain a pesticide (for example, an insecticide such as chlorpyrifos or tefluthrin) and minimize or eliminate the amount of pesticide that enters the vascular system of the plant. As the term is used herein, insecticide entering the vascular system of the plant does not include transport of the insecticide into the plant by the pest. For example, a red palm larva weevil that begins burrowing into a palm tree coated with the coatings herein will ingest a lethal dose of the insecticide as the larva burrows through the coating. In some instances, the larva may not be killed by the pesticide in the coating until after having at least partially entered the central cylinder or cortex of the palm tree trunk.

[0047] The insecticide may be any single insecticide or combination of insecticides. Chlorpyrifos is an organophosphate insecticide, chemical name: o,o-diethyl-o-(3,5,6-trichloro- 2-pyridinyl) phosphorothioate). This insecticide is effective at controlling soil and foliage pests. Tefluthrin is a pyrethroid pesticide, chemical name:

(2,3,5,6-tetrafluoro-4-methylphenyl)methyl (lR,3R)-3-[(Z)-2-chloro-3,3,3-trifluoroprop-l- enyl]-2,2-dimethylcyclopropane-l-carboxylate. This insecticide is effective at controlling Coleoptera, Lepidoptera and Diptera. The insecticide(s) can also be carbamates, sodium channel modulators/voltage dependent sodium channel blockers, pyrethroids such as DDT, oxadiazines such as indoxacarb, acetylcholine-receptor agonists/antagonists, acetylcholine - receptor-modulators, nicotine, bensultap, cartap, chloronicotyinyls such as acetamiprid, clothianidin, dinotefuran, imidac loprid, nitenpyram, nithiazine, thiacloprid, and thiamethoxam, spinosyns such as spinosad, cyclodiene organochlorines such as camphechlor, chlordane, endosulfan, gamma-HCH, HCH, heptachlor, lindane, methoxychlor, fiproles such as acetoprole, ethiprole, fipronil, vaniliprole, chloride-channel, 6.1 mectins such as avermectin, emamectin, emamectin-benzoate, ivermectin, and milbemycin, juvenile-hormone mimics such as diofenolan, epofenonane, fenoxycarb, hydroprene, kinoprene, methoprene, pyriproxyfen, and triprene, ecdysone agonists/disruptors, diacylhydrazine, chromafenozide, halofenozide, methoxyfenozide, tebufenozide, chitin biosynthesis inhibitors, benzoylureas such as bistrifluron, chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron, triflumuron, buprofezin, cyromazine, oxidative phosphorylation inhibitors, ATP disruptors, diafenthiuron, organotins such as azocyclotin, cyhexatin, fenbutatin-oxide, pyrroles such as chlorfenapyr, dinitrophenols such as binapacryl, dinobuton, dinocap, DNOC, site -I electron transport inhibitors, METI's such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, hydramethyinon, dicofol, rotenone, acequinocyl, fluacrypyrim, spirodiclofen, spiromesifen, tetramic acids, carboxamides such as flonicamid, octopaminergic agonists such as amitraz, magnesium-stimulated ATPase inhibitors such as propargite, benzenedicarboxamindes (BDCAs) such as flubendiamide (N ² -[l,l-dimethyl-2- (methylsulfony ethy^-S-iodo-N^C -methyl^-fl^^^-tetrafluoro-l-

(trifluoromethyl)ethyl]phenyl]-l,2-benzenedicarboxamide), nereistoxin analogues such as thiocyclam hydrogen oxalate, and thiosultap sodium. Preferably the insecticide is one or more of chlorpyrifos and tefluthrin.

[0048] The insecticides used in the insecticide coatings of the present invention may include biological microorganisms suitable for controlling undesirable animal and plant pests and nuisance pests. Preferred biological microorganism insecticides include all microorganisms (bacteria and fungi) capable of forming resting forms, such as spores or conidia.

[0049] The insecticide can be mixed into the protective coating(s) and/or chemically bonded to an insecticide carrier. The insecticide carrier can be a particulate having an average particle size of less than about 50 to 120 microns. In some instances, the carrier can be talc, attapulgite clay, pyrophyllite, chalk, diatomaceous earth (e.g., kieselguhr), vermiculite, calcium phosphates, calcium and magnesium carbonates, sulfur, flours, and/or other organic and inorganic solids which act as carriers. The insecticide bound to the carrier can then be mixed with the protective coatings of the present invention.

[0050] The insecticide-containing layer can be of a thickness that is sufficient for ingestion of a lethal dose of insecticide by a pest attempting to enter or bore into plant. The thickness of the insecticide-containing layer may vary depending on the concentration of insecticide present therein. In some embodiments, the pesticide-containing layer has a thickness of from 10 μπι to 1 millimeter, preferably from 50 μπι to 950 μπι, from 100 μπι to 900 μπι, 150 μπι to 850 μπι, 200 μιη to 800 μτη, 250 μιη to 750 μτη, 300 μιη to 700 μτη, 350 μιη to 650 μτη, 400 μιη to 600 μηι, 450 μηι to 550 μηι, or about 500 μιη. The thickness of the insecticide- containing layer is an average determined by cross sectional analysis or the use of a thickness gauge such as an Erichsen 455 paint inspection gauge.

[0051] The insecticide-containing layer comprises an insecticidally-effective amount of one or more of the insecticides. The term "insecticidally-effective amount" describes a concentration of insecticide in the insecticide-containing layer sufficient to deliver a lethal and/or repellent dose of insecticide to a pest as it ingests or absorbs a portion of the insecticide- containing layer while feeding on plant coated with the insecticide-containing layer or attempting to burrow into the plant through the insecticide-containing layer. An insecticidally- effective amount is an amount sufficient to kill the pest in one or more of its life cycle forms including pupa, egg, larva, emergent, and/or adult. A repellent-effective amount is an amount that is sufficient for deterring a pest from penetrating the epidermis or cortex of a plant and/or an amount sufficient to deter a pest from depositing an egg thereon.

[0052] The amount of insecticide that is present in the insecticide-containing layer may vary depending on the effectiveness (lethality) of the pesticide.

[0053] The insecticide is effective for preventing and/or treating infestations of numerous pests. Non-limiting examples of pests include insets can include the Coleptera, Lepidoptera Hemiptera, Orthoptera, Isoptera, Diptera, Acarina, and Nematoda insect families. Coleptera family insects can include Rhynchophorus ferrugineus (red palm weevil), Callosobruchus Chinensis (adzuki bean weevil), Sitophilus zeamais (maize weevil), Tribolium castaneum (red flour beetle), Epilachna vigintioctomaculata (large 28-spotted lady beetle), Agriotes fuscicollis (barley wireworm), Anomala rufocuprea (soybean beetle), Leptinotarsa decemlineata, Diabrotica spp., Monochamus alternatus (Japanese pine sawyer), Lissorhoptrus oryzophilus (rice water weevil), Lyctus (powderpost beetle), etc..

[0054] Lepidoptera family insects can include Lymantria dispar (gypsy moth), Malacosoma neustria, Pieris rapae, Spodoptera litura (common cutworm), Mamestra brassicae (cabbage armyworm), Chilo suppressalis (Asiatic rice borer), Pyrausta nubilalis (oriental corn borer), Ephestia cautella, Adoxophyes orana (smaller tea tortrix), Carpocapsa pomonella, Agrotis (cutworm), Galleria mellonella (greater wax moth), Plutella maculipennis (diamondback moth), Heliothis Phyllocnistis citrella, etc.

[0055] Hemiptera family insects can include Nephotettix cincticeps (green rice leafhopper), Nilaparvata lugens (brown rice planthopper), Pseudococcus comstocki (Comstock mealyburg), Unaspis yanonensis (arrowhead scale), Myzus persicae (green peach aphid), Aphis pomi (green apple aphis), Aphis gossypii (cotton aphid), Rhopalosiphum pseuddobrassicas (turnip aphid), Stephanitis nashi (pear lace bug), Nazara spp., Cimex lectularius, Trialeurodes vaporariorum (greenhouse whitefly), Psylla spp. (jumping plantlice), etc. Orthoptera family insects can include Blatella germanica (German cockroach), Periplaneta americana (American cockroach), Gryllotalpa africana (mole cricket), Locusta migratoria migratoriodes, etc.

[0056] Isoptera family insects can include Reticulitermes speratus (Japanese white birch aphid), Coptotermes formosanus (Formosan subterranean termite), and Thysanoptera, such as Thrips palmi karny.

[0057] Diptera family insects can include Musaca domestica (oriental house fly), Aedes aegypti, Hylemia platura (seed-corn maggot), Culex pipiens, Anopheles sinensis, Culex tritaeniorhynchus, etc.

[0058] Acarina family insects can include Tetranychus telarius (carmine spider mite), (tow- spotted spider mite), Panonychus citri (citus red mite), Aculops pelekassi (pink citrus rust mite), Tarsonemus spp. (tarsonemid mites), etc.

[0059] Nematoda family insects can include Meloidogyne incognita (southern root-knot nematode), Bursaphelenchus lignicolus mamiya et kiyohara, Aphelenchoides bessey (rice white-tip nematode), Heterodera glycines (soybean cyst nematode), Pratylenchus spp. (root- lesion nematode), etc.

iii. Surface Hardening Agent

[0060] The insecticidal coating and/or the overcoating can be capable of forming a hardened or durable surface. The protective coating(s) can withstand severe abrasive conditions, such as those of desserts where the coating needs to withstand windblown sand, high humidity, or rain. The insecticidal coating and/or overcoating can contain an additive which enhances the surface hardness of the coating. The presence of a surface hardening additive can enhance the surface hardness of the coating or an overcoating after it is formed on the plant and can improve the durability of the coating. In some instances, the coating is not hardened to the point where the formation of cracks occur upon impact of the coating (indicating a high modulus). The surface hardened coating can have an extended useful life and reduce the frequency of re-applications required.

[0061] Surface hardening additives that can be used in the protective coating(s) include any hardening agent. Non-limiting examples of hardening agent include organic acids, inorganic acids, and mixtures thereof. The surface hardening additive can be sulfuric acid and/or derivatives thereof. Derivatives of sulfuric acid can include sulfonic acids, such as straight or branched chain aliphatic sulfonic acids and/or aromatic sulfonic acids having 1 to 20 carbon atoms. Non-limiting examples of sulfonic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, naphthalenesulfonic acid, ^-toluenesulfonic acid, camphor sulfonic acid, and dodecylbenzenesulfonic acid.

[0062] In some instances, the surface hardening additive can be chlorpyrifos or a derivative thereof, such as an acidic chlorpyrifos derivative. The composition containing chlorpyrifos can have a neutral or a basic pH at the time it is added to the insecticidal coating so that hardening of the insecticidal coating is not induced at the time it is added. The initial amount of chlorpyrifos added to the protective coating(s) can be less than that which is required to induce hardening of the insecticidal coating at the time it is added. The degradation of chlorpyrifos alone or in combination with other surface hardening additives can be sufficient to harden the protective coating(s).

[0063] The protective coating(s) can contain no surface hardening additive other than sulfuric acid, a sulfuric acid derivative, chlorpyrifos, and/or a chlorpyrifos degradation product. In some instances, no acid-based surface hardening additive is added to the protective coating(s). In certain aspects, the protective coating(s) can contain no acid. In some aspects, the protective coating(s) can contain no surface hardening additive when the components of the composition are combined, but the degradation and/or reaction of one or more of the components therein forms a surface hardening additive.

iv. Photoprotectant

[0064] The photoprotectant can be any photoprotectant. The photoprotectant can be an ultraviolet light blocking or absorbing component. In some instances, the photoprotectant is carbon black. In some instances, the photoprotectant is imidazole derivatives, salicylates, triazone derivatives, triazol derivatives, dibenzoylmethanes, amino substituted hydroxybenzophenones, phenyl-benzimidazoles, anthranilates, phenyl-benzoxazoles, 1,4- dihydropyranesacrylates, p-aminobenzoates, camphor derivatives, cinnamates, benzophenones, esters of benzalmalonic acid, esters of 2-(4-ethoxy anilinomethylene)propanedioic, and others, and mixtures thereof.

v. Antioxidant and/or a Hydrolysis Resistant Additive

[0065] Non-limiting examples of antioxidants and hydrolysis resistant additives that can be used in the context of the present invention include citric acid, phosphoric acid, benzoic acid, a combination of citric acid and phosphoric acid, an amino acid, an amino acid derivative, imidazole, an imidazole derivative, a metal-chelator, β-hydroxyacids (e.g., citric acid, lactic acid, malic acid, etc.), huminic acid, gallic acid, gallic extracts, bilirubin, biliverdin, ethylenediaminetetraacetic acid (EDTA), ethylene glycol tetraacetic acid (EGTA), an EGTA derivative, unsaturated fatty acids, derivatives of unsaturated fatty acids (e.g., γ-linoleic acid, linolic acid, oleic acid, etc.), folic acid, derivatives of folic acid, ubiquinone, ubiquinol, a ubiquinone derivative, a ubiquinol derivative, vitamin C, a vitamin C derivative, urea, a urea derivative, mannose, a mannose derivative, zinc, a zinc derivative {e.g., ZnO and/or ZnS0 ₄ ), selen, a selen derivative {e.g., selenomethionin), a stilbene, a stilbene derivative {e.g., stilbenoxide and trans-stilbenoxide), and any combination or derivative thereof.

[0066] In some instances, the coating may contain other stabilizing additives as well.

B. Method of Making Protective Coating(s)

[0067] The protective coating(s) can be made by combining all or some of the components of the protective coating(s) and mixing. The polymer and water can be combined with all, some, or none of the additives, such as an insecticide, a photoprotectant, an antioxidant, a hydrolysis resistant additive, and/or a surface hardening additive, and mixed. If additives are included, the additives can then be added to the mixture and mixed. Mixing can be performed by any means known, such as stirring, vortexing, homogenizing, shaking, etc.

[0068] The protective coating(s) can be applied to a plant by any means, such as painting, spraying, dip coating, pouring, etc.

[0069] The protective coating(s) can be dried and/or cured by any means, including air drying, blowing air, applying a hardening activator, exposing to conditions that activate hardening, etc. During drying, the aqueous phase of the protective coating composition can evaporate. Additives that were solubilized or dispersed in the aqueous phase can be dispersed in the polymers after drying.

C. Use of Protective Coating(s)

[0070] The protective coating(s) can be used to protect a plant from a pest. The protective coating(s) can be used as a coating that directly contacts a surface of the plant and/or directly contacts the surface of one or more underlying layer(s) between the protective coating(s) and the plant. In some instances, the protective coating(s) are used as a single layer and/or a first layer contacting a surface of a plant and an overcoating for the first layer. The first layer and the overcoating can be different protective coating compositions.

[0071] Non-limiting examples of plants that can benefit from the protective coating(s) of the present invention include vines, trees, shrubs, stalked plants, ferns, etc. The plants may include orchard crops, vines, ornamental plants, food crops, timber, and harvested plants. The plants may include Gymnosperms, Angiosperms, and/or Pteridophytes. Gymnosperms may include plants from the Araucariaceae, Cupressaceae, Pinaceae, Podocarpaceae, Sciadopitaceae, Taxaceae, Cycadaceae, and Ginkgoaceae families. Angiosperms can include plants from the Aceraceae, Agavaceae, Anacardiaceae, Annonaceae, Apocynaceae, Aquifoliaceae, Araliaceae, Arecaceae, Asphodelaceae, Asteraceae, Berberidaceae, Betulaceae, Bignoniaceae, Bombacaceae, Boraginaceae, Burseraceae, Buxaceae, Canellaceae, Cannabaceae, Capparidaceae, Caprifoliaceae, Caricaceae, Casuarinaceae, Celastraceae, Cercidiphyllaceae, Chrysobalanaceae, Clusiaceae, Combretaceae, Cornaceae, Cyrillaceae, Davidsoniaceae, Ebenaceae, Elaeagnaceae, Ericaceae, Euphorbiaceae, Fabaceae, Fagaceae, Grossulariaceae, Hamamelidaceae, Hippocastanaceae, Illiciaceae, Juglandaceae, Lauraceae, Lecythidaceae, Lythraceae, Magnoliaceae, Malpighiaceae, Malvaceae, Melastomataceae, Meliaceae, Moraceae, Moringaceae, Muntingiaceae, Myoporaceae, Myricaceae, Myrsinaceae, Myrtaceae, Nothofagaceae, Nyctaginaceae, Nyssaceae, Olacaceae, Oleaceae, Oxalidaceae, Pandanaceae, Papaveraceae, Phyllanthaceae, Pittosporaceae, Platanaceae, Poaceae, Polygonaceae, Proteaceae, Punicaceae, Rhamnaceae, Rhizophoraceae, Rosaceae, Rubiaceae, Rutaceae, Salicaceae, Sapindaceae, Sapotaceae, Simaroubaceae, Solanaceae, Staphyleaceae, Sterculiaceae, Strelitziaceae, Styracaceae, Surianaceae, Symplocaceae, Tamaricaceae, Theaceae, Theophrastaceae, Thyme laeaceae, Tiliaceae, Ulmaceae, Verbenaceae, and/or Vitaceae family. In some instances, the plant protected is a palm tree. Palm trees may include coconut palm (Cocos nucifera), oil palm (Elaeis guineensis), Areca catechu, Arenga pinnata, Borassus flabellifer, Calamus merillii, Cargota maxima, Cargota cumingii, Corypha gebanga, Corypha elata, Livistona decipiens, Metroxglon sagu, Oreodoxa regia, Phoenix sylvestris, Sabal umbraculifera, Trachycarpus fortunei, Washingtonia spp., and other palm like plants such as Agave Americana, Saccharum qfficinarum, and Chamaerops humilis (known as Mediterranean dwarf Palm). In some aspects of the present invention, preferred plants for protection from pests include palm trees selected from Phoenix dactylifera or Phoenix canariensis.

EXAMPLES

[0072] The following examples are included to demonstrate preferred embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention. Example 1

(Surface Hardened Insecticidal Coatings)

[0073] Production. An insecticidal coating composition containing polyvinyl acetate (VINAVIL® (Vinavil S.p.A, Italy) glue with the water content of 60%) and master-batch of chlorpyrifos anchored onto inorganic fillers in water was prepared to test the durability of the coating in comparison to a similar coating that did not contain chlorpyrifos. The composition was prepared by vortexing the composition for 5 min, followed by shaking for 2 h. The master- batch of chlorpyrifos appeared uniformly dispersed within the formulation. The uniform dispersion was applied onto glass substrates using a doctor blade set-up and dried at room temperature over 2 days to ensure the complete evaporation of the water and a uniform coating (thickness of about 120 microns). In comparison, a control coating composition the same as that above, but without master-batch of chlorpyrifos anchored onto inorganic fillers was made and similarly applied onto a glass substrate to form a uniform coating. The control coating appeared uniform upon visual inspection after the complete evaporation of water.

[0074] Characterization. The coating samples with and without chlorpyrifos were subjected to similar accelerated weathering conditions to infer their physical properties. Weathering exposure was carried out in a Ci5000 weatherometer from Atlas Material Testing Groups. Two different accelerated weathering conditions were selected for this study. The first test conditions as per ISO 4892-2A, used an irradiation level of 0.51 W/m2 @ 340 nm optical filter, BST (Black Standard Temperature) was 65 °C, the RH (Relative Humidity) was 50%), and the specimen was sprayed for 18 mins at every 120 mins. The second test conditions used an irradiation level of 0.51 W/m2 @ 340 nm optical filter, BST (Black Standard Temperature) was 65 °C, and the RH (Relative Humidity) was 70%> with continuous light and no specimen spray.

[0075] The coating which contained master-batch of chlorpyrifos anchored onto inorganic fillers (working example- 1) was found to be slightly harder than that of the control coating without master-batch of chlorpyrifos (control- 1), as evidenced from the preliminary imaging measurements and physical touch. Not to be bound by theory, the observed enhanced surface hardness of the working example- 1 may be related to the presence of inorganic fillers and/or to the crosslinking of the binder in the presence of small quantities of the by-products derived from the degradation of the chlorpyrifos. Such cross-linking of the binder seems to be continued and/or augmented under the accelerated weathering conditions, leading to further enhanced hardness of the coating. It is clear that such crosslinking and hardening of the VINAVIL® glue binder does not occur under similar weather conditions in the absence of master-batch of chlorpyrifos anchored onto the inorganic fillers in the coating (control-1).

[0076] FIG. 1 shows the effect of accelerated weathering on glue coatings with or without chlorpyrifos at 0 hours (h) and 200 h exposure. In particular, and with reference to FIG. 1, the effect of accelerated weathering at 70% relative humidity (RH) on glue coating is shown for: A) glue without chlorpyrifos at 0 h exposure; B) glue without chlorpyrifos at 200 h exposure; C) glue with chlorpyrifos at 0 h exposure; D) glue with chlorpyrifos at 200 h exposure. Glue coating in absence of chlorpyrifos undergoes some surface erosion due to the intense weathering conditions at 200 h as shown by defects on the surface. However in presence of chlorpyrifos, the surface erosion of the coating is not very significant.

[0077] FIG. 2 shows the effect of accelerated weathering with water spray on glue coatings with our without chlorpyrifos at 0 h and 200 h exposure. In particular, and with reference to FIG. 2, the effect of accelerated weathering with water spray and 30% RH on glue coating is shown for: A) glue without chlorpyrifos at 0 h exposure; B) glue without chlorpyrifos at 200 h exposure; C) glue with chlorpyrifos at 0 h exposure; D) glue with chlorpyrifos at 200 h exposure. Again, the presence of chlorpyrifos reduces the surface erosion. A similar observation is made while immersing in water the coating samples containing chlorpyrifos in polyvinyl acetate (working example-2) and the polyvinyl acetate alone (control-2). While the control-2 coating can be easily wiped-off (with the finger), the working example-2 coating could not be removed easily/completely. Moreover, both working example- 1 and 2 coatings were found to have strong adhesion onto the glass, as compared to control-1 and 2 samples. These observations indicate that the presence of chlorpyrifos helps in stabilizing the coatings.

[0078] Further, polyvinyl acetate (PVAc) which contains chlorpyrifos shows an increase in polydispersity. Not to be bound by theory, this may be due to the chain incision and also increased branching of the PVAc. FIG. 3 shows the effect of accelerated weathering on PVAc polydispersity from 0 to 648 h of accelerated weathering for the control and the films containing chlorpyrifos. FIG. 4 shows the effect of accelerated weathering on the polydispersity of PVAc until 350 h of accelerated weathering for the control and the films containing different pesticides, including tefluthrin, and high and low concentrations of chlorpyrifos. These observations indicate that polydispersity is increased over time for PVAc containing chlorpyrifos. Accordingly, chlorpyrifos can be used to harden a surface in a first coating, or any one or more layers of a multi-layer coating, such as in an overcoating. Example 2

(Insecticidal Coatings with a Pigment/UV Additives)

[0079] Production. A pigment additive(s) (for example, carbon black as a pigmnet, a light stabilizer (CHIMASSORB® 944, BASF, U.S.A.), a light absorber (CYASORB CYNERGY SOLUTIONS® 5411, Cytec Sovay Group, U.S.A.), etc.) was incorporated into a different coating composition to determine if it protected chlorpyrifos from photodegradation. Not to be bound by theory, it is believed that pigment additives that are known to absorb the sun light efficiently would protect chlorpyrifos from degradation by sunlight. For example, a UV stabilizer can filter out the UV light that is harmful to the pesticide before (PZ)* has had a chance to form (See, FIG. 5). It was shown that the pigment additive can work efficiently in coating compositions even a low concentrations (for example, ~ 1% by weight of total solid content of the whole formulation). It was observed that most of the pesticides remained intact within the coating even after exposed to accelerated weathering conditions, as compared to the control coating composition which does not contain any pigment additive.

[0080] The procedure used to prepare the pesticide formulation with and without a pigment or UV additive was as follows. The required amount of polyvinyl acetate (VINAVIL® glue) and water (see Table 1) was mixed in a plastic vial, vortexed for 5 min, and then shaken for 1 hour. A pesticide masterbatch (7.5% of chlorpyrifos, particle size 53 to 120 micron) and pigment additives 0% to 5% of total solid content were then added. The mixture was shaken for 2 hours and then further vortexed for uniform mixing. The pigment additive and the master- batch of chlorpyrifos appeared uniformly dispersed within the mixture and the uniform dispersion was applied onto glass plates to prepare coated samples for testing under accelerated weathering conditions. The mixture was spread on to the glass plates (75mm long x 25 mm width x 1mm thick) to produce a polymeric films by using an automatic film applicator and a doctors blade. The prepared polymeric film was air dried for two days or until all the water evaporated. The coated samples visually appeared uniform after the complete evaporation of water. A control coated sample was similarly prepared that did not contain a pigment additive. The coating mixtures were prepared as shown in Table 1.

Table 1

Weight of ingredient s in various coatings ( ;g)

Ingredients Control Carbon Black, <500 CHIMASSORB® CYASORB nm mesoporous 944 ® 5411

VINAVYL® glue 11 11 11 11

Water 6 6 6 6

[0081] Characterization. The control and test coatings were subjected to similar accelerated weathering conditions. Weathering exposure was carried out in a Ci5000 weatherometer from Atlas Material Testing Groups. Two different accelerated weathering conditions were selected for this study. The first test conditions as per ISO 4892-2A, used an irradiation level of 0.51 W/m2 @ 340 nm optical filter, BST (Black Standard Temperature) was 65 °C, the RH (Relative Humidity) was 50%, and the specimen was sprayed for 18 mins at every 120 mins. The second test conditions used an irradiation level of 0.51 W/m2 @ 340 nm optical filter, BST (Black Standard Temperature) was 65 °C, and the RH (Relative Humidity) was 70% with continuous light and no specimen spray.

[0082] The samples were withdrawn from the weathering chambers every 50 hours to infer the residual pesticide in the coating sample. For this purpose, the residual pesticides were extracted from the coating sample by a standard extraction procedure and analyzed by HPLC. FIG. 6 shows the residual pesticide as a function of time of accelerated weathering plotted to understand the efficacy of pigment additive towards protecting the chlorpyrifos from the photodegradation. As shown in FIG. 6, the amount of remnant pesticide mostly remained intact in the coating composition which contained the carbon black, as compared to the blank control coating sample i.e. without carbon black. Other pigment additives like CHIMASSORB® 944 (poly((6-((l,l,3,3-tetramethylbutyl)amino)-l,3,5-triazine-2, 4-diyl)((2,2,6,6-tetramethyl-4- piperidinyl)imino)-l,6-hexanediyl((2,2,6,6-tetramethyl-4-pip eridinyl)imino))) and CYASORB® 5411 (2-(2H-l,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-y l)phenol) were also investigated. As shown in Table 2, All additives shows good performance in keeping the remnant pesticide for longer period of time over blank polymer composition. The carbon black containing polymer composition shows better performance than CHIMASSORB® 944 and CYASORB® 5411. Among the additives tested the efficacy of performance was in the following order: Carbon black > CHIMASSORB® 944 > CYASORB® 5411 (FIG. 6). These lab-scale results demonstrate that the incorporation of the pigment additives such as carbon black significantly improves the stability of chlorpyrifos in the coating composition.

[0083] Briefly, the coatings were tested by loading each glass plate coated with polymeric composition into an accelerated weathering chamber. The samples were withdrawn every 50 hours from the weathering chamber, extracted, and analyzed for the residual amount of pesticide by HPLC. The results are shown in Fig. 6 and Table 2.

Table 2

Comparison of Remnant Pesticide in Weathered Polymeric Composition (weight %)

CYASORB® 5411

Example 3

(Insecticidal Coatings with Antioxidants and/or Hydrolysis Resistant Additives)

[0084] Production. Various additives, including antioxidants (such as phosphoric acid, benzoic acid, citric acid, ascorbic acid, etc), hydrolysis resistant additives, and their mixtures were added to coating formulations of aqueous dispersion of polyvinyl acetate, master-batch of chlorpyrifos anchored onto inorganic fillers, and water. A typical loading of the antioxidant was about 0.5 - 1% by weight of total solid content in the whole formulation. The additive can be either liquid or solid. It was demonstrated that these additives did not adversely affect the stability of the pesticide.

[0085] Briefly, the coatings were produced by mixing the required amount of polyvinyl acetate (VINAVIL® glue) and water in a plastic vial by vortexing for 5 min and then shaking for 1 h. A pesticide masterbatch (7.5% of chlorpyrifos, particle size 53 to 120 micron) and antioxidant additives 0% to 5% of total solid content were mixed in the coating mixture by shaking for 2 h and vortexing for uniform mixing. The additive and the master-batch of chlorpyrifos appeared to be uniformly dispersed within the mixtures. The mixtures were then spread on to glass plates (75 mm long x 25 mm width x 1 mm thick) to produce polymeric films by using an automatic film applicator with a doctors blade. The prepared polymeric film was air dried for two days or until all the water evaporated. The coated samples visually appeared uniform after the complete evaporation of water. The coating mixtures were prepared as shown in Table 3.

Table 3

Weig tit of ingredier its in varioi is coatings (g)

Ingredients Control Citric Phosphoric Benzoic citric acid + acetic acid acid acid phosphoric acid acid

VINAVYL® glue 11 11 11 10 10 11

[0086] Characterization. The control and test coatings were subjected to similar accelerated weathering conditions. The samples were withdrawn from the weathering chambers every 50 h to determine the residual pesticide in the coating sample. The residual pesticides were extracted from the coating sample by a standard extraction procedure and analyzed by HPLC.

[0087] FIG. 7 is a plot of the residual pesticide as a function of time of exposure to accelerated weathering. The plot demonstrates the efficacy of the stabilizing additive towards protecting the chlorpyrifos from the degradation. As shown in the FIG. 7 and in Table 4, all additives showed good performance in keeping the remnant pesticide for longer period of time over blank polymer composition, with antioxidants retaining higher amounts of pesticide as compared to the control coating sample without any antioxidant. In comparison, the citric acid containing polymer composition shows better performance than the remaining additives (FIG. 7).

[0088] These lab-scale results demonstrate that the incorporation of the stabilizing additives such as antioxidant significantly improves the stability of chlorpyrifos in the coating composition.

Table 4

Comparison of remnant pesticide in weathered polymeric composition in weight %

C = Chlorpyrifos i.e., control; Al = citric acid; A2 = phosphoric acid; A3 = Benzoic acid; A4 = citric acid + phosphoric acid; A5 = acetic acid.

Example 4

(Two Layered Protective Coatings)

[0089] Production. A first coating containing polyvinyl acetate (VINAVIL® glue with the water content of 60%) and either tefluthrin or master-batch of chlorpyrifos anchored onto inorganic fillers was produced. A second coating that can block or absorb ultraviolet light was applied to the first coating to produce a two layered protective coating. The second coating contained polyvinyl acetate (VINAVIL® glue). The second coating can block or absorb ultraviolet light by itself or may optionally contain light absorbing additives. The coatings were tested for their ability to protect the chlorpyrifos or from photodegradation.

[0090] A coating mixture was produced by mixing the required amount of polyvinyl acetate (VINAVIL® glue) and water in a plastic vial by vortexing for 5 min and then shaking for 1 h. Zelig (pesticide master-batch, 0.2% of tefluthrin, particle size 53 to 120 micron) or master-batch of chlorpyrifos was mixed in the coating mixture by shaking for 2 h and vortexing to achieve uniform mixing. The additive and the master-batch tefluthrin or chlorpyrifos appeared to be uniformly dispersed within the mixtures. The mixtures were then spread on to glass plates (75 mm long x 25 mm width x 1 mm thick) to produce a first layer of a polymeric film by using an automatic film applicator with a doctor blade. The prepared polymeric film was air dried for two days or until all the water evaporated. The coated samples visually appeared uniform after the complete evaporation of water. The dried coatings were uniform with a thickness of about 120 microns.

[0091] The second layer was applied on the top of the dry first layer using a wire-bar setup and dried for another 2 days. The thickness of the overcoat was about 30 microns. The greater thickness of the first layer can be attributed to the higher loading of VINAVIL® glue (70%) and the presence of master-batch of chlorpyrifos. In comparison, the second layer formulation used a relatively diluted aqueous dispersion (loading of VINAVIL® glue about 50%). No visual disintegration of first layer was evident when aqueous dispersion of VINAVIL® glue was applied on the top. The coated samples appeared uniform after complete evaporation of water.

[0092] Characterization. The glass plates with the two layered protective coatings were tested under accelerated weathering conditions. A control coated sample was also prepared without the second overcoat layer, under similar conditions and subjected to similar accelerated weathering conditions. The samples were withdrawn from the weathering chambers after specific time intervals to determine the residual pesticide in the samples. The residual pesticides were extracted from the coating sample by a standard extraction procedure and analyzed by HPLC.

[0093] The residual pesticide as a function of time of accelerated weathering was plotted to understand the efficacy of the overcoat in protecting the chlorpyrifos (FIG. 10) and tefluthrin (FIG. 1 1) from the photodegradation and other degradation pathways (for example, oxidation and hydrolysis). FIG. 8 and FIG. 9 also show the amount of degradation of a higher concentration of chlorpyrifos (-2.6%) and a lower concentration of chlorpyrifos (-1.6%) at each tested time period for up to 200 hours. In these experiments, the starting concentration of the pesticide (chlorpyrifos or tefluthrin) in the overcoated samples was less than the starting concentration in the non-overcoated samples, as shown in FIG. 10 and FIG. 11, due to the addition of an overcoating that did not contain pesticide. The first layer coating contained the same amount of pesticide. There was no evidence that the addition of the overcoating itself decreased the amount of pesticide in the first layer coating. The results demonstrate that the bilayer coating samples retained a higher percent of the starting amount of pesticide after exposure to accelerated weather conditions than the control coating samples, which did not contain an overcoat. Not to be bound be theory, it is believed that the filtering effect of the overcoat layer to sunlight provided protection for the pesticide. Polyvinyl acetate (PVAc) has an absorption in the UV region (Liu et al., Progress in Photovoltaics Research and Applications 2013; 21(4): 668-675) and an overcoating containing PVAc, or other UV blocking or absorbing components, will cut off some amount of UV light which can reduce the degradation of the pesticide.

[0094] In addition, images of the overcoated samples and the control single layer coatings showed that the surface erosion of the overcoated samples is reduced in comparison to the single-layer control coatings (FIG. 12).

[0095] These lab-scale results demonstrate that the presence of overcoat on the top of the first layer significantly improves the stability of a pesticide in the first layer.