CN110691513A - Pesticide - Google Patents

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CN110691513A
CN110691513A CN201880029323.XA CN201880029323A CN110691513A CN 110691513 A CN110691513 A CN 110691513A CN 201880029323 A CN201880029323 A CN 201880029323A CN 110691513 A CN110691513 A CN 110691513A
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nanoemulsion
pesticide
oil
horticultural
solvent
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张英顺
布鲁克·C·莫菲
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Agricultural Insurance Technology Private Ltd
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Agricultural Insurance Technology Private Ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/02Biocides, 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 liquids as carriers, diluents or solvents
    • A01N25/04Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N63/00Biocides, pest repellants or attractants, or plant growth regulators containing microorganisms, viruses, microbial fungi, animals or substances produced by, or obtained from, microorganisms, viruses, microbial fungi or animals, e.g. enzymes or fermentates

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  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • Virology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to a pesticide nanoemulsion comprising: (a) horticultural oils as active ingredients; (b) a mixture of inert ingredients comprising: (i) an emulsifier; (ii) a stabilizer; and (iii) a surfactant; and (c) a solvent, wherein the horticultural oil is dispersed in the solvent in the form of droplets to form the nanoemulsion. Preferably, the droplets have an average size of 50-350 nm or 100-250 nm. In other embodiments, the inert ingredient mixture further comprises a binder, or the horticultural oil may be soybean oil or palm oil. In another embodiment, the amount of the horticultural oil is 45.0% w/w of the pesticidal nanoemulsion and the concentration of the inert ingredient mixture is 55.0% w/w of the pesticidal nanoemulsion. Preferably, the pesticide nanoemulsion is adapted to be diluted from about 100-fold to 800-fold to form a dilute pesticide nanoemulsion, wherein the concentration of the horticultural oil ranges from 0.056% to 0.45% v/v of the dilute pesticide nanoemulsion.

Description

Pesticide
Cross Reference to Related Applications
The present application claims the benefit of singapore patent application No. 10201703634R filed on 5, 3, 2017.
Technical Field
The invention relates to a pesticide. Specifically, the present invention relates to an oil-based pesticide formulation and an oil-based pesticide adjuvant for use on plants and soil.
Background of the prior art
The following discussion of the background to the invention is intended only to facilitate an understanding of the present invention. It should be appreciated that the discussion is not an acknowledgement or admission that any of the material referred to was published, known or part of the common general knowledge of the person skilled in the art at the priority date of the invention.
Damage to agricultural produce (e.g., fruits and vegetables) by pests results in losses of about 30% of the crop in the united states and as much as 50% of the crop worldwide. Crop losses are mainly caused by insect pest damage and plant diseases. Furthermore, insects may also act as vectors for bacterial or viral plant diseases. Therefore, there is a need to develop and use pesticides to prevent crop loss.
Chemical pesticides have been developed and are typically formulated as solid compositions such as water dispersible granule compositions and wettable powder compositions. Conventional solid compositions comprise an active compound, a mineral carrier, and a wetting and/or dispersing agent (see, e.g., U.S. patent No. 6,093,682, U.S. patent No. 5,595,749, U.S. patent No. 4,804,399). The pesticidal active ingredient is also delivered in solid carriers such as kaolin, chalk, limestone, sodium and potassium aluminium silicates, corn flour, sawdust, cellulose powder, activated charcoal and the like. However, such compositions often leave toxic residues which may have long-term effects on humans and the environment.
Thus, liquid pesticides have been developed to overcome some of the disadvantages of solid pesticides. However, due to solubility limitations, liquid pesticides may be limited in the number and amount of components that may be present in the liquid pesticide composition. The inability to have a high percentage of certain components dissolved in the liquid pesticide composition is a major disadvantage. Furthermore, there may be incompatibilities between the different components, which in turn makes it difficult to manufacture or to store for long periods of time.
Concentrated liquid pesticide compositions are advantageous because the high cost of shipping large volumes can be minimized. However, concentrated liquid pesticides may have phase stability problems because solid components may precipitate out or settle, or liquid components may form separate liquid phases. Accordingly, there is a need to develop a concentrated liquid pesticide that can effectively kill pests and exhibit improved phase stability over conventional concentrated liquid pesticides even when diluted prior to use.
In addition, high percentages of certain components (e.g., oil) can cause clogging of the spray equipment, uneven and problematic application, and reduce the efficiency of the application machinery. Importantly, crop damage can occur due to the use of high percentages of certain components. Therefore, there is a need to develop a liquid pesticide which can effectively kill pests and avoid the above-mentioned problems.
Therefore, there is a need in the art for a pesticide that ameliorates the above-mentioned problems.
The present invention seeks to solve and/or ameliorate the problems of the prior art by providing an oil-based pesticide formulation and oil-based pesticide adjuvant that is capable of controlling plant pests.
Summary of The Invention
According to one aspect of the present invention, there is provided a pesticide nanoemulsion comprising: (a) horticultural oils as active ingredients; (b) a mixture of inert ingredients comprising: (i) an emulsifier; (ii) a stabilizer; and (iii) a surfactant; and (c) a solvent, wherein the horticultural oil is dispersed in the solvent in the form of droplets to form the nanoemulsion.
In some embodiments, the droplets comprise an average size in the range of 50nm to 350 nm.
In some embodiments, the droplets comprise an average size in the range of 100nm to 250 nm.
In some embodiments, the concentration of the stabilizer ranges from 0.5% to 5.0% w/w of the pesticide nanoemulsion.
In some embodiments, the inert ingredient mixture further comprises a binder at a concentration ranging from 0.25% to 3.00% w/w of the pesticide nanoemulsion.
In some embodiments, the horticultural oil is present in a concentration range of less than 90% w/w of the pesticidal nanoemulsion.
In some embodiments, the concentration of the horticultural oil ranges from 20.0% to 70.0% w/w of the pesticidal nanoemulsion and the concentration of the inert ingredient mixture ranges from 30.0% to 80.0% w/w of the pesticidal nanoemulsion.
In some embodiments, the amount of the horticultural oil is 45.0% w/w of the pesticidal nanoemulsion and the concentration of the mixture of inert ingredients is 55.0% w/w of the pesticidal nanoemulsion.
In some embodiments, the concentration of the emulsifier ranges from 0.1% to 10.0% w/w of the pesticide nanoemulsion.
In some embodiments, the surfactant concentration ranges from 0.5% to 30.0% w/w of the pesticide nanoemulsion.
In some embodiments, the solvent is at least 0.25% w/w of the pesticide nanoemulsion.
In some embodiments, the solvent comprises a first solvent and a second solvent, wherein the first solvent is water and the second solvent is at least 0.25% w/w of the pesticide nanoemulsion.
In some embodiments, the pesticide nanoemulsion is adapted to be diluted from about 100-fold to 800-fold to form a diluted pesticide nanoemulsion.
In some embodiments, the concentration of the horticultural oil ranges from 0.056% to 0.45% v/v of the dilute pesticide nanoemulsion.
In some embodiments, the concentration of the stabilizer ranges from 0.001% to 0.017% v/v of the dilute pesticide nanoemulsion.
In another aspect of the invention, there is a pesticide formulation comprising an effective amount of at least one pesticide and an adjuvant nanoemulsion comprising the following components: (a) horticultural oils as active ingredients; (b) a mixture of inert ingredients comprising: (i) an emulsifier; (ii) a stabilizer; and (iii) a surfactant; and (c) a solvent, wherein the horticultural oil is dispersed in the solvent in the form of droplets to form the adjuvant nanoemulsion.
Brief description of the drawings
The invention will now be described, by way of example only, with reference to the accompanying drawings, in which:
figures 1A and 1B show the efficacy results of a formulation of an embodiment of a pesticide according to the present invention comprising the following two amounts, as compared to an existing pesticide in an amount of 7.0 fluid ounces (fl.oz)/25 gallons (gal), on spider mite eggs (figure 1A) and spider mite adults and larvae (figure 1B), respectively: (a) a quantity of 4.8 fluid ounces/25 gallons, (b) a quantity of 9.75 fluid ounces/25 gallons; fig. 1A shows the average spider mite egg count per tomato leaf versus the number of Days After Treatment (DAT). Pesticide 1 exhibited a significant egg number reduction at both dilution rates relative to the untreated control on all days except DAT 14. Pesticide 1 also showed comparable control to the industry standard pesticide C1-C2 on all dates except DAT28, with pesticide 1 maintaining a significantly lower egg count; figure 1B shows the average spider mite adult and young insect number per tomato leaf versus the number of Days After Treatment (DAT). Pesticide 1 exhibited a significant egg number reduction at both dilution rates on all days relative to the untreated control. Pesticide 1 also showed no significant difference compared to the industry standard pesticides C1-C2 on all days.
Detailed Description
Specific embodiments of the present invention will now be described with reference to the accompanying drawings. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. Other definitions of selected terms used herein may be found in the detailed description of the invention and applied throughout this specification. In addition, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.
In this specification, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.
Furthermore, in this specification, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.
As used herein, the term "about" generally means +/-5% of the stated value, more typically +/-4% of the stated value, more typically +/-3% of the stated value, more typically +/-2% of the stated value, even more typically +/-1% of the stated value, and even more typically +/-0.5% of the stated value.
In the present invention, certain embodiments may be disclosed in a scope format. It is to be understood that the description of the range format is merely for convenience and brevity and should not be construed as a limitation on the scope of the disclosure. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, a description of a range such as 1 to 6 should be considered to have specifically disclosed sub-ranges such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., as well as individual values within that range, such as 1, 2, 3, 4, 5, and 6. Ranges are not limited to integers and may include decimal measurements, as applicable. Regardless of the breadth of the range.
As used herein, the term "concentrate" refers to a formulation that can be diluted to form a use solution. For example, the concentrate may be easier and cheaper to transport than a dilute solution.
As used herein, the term "highly concentrated formulation" refers to a formulation that requires significant dilution so that the appropriate desired dosage/use concentration can be achieved.
As used herein, the terms "emulsion" and "nanoemulsion" are used interchangeably and refer to a mixture of two immiscible substances. One material (the dispersed phase) may be dispersed in the other material (the continuous phase). For example, it will be appreciated that in the pesticidal formulations of the present invention, the horticultural oil is present as tiny droplets (which include, but are not limited to, micro and nano droplets) or micelles dispersed in a solvent, wherein the oil and solvent are immiscible with each other. The oil droplets may be uniformly and homogeneously distributed in the solvent, but it will be appreciated that the oil droplets may be non-uniformly distributed in the solvent, for example when the pesticide emulsion is allowed to stand for a considerable period of time. As used herein, the term "nanoemulsion" refers to emulsions having oil droplets in the size range of about 50nm to about 400 nm.
The present invention relates to a pesticide formulation, which may be liquid, for plants and/or soil, which provides a physical mode of action. The various components of the pesticide formulation may be multifunctional. For example, the particular components may be emulsifiers and binders; or stabilizers and emulsifiers. As an example, the polysaccharide or derivative thereof may be both a stabilizer and an emulsifier, and thus are considered two inert ingredients for the purposes of the present invention. Thus, the present invention is useful for controlling the growth and spread of pests and plant diseases. Examples of pests that can be controlled and/or eliminated by the pesticide formulations of the present invention include, but are not limited to, insects (e.g., mosquitoes, flies, wasps, ants, bed bugs, locusts, grasshoppers, aphids, stinkbugs, citrus rust mites, spider mites, pelagic and mealybugs, pink beetles, whiteflies, leaf rollers, leaf miners, gnats, nematodes, gnats, thrips), fungi, or combinations thereof. Plant diseases include, but are not limited to, leaf blight, silver rot, and powdery mildew.
One aspect of the present invention is a pesticide nanoemulsion comprising: (a) horticultural oils as active ingredients; (b) a mixture of inert ingredients comprising: (i) an emulsifier; (ii) a stabilizer; and (iii) a surfactant; and (c) a solvent, wherein the horticultural oil is dispersed in the solvent in the form of droplets to form the nanoemulsion. The droplets may have an average size in the range of about 2 nanometers (nm) to about 400 nm. In the present invention, horticultural oils are not carriers, for example carriers for other active ingredients. Surprisingly, the inventors have found that other active ingredients are not necessary, as horticultural oils are found to be effective active ingredients even at relatively low concentrations. The term "relatively low concentration" refers to a horticultural oil concentration that is lower than prior art horticultural oil-based pesticides, which typically comprise horticultural oil at a concentration ranging from about 90% to 98% w/w of the formulation. In addition, no or negligible toxic residue remains. Thus, the horticultural oil-based pesticides of the present invention have low toxicity and low impact on non-target beneficial insects, humans and the environment. In contrast, prior art pesticides often leave toxic residues that may have long-term effects on humans and the environment. Depending on the application and need, the pesticide nanoemulsion may be diluted prior to use, or may be used directly as a concentrated formulation (i.e., "concentrate"). Advantageously, the pesticide nanoemulsion is phase stable and can kill pests at least as well as known pesticides. Preferably, the horticultural oil droplets and the solvent are immiscible with each other. The oil droplets are adapted to associate and/or interact with emulsifiers, stabilizers, surfactants and/or other components of the pesticide nanoemulsion to form micelles. It will be appreciated that if the horticultural oil comprises both hydrophobic and hydrophilic groups, the horticultural oil may itself form micelles which are also suitable for association and/or interaction with the emulsifier, stabiliser, surfactant and/or other components in the pesticidal nanoemulsion. Thus, the term "droplet" as used throughout this specification includes, but is not limited to, a micelle.
In some embodiments, the horticultural oil used contains little to no volatile organic compounds and the primary mode of action is death by asphyxiation of arthropod and plant pathogens, where the physical action of the oil is the active ingredient, as the oil coat prevents respiration and kills pests. Examples of oils containing little to no volatile organic compounds include, but are not limited to, vegetable oils such as olive oil, soybean oil, palm oil, cottonseed oil, corn oil, coconut oil, peanut oil, and rapeseed oil.
In some embodiments, the droplets have an average size of about 50nm to about 400nm, about 50nm to about 350nm, about 50nm to about 300nm, about 50nm to about 250nm, about 50nm to about 200nm, about 50nm to about 150nm, about 100nm to about 350nm, about 100nm to about 300nm, about 150nm to about 350nm, about 150nm to about 250nm, about 200nm to about 350nm, about 250nm to about 350nm, and even more preferably about 100nm to about 250 nm. The small oil droplet size facilitates effective penetration of insect pests while at the same time reducing phytotoxicity in plants, since the droplets do not block the stomata. The uniform distribution of the oil can also be maintained without agitation for a longer period of time. Stable formulations with uniform oil distribution provide greater efficacy against pests than known oil pesticide products, even when the oil of the present invention is at a lower concentration than known pesticide formulations. At the same time, problems such as clogging of the spraying equipment, uneven and problematic application, reduced efficiency of the application machinery and crop damage can be reduced or avoided.
Advantageously, the pesticides of the present invention provide a physical mode of action whereby an oil layer can form on the plant and suffocate pests and/or interfere with or destroy their normal biological and/or physiological functions. More advantageously, the pests will not be likely to develop resistance to the horticultural oil-based pesticides of the present invention. More advantageously, the horticultural oil-based pesticides of this invention have low toxicity and low impact on non-target beneficial insects due to the minimization or absence of any residual effects of the formulation of this invention. Thus, the pesticides of this invention can selectively target pests with minimal or no harm to beneficial insects.
The above-mentioned advantages result from the nanoemulsification of horticultural oils which are present in pesticides as active ingredients in order to kill pests. In particular, when the pesticide is sprayed on a plant, such as a plant surface, the nanoemulsion may improve the delivery and distribution of small oil droplets, as the relatively small size of the droplets as described above significantly increases the number of small droplets, which in turn increases the probability of the horticultural oil contacting the pest. Horticultural oils, when contacted by pests, can suffocate the pests and/or interfere with or destroy their normal biological and/or physiological functions with minimal or negligible toxicity to the plant. In addition, the pests may be selectively targeted so that non-target beneficial insects are not damaged or are damaged to a minimum.
Furthermore, the reduced droplet size of the pesticide may increase the surface area of the plant contacted by the horticultural oil, thereby improving the efficacy of the pesticide.
In various embodiments, the concentration of the mixture of inert ingredients is from about 30.0% to about 80.0% w/w of the pesticide nanoemulsion. As mentioned above, the inert ingredient mixture comprises an emulsifier, a stabilizer and a surfactant. When the inert ingredient mixture concentration is from about 30.0% to about 80.0% w/w of the pesticidal nanoemulsion, the concentration of the horticultural oil ranges from about 20.0% to about 70.0% w/w of the pesticidal nanoemulsion.
In various embodiments, the stabilizing agent may comprise a polysaccharide or a derivative thereof. The concentration of the stabilizer may range from about 0.5% to 5.0% w/w of the pesticide nanoemulsion. This concentration range of the stabilizer is advantageous for maintaining the size and dispersibility of the droplets in the pesticide nanoemulsion. The stabilizer may have emulsifying properties and may be considered a co-emulsifier.
In some embodiments, the inert ingredient mixture of the pesticide nanoemulsion further comprises a binder at a concentration ranging from about 0.025% to about 1.500% w/w of the pesticide nanoemulsion. In some embodiments, the concentration of the binder ranges from about 0.25% to 3.00% w/w of the pesticide nanoemulsion. The binder preferably comprises solid particles of Pickering emulsion (Pickering emulsion) suitable for obtaining a pesticide nanoemulsion. The adhesive may have emulsifying properties and may be considered a co-emulsifier.
In various embodiments, nanoemulsification of horticultural oils facilitates reduction of oil concentration sufficient to control pests while mitigating the risk of damage to plants by the horticultural oils. Preferably, the horticultural oil concentration ranges from less than about 90.0% w/w of the pesticidal nanoemulsion, less than about 50.0% w/w of the pesticidal nanoemulsion, less than about 1.0% w/w of the pesticidal nanoemulsion. In various embodiments, the horticultural oil is at a concentration in the range of from about 0.15% to about 85.0% w/w of the pesticidal nanoemulsion, from about 0.15% to about 50.0% w/w of the pesticidal nanoemulsion, from about 5.0% to about 85.0% w/w of the pesticidal nanoemulsion, from about 5.0% to about 80.0% w/w of the pesticidal nanoemulsion, from about 5.0% to about 70.0% w/w of the pesticidal nanoemulsion, from about 5.0% to about 60.0% w/w of the pesticidal nanoemulsion, from about 5.0% to about 50.0% w/w of the pesticidal nanoemulsion, from about 10.0% to about 80.0% w/w of the pesticidal nanoemulsion, from about 10.0% to about 70.0% w/w of the pesticidal nanoemulsion, from about 10.0% to about 60.0% w/w of the pesticidal nanoemulsion, preferably from about 10.0% to about 50.0% w/w of the pesticidal nanoemulsion, more preferably from about 5.0% w/w of the pesticidal nanoemulsion, and even more preferably from about 5.0% to about 45.0% w/w, from about 5.0% to about 50.0% w/w, or from about 10.0% to about 50.0% w/w of the pesticide nanoemulsion.
In some embodiments, the concentration of the emulsifier ranges from about 0.05% to about 10.0% w/w of the pesticide nanoemulsion. In some embodiments, the concentration of the emulsifier ranges from about 0.1% to about 10.0% w/w of the pesticide nanoemulsion. In some embodiments, the emulsifier does not comprise a polysaccharide or derivative thereof.
Preferably, the concentration of the surfactant ranges from about 0.5% to about 30.0% w/w of the pesticide nanoemulsion.
In contrast, prior art horticultural oil-based pesticide concentrates typically comprise a horticultural oil at a concentration ranging from about 90% to 98% w/w of the formulation, and an emulsifier and surfactant at a concentration ranging from about 2% to 10% w/w of the formulation to produce a stable emulsified concentrate formulation. Thus, the pesticide nanoemulsion of the present invention advantageously can kill pests at lower concentrations at least as effectively as prior art horticultural oil-based pesticide concentrates. Furthermore, prior art horticultural oil-based pesticides use horticultural oils with relatively large droplet sizes, which in turn negatively impact plant physiology, such as causing leaf burning, reduced photosynthesis, reduced transpiration, and reduced flowering and fruit set. Thus, the pesticide nanoemulsions of the present invention may exhibit reduced phytotoxicity, as the relatively small droplet size as described above may result in a reduced likelihood of blocking transpiration through the leaf surface and through air holes, thereby resulting in unhindered transpiration, avoiding or minimizing growth retardation, and/or avoiding or minimizing crop yield reduction.
In some embodiments, the solvent is at least 0.25% w/w of the pesticide nanoemulsion. The solvent may comprise a first solvent and a second solvent, wherein the first solvent is water and the second solvent is at least 0.25% w/w of the pesticide nanoemulsion.
The pesticide nanoemulsion as described above can be used directly in the form of a concentrated formulation (i.e., a "concentrate") or suitable for dilution. In some embodiments, the dilution factor is about 150-fold to 700-fold to form a dilute pesticide nanoemulsion. In some embodiments, the dilution factor is about 100-fold to 800-fold to form a dilute pesticide nanoemulsion. The pesticide nanoemulsion of the present invention can exhibit dilution thickening characteristics. Specifically, the viscosity of the pesticide nanoemulsion can initially increase with increasing dilution, reaching a maximum, and then decrease with further dilution. An increase in viscosity with increasing dilution may correspond to an increase in the concentration of the stabilizing agent, such as the water-soluble polysaccharide, as the concentration of other components, such as the surfactant and/or salt components, decreases with increasing dilution.
Another aspect of the present invention is a dilute pesticidal emulsion comprising (a) a horticultural oil as an active ingredient; (b) a mixture of inert ingredients comprising: (i) an emulsifier; (ii) a stabilizer; and (iii) a surfactant; and (c) a solvent, wherein the horticultural oil is dispersed in the solvent in the form of droplets to form the dilute pesticidal nanoemulsion. In some embodiments, the droplets have an average size in the range of about 2nm to about 400 nm. In some embodiments, the droplets have an average size of about 50nm to about 350 nm. The various components of the dilute pesticide emulsion may be multifunctional. For example, the particular components may be emulsifiers and binders; or stabilizers and emulsifiers. As an example, the polysaccharide or derivative thereof may be both a stabilizer and an emulsifier, and thus are considered two inert ingredients for the purposes of the present invention.
In the dilute pesticide nanoemulsion, the horticultural oil droplet and the solvent are immiscible with each other. The oil droplets are adapted to associate and/or interact with emulsifiers, stabilizers, surfactants and/or other components of the pesticide nanoemulsion to form micelles. It will be appreciated that if the horticultural oil comprises both hydrophobic and hydrophilic groups, the horticultural oil may itself form micelles which are also suitable for association and/or interaction with the emulsifier, stabiliser, surfactant and/or other components in the pesticidal nanoemulsion. In some embodiments, the droplets have an average size of about 50nm to about 400nm, about 50nm to about 350nm, about 50nm to about 100nm, about 100nm to about 250 nm. The small oil droplet size facilitates effective penetration of insect pests while at the same time reducing phytotoxicity in plants, since the droplets do not block the stomata. The uniform distribution of the oil can also be maintained without agitation for a long period of time. Stable formulations with uniform oil distribution provide greater efficacy against pests than known oil pesticide products, even when the oil of the present invention is at a lower concentration than known dilute pesticide formulations. At the same time, problems such as clogging of the spraying equipment, uneven and problematic application, reduced efficiency of the application machinery and crop damage can be reduced or avoided.
It is known that oil-based liquid pesticide concentrates are typically diluted to oil concentrations of 1.0% to 2.0% w/w. At such oil concentrations, there is a risk of negative secondary effects, including plant damage (phytotoxicity), which may occur depending on the plant type, climatic factors, and the quality and stability of the oil-water diluted mixture. In particular, phytotoxicity may occur due to direct damage of leaf epidermal cells by condensed oil droplets or photosynthesis due to reduction of plant stomatal blockage. Damage to plants may also occur because dilute oil-based pesticides are inherently unstable and therefore require constant energy input through agitation to be maintained as a dilute oil dispersion. Inadequate agitation often results in poor distribution of the oil in the water/solvent due to coalescence of oil droplets, which in turn form larger oil droplets. When larger small oil droplets are sprayed on the leaf surface, they result in uneven distribution of the oil, which in turn may cause efficacy changes against the target pests and increase the risk of phytotoxicity. Although the horticultural oil-based pesticide of the present invention is capable of use at known oil concentrations and kills pests at least as efficiently as known formulations, the horticultural oil-based pesticide formulation of the present invention is advantageously capable of effectively killing pests at even lower dilutions having oil concentrations of from about 0.056% to about 0.5% v/v, from about 0.056% to about 0.45% v/v, from about 0.15% to about 0.5% v/v, or from about 0.15% to about 0.3% v/v of the pesticide nanoemulsion. Furthermore and more importantly, less than 1% v/v of horticultural oil in the diluted formulation reduces the risk of phytotoxicity.
In various embodiments, the stabilizing agent may comprise a polysaccharide or a derivative thereof. Preferably, the concentration of the stabilizer ranges from about 0.001% to about 0.017% v/v of the dilute pesticide nanoemulsion. This concentration range of the stabilizer is advantageous for maintaining the size and dispersibility of the droplets in the pesticide nanoemulsion. The stabilizer may have emulsifying properties and may be considered a co-emulsifier.
Preferably, the dilute pesticide nanoemulsion comprises a binder. The binder preferably comprises solid particles of a pickering emulsion suitable for obtaining a pesticide nanoemulsion. The adhesive may have emulsifying properties and may be considered a co-emulsifier.
Preferably, the concentration of the horticultural oil ranges from about 0.01% to about 0.32% v/v of the dilute pesticide nanoemulsion, more preferably from 0.01% to about 0.27% v/v of the dilute pesticide nanoemulsion, and even more preferably from 0.01% to about 0.15% v/v of the dilute pesticide nanoemulsion.
Preferably, the emulsifier does not comprise a polysaccharide or a derivative thereof.
Preferably, the dilute pesticide emulsion comprises a surfactant.
Another aspect of the invention is a pesticide formulation comprising an effective amount of at least one pesticide and an adjuvant nanoemulsion comprising the following components: (a) horticultural oils as active ingredients; (b) a mixture of inert ingredients comprising: (i) an emulsifier; (ii) a stabilizer; and (iii) a surfactant; and (c) a solvent, wherein the horticultural oil is dispersed in the adjuvant nanoemulsion in the form of droplets. The average size of the droplets may range from about 50nm to about 350 nm.
Another aspect of the invention is a pesticide formulation comprising an effective amount of at least one pesticide and a dilute adjuvant nanoemulsion comprising the following components: (a) horticultural oils as active ingredients; (b) a mixture of inert ingredients comprising: (i) an emulsifier; (ii) a stabilizer; and (iii) a surfactant; and (c) a solvent, wherein the horticultural oil is dispersed in the form of droplets in the thin-adjuvant nanoemulsion. The average size of the droplets may range from about 50nm to about 350 nm.
The pesticide nanoemulsion, dilute pesticide nanoemulsion, and pesticide formulation can be applied to plants, soil, and/or desired areas by means known in the art, including (but not limited to) spraying, sprinkling, aerosolizing, and/or direct pouring. The various components of the pesticide nanoemulsion, the dilute pesticide nanoemulsion, and the pesticide formulation can be multifunctional. For example, the particular components may be emulsifiers and binders; or stabilizers and emulsifiers. As an example, the polysaccharide or derivative thereof may be both a stabilizer and an emulsifier, and thus are considered two inert ingredients for the purposes of the present invention. The present invention is useful for a variety of plants including, but not limited to, ornamental plants such as camellia and lilac; cereals and field crops, such as oats, barley, wheat, rye, cotton, tobacco, maize, peanuts or soybeans; fruits such as blueberry, cranberry, strawberry, banana, peach, nectarine, apple, pear, orange, lemon, grapefruit, walnut, avocado, grape or tomato; vegetables, such as broccoli, cabbage, cauliflower, cabbage mustard, lettuce, spinach, celery, onion or asparagus. The invention is applicable to seeds of plant, aquatic agricultural plants, root and tuber crops, such as almonds or coffee beans; a bulb; a bulb; flowers, such as hops; a stem; a blade; and (4) fruits.
The oil-based pesticidal formulation and oil-based pesticidal adjuvant of the present invention may contain other additives including wetting agents and spreading agents that improve the spreading and area coverage of the applied formulation on a surface.
Horticultural oil
The pesticide nanoemulsions, dilute pesticide nanoemulsions and formulations of the present invention comprise horticultural oils. Horticultural oils are preferably present in the formulations of the present invention in the form of droplets. Due to the hydrophobic nature of the oil, the droplets preferably associate and/or interact with emulsifiers, surfactants, stabilizers, and/or adhesives in the formulation, thereby forming micelles. It will be appreciated that if the horticultural oil comprises both hydrophobic and hydrophilic groups, the horticultural oil may itself form micelles that associate and/or interact with the emulsifiers, surfactants, stabilizers and/or binders in the formulation. The size of the droplet (measured as its diameter) may range from a few nanometers to a few micrometers, preferably from about 2nm to about 400nm, more preferably from 50nm to about 400nm, and even more preferably from about 50nm to about 100 nm. The size of the droplets may be influenced by the method of synthesis, for example the rate of agitation used to disperse the hydrophobic horticultural oil in the solvent. In various embodiments, higher agitation rates can form droplets of smaller size.
The horticultural oil used in the present invention is effective as a pesticide for pest control. In particular, horticultural oils may be capable of killing, destroying and/or controlling pests and/or their growth and spread. When used, the oil layer on the plants and/or soil suffocates pests and/or interferes with their normal biological function.
Horticultural oils include hydrophobic or substantially hydrophobic dormant and summer oils (also known as super summer oil). Dormant oils are commonly used for cold season pest control, allowing plants to overwinter, while summer oils are commonly used during the growing season.
Horticultural oils for use in the present invention are vegetable (including vegetable) oils, hydrocarbon oils or animal fatty oils typically processed into emulsified concentrated formulations for dilute spray application to growing or harvested agricultural crops for the purpose of controlling arthropod and fungal crop pests. Typical oils used include super refined paraffin oil and vegetable oils such as soybean oil, palm oil, cottonseed oil or rapeseed oil. These oils contain little to no volatile organic compounds and the primary mode of action is death by asphyxiation of arthropod and plant pathogens, where the physical effect of the oil is the active ingredient, as the oil coating prevents respiration and kills pests. Examples of oils containing little to no volatile organic compounds include, but are not limited to, vegetable oils such as olive oil, soybean oil, palm oil, cottonseed oil, corn oil, coconut oil, peanut oil, and rapeseed oil.
Volatile vegetable oils, on the other hand, are oils that have been used in recent years for their insecticidal properties. These oils are highly aromatic due to the presence of various Volatile Organic Compounds (VOCs), often referred to as secondary phytochemicals. Many volatile compounds have shown biocidal activity against a wide range of diseases and pest types and are believed to be useful as plant defense chemicals. It has been used in a variety of applications ranging from pharmaceuticals to structural and agricultural pest control. Common examples of volatile vegetable oils include rosemary oil, garlic oil, clove oil, neem oil, and eucalyptus oil. The main difference between the horticultural oils used in the present invention and the volatile vegetable oils used in the prior art is the difference in the main mode of action. Volatile vegetable oils rely on the toxic effects of VOCs, while horticultural oils use a physical mode of action.
Nanoemulsions are a relatively new formulation technique for oil-in-water (o/w) emulsion systems. Nanoemulsions are typically defined by a reduction in oil droplet size to the range of 50nm to 400nm, whereas known o/w emulsions are typically >400 nm. The advantage of nanoemulsions over known emulsion formulations is that smaller droplet sizes can improve the distribution and targeting of oil droplets to the target. Nanoemulsions have been used in various industrial, medical and agricultural applications as a way to increase the efficiency of delivering oil-miscible active ingredients in volatile vegetable oils to specific targets. However, the main role of oils in these applications has been as a carrier for oil-miscible active ingredients. In agriculture, for example, nanoemulsion formulations have been used to enhance the efficacy of oil-miscible pesticidal active ingredients at a given dose to increase pest mortality, or as a means of reducing the required dose required to achieve a desired level of control.
On the other hand, the present invention is to improve the efficacy of horticultural oils using nanoemulsion technology in a completely different way, where the oil does not act as a carrier for the oil miscible active ingredient, in fact where the physical properties of the oil droplets themselves act as the active ingredient.
Viscosity affects the flow and spreading of horticultural oils over surfaces. Lighter oils are more uniformly dispersed, while heavier oils tend to bead to a greater extent on the surface.
Horticultural oils may include synthetic oils and semi-synthetic oils. Preferably, the horticultural oil used in the composition/formulation of the present invention is edible. One or more horticultural oils may be used in the compositions/formulations of the present invention.
Emulsifier
The pesticide nanoemulsions, dilute pesticide nanoemulsions and formulations of the present invention comprise an emulsifier. The emulsifier aids in the formation of the emulsion or prevents the emulsion from separating into its constituent phases. The emulsifier comprises a hydrophilic head that interacts with a hydrophilic solvent and a hydrophobic tail that interacts with a hydrophobic horticultural oil. In emulsions, the emulsifier is located at the oil-solvent interface and maintains separation of the oil from the solvent by reducing surface tension.
Emulsifiers include, but are not limited to, acrylates, acrylate copolymers, agar, alginic acid and its derivatives, alginate derivatives (including, but not limited to, ammonium alginate, calcium alginate, potassium alginate, sodium alginate and propylene glycol alginate), acacia, arabinogalactan, beta-glucan, carrageenan, cellulose polymers, ceramides, chitin, dextran, diutan gum (diutan gum), furcellaran gum, fucoidan gum, gellan gum, glycogen, guar gum, chicle gum, galagana gum, laminaran, lecithin, ligno locust bean gum, methacrylates, methylmethacrylate, modified starches, pectin, psyllium, polyvinylpyrrolidone, rhamsan gum, saponin and its derivatives (including, but not limited to, latex saponin), scleroglucan, sulfonic acid, starch hydroxyethyl ether, saponin and its derivatives (including, but not limited to, latex saponin), scleroglucan, sulfonic acid, starch, hydroxyethyl ether, and derivatives thereof, Amylodextrin, tragacanth gum and xanthan gum. Cellulosic polymers include, but are not limited to, bacterial cellulose, carboxymethyl cellulose, ethyl-hydroxyethyl cellulose, hydroxypropyl methyl cellulose, microparticulate cellulose, and sodium carboxymethyl cellulose.
Preferably, the emulsifier does not comprise a polysaccharide or a derivative thereof or is not a polysaccharide or a derivative thereof, especially when the stabiliser comprises a polysaccharide. However, in various embodiments, both the stabilizer and the emulsifier may comprise a polysaccharide, i.e., two polysaccharides will be present in the formulation. In such embodiments, preferably, the two polysaccharides are different polysaccharides.
Stabilizer
The pesticide nanoemulsions, dilute pesticide nanoemulsions and formulations of the present invention comprise a stabilizer. The stabilizer stabilizes the emulsion by maintaining a homogeneous dispersion of the horticultural oil droplets in the solvent and preventing the horticultural oil from separating from the solvent (i.e. the droplets dissociate to form separate horticultural oil and solvent layers). Stabilizers may have emulsifying properties and certain stabilizers may be used as emulsifiers or co-emulsifiers. Preferably, the stabilizing agent in the composition/formulation of the present invention is not a true emulsifier and is primarily used to stabilize the emulsion.
Stabilizers include, but are not limited to, proteins, polysaccharides, and derivatives thereof. Specifically, stabilizers include, but are not limited to, acacia gum, agar, alginic acid and derivatives thereof, alginate derivatives (including, but not limited to, ammonium alginate, calcium alginate, potassium alginate, sodium alginate, and propylene glycol alginate), acacia gum, carboxymethylcellulose, carrageenan, gelatin, glycerol, glycogen, guar gum, caraa gum, locust bean gum, mannitol, pectin and derivatives thereof, saponin or derivatives thereof, tara gum, tragacanth gum, and xanthan gum.
Preferably, the stabilizer used in the composition/formulation of the present invention comprises a polysaccharide or a derivative thereof. More preferably, the stabilizer used in the composition/formulation of the present invention is a polysaccharide or a derivative thereof. Polysaccharides are polymeric carbohydrate molecules in which monosaccharide units (i.e., sugars) are bonded by glycosidic bonds. Polysaccharides include linear and branched structures, and may be homogeneous repeats of one type of monosaccharide unit (homopolysaccharides) or heterogeneous repeats of more than one type of monosaccharide unit in a random or non-random arrangement (also referred to as heteropolysaccharides). As used herein throughout the specification, polysaccharides and derivatives thereof include structures having more than three monosaccharide units and thus include (but are not limited to) oligosaccharides. Polysaccharide derivatives refer to polysaccharide chains of monosaccharide units, wherein one or more side branches of one or more monosaccharide units are modified, e.g. the side branches may contain hydroxyl, amino and/or carboxylic acid groups. Advantageously, the polysaccharide may adjust the viscosity of the composition/formulation of the invention. When the polysaccharide is used in combination with solid particles (e.g., clay particles) and the emulsion comprises droplets having an average size of about 2nm to about 400nm, the emulsion may remain without separating into its constituent phases even upon dilution. Accordingly, coalescence and phase separation can be prevented, and the dilute solution can be maintained as a suspension for a long period of time exceeding 30 days.
Preferably, the stabilizing agent in the compositions/formulations of the present invention includes, but is not limited to, acacia gum, agar, alginic acid and its derivatives, alginate derivatives (including, but not limited to, ammonium alginate, calcium alginate, potassium alginate, and sodium alginate and propylene glycol alginate), acacia gum, carboxymethylcellulose, carrageenan, glycogen, guar gum, caraa gum, saponin or its derivatives, locust bean gum, pectin and its derivatives, tara gum, tragacanth gum, or xanthan gum.
Polysaccharides may also be thickeners and gelling agents in the compositions/formulations of the present invention.
Solvent(s)
The pesticide nanoemulsions, dilute pesticide nanoemulsions and formulations of the present invention comprise a solvent. Solvents are used in the present invention as diluents and dissolve or partially dissolve and disperse or partially disperse the components of the compositions/formulations of the present invention. The solvent may comprise one or more of: water, aliphatic hydrocarbons, aromatic hydrocarbons, ketones, alcohols (linear or branched), esters, amides or ethers. The aliphatic hydrocarbons may comprise linear or branched alkanes, linear or branched alkenes (alkenes/olephins), and/or cyclic alkanes (cycloalkanes). Preferably, the solvent is hydrophilic or substantially hydrophilic. More preferably, the solvent is water.
When the solvent is water, a stable oil-in-water emulsion may be formed by: a microemulsion formulation comprising a polysaccharide or other polymer and solid particles is first constructed. Microemulsion formulations may be formed by blending various components. Polysaccharides or other polymers act as viscosity modifiers that operate to form micro-droplets to maintain the distribution of small oil globules of the dispersed phase, thereby stabilizing the emulsion. In addition, the solid particles act as co-emulsifiers to further stabilize the formulation in the pickering-type microemulsion. Thus, the polysaccharide or other polymer and the solid particles act in concert to stabilize the formulation. The micro droplet formulation (i.e., the microemulsion formulation) is then subjected to a high shear mixer to form a nano droplet emulsion that further reduces the globule size of the oil and enhances the stability of the emulsion. Thus, emulsion formulations may be formed that include oil droplets having an average size in the range of about 2nm to about 400 nm. Advantageously, nanoemulsion formulations in a particular particle size range are thermodynamically and kinetically stable. This can result in better penetration into insects and reduced phytotoxicity. Furthermore, emulsion formulations produce pesticide formulations with long shelf lives of more than two years, which can be easily diluted to the desired end use concentration.
Preferably, the solvent is an ester selected from the group consisting of: butyl acetate, dipropylene glycol methyl ether acetate, and ethyl acetate; an alcohol selected from the group consisting of: ethanol, isobutanol, isopropanol, methanol, phenol, and propylene glycol; or mixtures thereof.
One or more solvents may be used to dissolve and/or disperse the components of the compositions/formulations of the present invention. The solvent used to dilute the pesticide nanoemulsion may be different from the solvent in the pesticide nanoemulsion.
Surface active agent
The pesticide nanoemulsions, dilute pesticide nanoemulsions and formulations of the present invention may comprise one or more surfactants. The surfactant is capable of lowering the surface tension of the horticultural oil in the solvent. Surfactants include, but are not limited to, anionic, nonionic, cationic or amphoteric surfactants, block polymers or polyelectrolytes.
Anionic surfactants include, but are not limited to, alkali metal, alkaline earth metal, or ammonium salts of sulfates, sulfonates, phosphates, or carboxylates. Examples of sulfates are sulfates of fatty acids and oils, sulfates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols, and sulfates of fatty acid esters. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of dodecylbenzenes and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates and sulfosuccinamates. An example of a phosphate ester is a phosphate ester. Examples of carboxylic acid esters are carboxylic acid alkyl esters, carboxylated alcohols and alkylphenol ethoxylates.
Nonionic surfactants include, but are not limited to, alkoxylates, N-alkylated fatty acid amides, amine oxides, esters, and sugar-based surfactants. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids and fatty acid esters which have been alkoxylated. Ethylene oxide and/or propylene oxide may be used for the alkoxylation, with ethylene oxide being the preferred choice. Examples of N-alkylated fatty acid amides are fatty acid glucamides and fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerides and monoglycerides. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters and alkyl polyglucosides.
Examples of suitable cationic surfactants are quaternary ammonium surfactants (e.g. quaternary ammonium compounds having one or two hydrophobic groups) and salts of long chain primary amines.
Amphoteric surfactants include, but are not limited to, alkyl betaines and imidazolines.
Block copolymers include, but are not limited to, block copolymers of the a-B and a-B-a types comprising blocks of polyethylene oxide and polypropylene oxide, and block copolymers of the a-B-C type comprising alkanols, polyethylene oxide and polypropylene oxide.
Polyelectrolytes include, but are not limited to, polyacids and polybasic bases. An example of a polyacid is an alkali metal salt of polyacrylic acid. Examples of polybasic bases are polyvinylamine (polyvinyiamine) and polyethyleneamine (polyethylenimine).
The ability of surfactants to reduce the surface tension of tiny droplets/micelles depends on the molecular structure of the surfactant. In particular, the Hydrophilic Lipophilic Balance (HLB) determines whether the surfactant is soluble in water and whether the water-immiscible droplets can be stabilized (i.e. emulsified) in water. The HLB value of a surfactant indicates the overall polarity of the molecule and is in the range of 1 to 40, while the HLB value of the most common commercial surfactants is 1 to 20. The HLB value increases with increasing hydrophilicity. Surfactants having an HLB value of 0 to 7 are considered to be lipophilic, surfactants having an HLB value of 12 to 20 are considered to be hydrophilic, and surfactants having an HLB value of 7 to 12 are considered to be neutral. Preferably, nonionic surfactants are used in the present invention, wherein the nonionic surfactants can have an intermediate HLB value, depending on factors such as chain length and degree of ethoxylation. Preferably, the surfactant comprises one or more nonionic surfactants selected from the group consisting of: linear alcohol ethoxylates, such as polyoxyethylene lauryl ether; phenol ethoxylates such as nonylphenol ethoxylate, octylphenol ethoxylate and dodecylphenol ethoxylate; polyoxyethylene sorbitan fatty acid esters such as polysorbate 20; sorbitan fatty acid esters such as sorbitan monostearate; sucrose fatty acid esters such as sucrose stearate; and vegetable oil surfactants such as polyoxyethylene castor oil or derivatives thereof.
Adhesive/bonding agent
The pesticide nanoemulsions, dilute pesticide nanoemulsions and formulations of the present invention may comprise one or more adhesives and binders. Adhesives and bonding agents may be used to help maintain the compositions/formulations of the present invention on a surface (e.g., a blade surface) for extended periods of time. In particular, the adhesion and bonding agent may increase the adhesion of the droplets to the surface to which the composition/formulation of the present invention is applied. The thickener that increases the viscosity of the composition/formulation may also be an adhesive, however the adhesive may not be a thickener, i.e., it does not increase the viscosity of the composition/formulation. Increasing the adhesion of the droplets on the application surface increases the residence time, which improves the effect of the formulation on pests. Charged adhesion and adhesives also improve the penetration of the droplets into the pests, thereby better killing the pests.
The adhesive and binder may be charged or uncharged. Charged adhesives include positively and/or negatively charged molecules. Preferably, the adhesive is positively charged to improve adhesion of the tiny droplets/micelles to negatively charged parts of the plant (e.g. leaves).
The adhesive and binder include, but are not limited to, clay, cellulose, charcoal, diatomaceous earth, natural or synthetic silicates, titanium dioxide, magnesium silicate, aluminum silicate, talc, pyrophyllite clay, silica, attapulgite clay, chalk, limestone, calcium carbonate, bentonite or Fuller's earth. Preferably, the adhesive and binder is one or more of the following: cellulose, chalk, charcoal, diatomaceous earth, kaolinite, limestone or silica.
The adhesive and bonding agent may have other properties, such as wetting and spreading properties. The adhesive and binder may also have emulsifying properties and may be considered co-emulsifiers.
Pesticide
The pesticide nanoemulsion and its diluted formulations can be used as adjuvants in pesticide compositions/formulations. Thus, the pesticide nanoemulsion and diluted forms thereof may be used and/or mixed with one or more chemical and/or biological pesticides as active ingredients to form pesticide compositions/formulations. When used as an adjuvant, the pesticide nanoemulsion may be considered an adjuvant emulsion concentrate, while the dilute pesticide nanoemulsion may be considered a dilute adjuvant nanoemulsion.
As used herein throughout the specification and when the pesticide nanoemulsion and/or dilute formulations thereof are used as adjuvants in pesticide compositions/formulations, "pesticide" refers to a chemical or biological agent that kills, kills and/or controls pests and/or their growth and spread. Examples of pesticides that may be combined with the pesticide nanoemulsion and/or dilute formulations thereof include, but are not limited to, fungicides, herbicides, insecticides, acaricides, bactericides, nematicides, and algicides. Those skilled in the art are aware of the many types and classes of pesticides that are available.
In various embodiments, more than one oil may be present in the pesticide composition/formulation, such as an adjuvant nanoemulsion comprising a vegetable oil (as the horticultural oil component) and an essential oil (as the pesticide component).
Examples
Example 1
Pesticide nanoemulsions according to embodiments of the present invention were developed for controlling insect and disease pests in vitis vinifera (pesticide 1). Pesticide 1 is a soybean oil based pesticide comprising 45% w/w soybean oil and 55% w/w inert ingredients. When mixed with water to form a dilute pesticide nanoemulsion and applied directly to plants (including leaves, stems, flowers and roots) at a specified rate, tests have shown that economic control of vineyard pests, particularly fungal pests such as Botrytis (Botrytis) and/or powdery mildew is achieved; and insect pests such as aphids, whiteflies, leafhoppers and/or mites (e.g. spider mites).
Pesticide 1 is characterized as follows:
highly concentrated formulation-about 1.50 liters of pesticide 1/hectare
Readily miscible in water
Can be mixed with most crop protection products and nutrient tanks. Used under warm or cold growth conditions
Vine safety (Vine-safe) for all varieties of grapes used for wine brewing
Compatibility with Integrated Pest Management (IPM) organic and sustainable production practices
Products that can be used as biocontrol substitutes (BCA)
Zero-day post-harvest intervals (PHI) requiring minimal personal equipment due to no or negligible toxicity to humans
4 hours reentry period
Enhanced efficacy against pests while minimizing the risks associated with known horticultural oils
Without affecting vine respiration or turnover (veraison) (i.e. onset of ripening)
Odorless, no detectable residue
Extremely low risk of pest resistance
Low Volatile Organic Compounds (VOC)
Example 2
The efficacy of pesticide 1 was compared to a pesticide mixture comprising a commercially available emulsifiable suspension fungal insecticide (pesticide C1) and a commercially available microbial insecticide (pesticide C2). Pesticide C1 contained 11.3% active ingredient (zombiella alba (beauveria bassiana) strain GHA) and 88.7% inert ingredient, and pesticide C2 contained the naturally occurring fungus (Paecilomyces fumosoroseus).
A formulation comprising pesticide 1 in an amount of 4.8 fluid ounces (fl.oz)/25 gallons (gal) and another formulation comprising pesticide 1 in an amount of 9.75fl.oz/25gal were prepared and compared to a formulation comprising pesticide C1-pesticide C2 in an amount of 7.0fl.oz/25 gal. Efficacy results against spider mite eggs are shown in fig. 1A, and efficacy results against adult and larval spider mites are shown in fig. 1B.
With respect to fig. 1A and 1B, it is shown that a formulation comprising an amount of pesticide 1 of 4.8fl.oz/25gal (0.15% v/v) shows superior results most of the time, even after an extended period of time, compared to a formulation comprising an amount of pesticide 1 of 9.75fl.oz/25gal (0.30% v/v). Advantageously, both formulations comprising pesticide 1 were able to reduce spider mite egg count, adult spider mites and larva count as evidenced by the dramatic reduction in spider mite egg count, adult spider mites and larva count relative to the untreated control. Unexpectedly, both formulations containing pesticide 1 also showed superior results at day 28 compared to the formulation containing pesticide C1-pesticide C2, confirming that pesticide 1 controls pests more reliably than the industry standard. Thus, it was also shown that a relatively small amount of pesticide 1 (0.15% v/v) was sufficient to reduce the egg count of spider mites, the adult spider mites and the number of young insects. In comparison, pesticide 1 works similarly to conventional horticultural pesticides known in the art applied at 1.0% -2.0% v/v formulation or 0.90 to 0.98% w/w horticultural oil. However, in the present invention, this level of pest control is achieved at levels as low as 0.15% v/v formulation or 0.068% v/v horticultural oil concentration.
Example 3
Another pesticide nanoemulsion (pesticide 2) according to an embodiment of the present invention was developed. Pesticide 2 is a non-volatile vegetable oil based pesticide comprising 34% w/w palm oil as active ingredient and 66% w/w inert ingredient.
Similar to pesticide 1, pesticide 2 also contained soy as an active ingredient and, according to table 1, it was shown to work well at a dilution rate of 9.75fl. oz/25gal (0.3% v/v or 3.0 ml/L). In particular, pesticide 2 was found to be effective in minimizing mites on strawberries and mini-roses, successfully reducing the incidence of gray mold on strawberry fruits, reducing the incidence of white rust on chrysanthemum, and effectively inhibiting/minimizing whitefly populations on tomatoes. The above mentioned performance data show consistency at lower horticultural oil concentrations (45% w/w in pesticide 1 versus 34% w/w in pesticide 2).
Table 1.
Testing Treatment efficacy (%)
Treatment efficacy on mites on strawberries 73.1
Treatment efficacy on Botrytis cinerea on strawberries 70.2
Treatment efficacy against mites on roses 85.4
Treatment efficacy against white rust on chrysanthemum 93.3
Treatment efficacy against whitefly on tomatoes 76.0
Treatment efficacy against powdery mildew on tomato 97.1
Tomato
Tomato
It will be further appreciated by those of ordinary skill in the art that variations and combinations of the features described above may be combined, rather than alternatives or alternatives, to form other embodiments within the intended scope of the invention.
Furthermore, while individual embodiments have been discussed, it is to be understood that the invention also encompasses combinations of the embodiments that have been discussed.

Claims (16)

1. A pesticide nanoemulsion, comprising:
(a) horticultural oils as active ingredients;
(b) a mixture of inert ingredients comprising:
(i) an emulsifier;
(ii) a stabilizer; and
(iii) a surfactant; and
(c) a solvent, a water-soluble organic solvent,
wherein the horticultural oil is dispersed in the solvent in the form of droplets to form the nanoemulsion.
2. The pesticide nanoemulsion of claim 1, wherein the droplets have an average size of 50nm to 350 nm.
3. The pesticide nanoemulsion of claim 2, wherein the droplets have an average size of 100nm to 250 nm.
4. The pesticide nanoemulsion of any one of the preceding claims, wherein the concentration of the stabilizer ranges from 0.5% to 5.0% w/w of the pesticide nanoemulsion.
5. The pesticide nanoemulsion of any one of the preceding claims, wherein the inert ingredient mixture further comprises a binder at a concentration ranging from 0.25% to 3.00% w/w of the pesticide nanoemulsion.
6. The pesticidal nanoemulsion of any one of the preceding claims, wherein the concentration of the horticultural oil ranges from less than 90% w/w of the pesticidal nanoemulsion.
7. The pesticidal nanoemulsion of claim 6, wherein the concentration of the horticultural oil ranges from 20.0% to 70.0% w/w of the pesticidal nanoemulsion and the concentration of the inert ingredient mixture ranges from 30.0% to 80.0% w/w of the pesticidal nanoemulsion.
8. The pesticidal nanoemulsion of claim 7, wherein the amount of horticultural oil is 45.0% w/w of the pesticidal nanoemulsion and the concentration of the inert ingredient mixture is 55.0% w/w of the pesticidal nanoemulsion.
9. The pesticide nanoemulsion of any one of the preceding claims, wherein the concentration of the emulsifier ranges from 0.1% to 10.0% w/w of the pesticide nanoemulsion.
10. The pesticide nanoemulsion of any one of the preceding claims, wherein the concentration of the surfactant ranges from 0.5% to 30.0% w/w of the pesticide nanoemulsion.
11. The pesticide nanoemulsion of any one of the preceding claims, wherein the solvent is at least 0.25% w/w of the pesticide nanoemulsion.
12. The pesticide nanoemulsion of claim 11, wherein the solvent comprises a first solvent and a second solvent, wherein the first solvent is water and the second solvent is at least 0.25% w/w of the pesticide nanoemulsion.
13. The pesticide nanoemulsion of any one of the preceding claims, wherein the pesticide nanoemulsion is adapted to be diluted between approximately 100-fold and 800-fold to form a diluted pesticide nanoemulsion.
14. The pesticidal nanoemulsion of claim 13, wherein the concentration of the horticultural oil ranges from 0.056% to 0.45% v/v of the dilute pesticidal nanoemulsion.
15. The pesticide nanoemulsion of claim 13 or 14, wherein the concentration of the stabilizer ranges from 0.001% to 0.017% v/v of the dilute pesticide nanoemulsion.
16. A pesticide formulation comprising an effective amount of at least one pesticide and an adjuvant nanoemulsion comprising the following components:
(a) horticultural oils as active ingredients;
(b) a mixture of inert ingredients comprising:
(i) an emulsifier;
(ii) a stabilizer; and
(iii) a surfactant; and
(c) a solvent, a water-soluble organic solvent,
wherein the horticultural oil is dispersed in the solvent in the form of droplets to form the adjuvant nanoemulsion.
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