Microencapsulated pheromone preparations

Abstract

Compositions containing microencapsulated pheromones are described herein. Methods for producing compositions containing microencapsulated pheromones are also described herein. Methods for controlling pests using the above compositions are also described herein.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority over U.S. Provisional Patent Application No. 63 / 471,196, filed on 5 June 2023, the contents of which are incorporated herein by reference.

[0002] Areas of disclosure Compositions containing microencapsulated pheromones are described herein. Methods for producing compositions containing microencapsulated pheromones are also described herein. Methods for controlling pests using such compositions are also described herein. [Background technology]

[0003] Background of Disclosure Pheromone compositions are difficult to formulate for numerous reasons, including reactions with other components in the formulation matrix, degradation of pheromones over time, and undesirable release rates of pheromones from the formulation. This is especially true when the pheromone is an active pesticide component that must be delivered at a constant release rate over time. Therefore, there is a need in this field for compositions containing pheromones with improved release rates and degradation characteristics. [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Microencapsulation provides a means of formulating pheromones for broad-area application in insect population control by disrupting pheromone-mediated communication. Microencapsulation also helps control the volatility of pheromones. However, although pheromone microencapsulation has been demonstrated previously, the need for improved formulations containing microencapsulated pheromones remains. [Means for solving the problem]

[0005] This disclosure provides formulations containing microencapsulated pheromones. These formulations have improved properties compared to conventional formulations containing microencapsulated pheromones. This disclosure enables the formulation of pheromones that can be used in sprayable agricultural formulations. Such sprayable formulations are essential for application to rows of crops.

[0006] Formulations containing microencapsulated pheromones according to this disclosure can be manufactured by known methods of interfacial polymerization and can be applied over a wide area using conventional spraying equipment. These have numerous variables (capsule wall composition, capsule wall thickness, capsule size, and internal composition) that can be manipulated to control their release characteristics.

[0007] Brief explanation of disclosure In one embodiment, the present disclosure relates to a composition comprising a core containing an antifreeze; a pheromone; and a solvent; and a microcapsule containing a shell that encloses the core, wherein the microcapsule has a d90 value of at least about 30 μm.

[0008] In another embodiment, the present disclosure relates to a method for producing a composition, the method comprising forming a mixture comprising: an antifreeze; a pheromone; and a core comprising a solvent; and a microcapsule comprising a shell enclosing the core, wherein the microcapsule has a d90 value of at least about 30 μm.

[0009] In yet another embodiment, the Disclosure relates to a method for controlling pests, comprising contacting a pest or its environment with a biologically effective amount of a composition, wherein the composition comprises a core containing: an antifreeze; a pheromone; and a solvent; and a microcapsule containing a shell enclosing the core, wherein the microcapsule has a d90 value of at least about 30 μm. [Modes for carrying out the invention]

[0010] Detailed explanation of disclosure This document uses examples to illustrate the disclosure in best form, and also to enable a person skilled in the art to implement the disclosure, including by manufacturing and using any of the compositions or systems and by carrying out the incorporated methods. The patentable scope of the disclosure is defined by the claims and may include other examples that a person skilled in the art could conceive. Such other examples are intended to be within the scope of the claims if they have elements that are not different from the language of the claims, or if they have equivalent elements that are not substantially different from the language of the claims.

[0011] The terms “comprises,” “comprising,” “includes,” “including,” “have,” “have,” “contain,” “contain,” “characterized by,” or any other variations thereof as used herein are intended to extend to non-exclusive inclusion and are subject to any expressly indicated limitations. For example, a composition, mixture, process, or method containing a list of elements is not necessarily limited to those elements alone, but may include other elements not expressly listed, or other elements specific to the above composition, mixture, process, or method.

[0012] The transitional clause “consist of” excludes any elements, processes, or components not explicitly stated. In the case of claims, the clause closes the claim in the event of inclusion of substances other than those described, except for impurities that are usually associated with them. If the clause “consist of” appears in a clause of the essential part of the claim rather than immediately following the preamble, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0013] The transitional phrase “essentially consisting of” is used to define a composition or method that includes substances, processes, features, components, or elements in addition to what is literally disclosed, but which do not substantially affect the fundamental and novel features of the claimed invention. The term “essentially consisting of” occupies an intermediate area between “including” and “consisting of.” The use of “essentially consisting of” herein allows the applicant to define the claimed invention as a lexicographer by excluding any materials, processes, features, etc. that the applicant considers not essential to the claimed invention, but which may be publicly known in the prior art or could be included in the claimed invention, regardless of whether or not their inclusion or exclusion is specifically stated in the specification. Any exclusion of any materials, processes, features, etc. by the applicant may be solely for the purpose of excluding elements of the prior art that would affect novelty and, consequently, affect the patentability of the claimed invention. Therefore, the use of “essentially consisting of” in this specification does not require explicit support from the specification to exclude any element of the prior art from the claimed invention if including that element would impair the patentability of the claimed invention.

[0014] When an invention or part thereof is defined using open-ended terms such as "contains," it should be readily understood that (unless otherwise stated) the description should also be interpreted as describing the invention using terms such as "essentially consisting of" or "consisting of."

[0015] Furthermore, unless explicitly stated otherwise, "or" refers to an inclusive or, not an exclusive or. For example, condition A or B is satisfied by one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0016] Also, the indefinite articles “a” and “an” before an element or component of the present invention are intended to be non - limiting with respect to the number of instances (i.e., occurrences) of that element or component. Thus, “a” or “an” should be understood to include one or at least one, and the singular form of a term for an element or component includes the plural as well, unless the number clearly means singular.

[0017] Depending on the context in which it is used, the term “about” as used herein provides an approximation of a value related to the claimed invention, where the approximated value is considered in the context of the description of the invention and is reasonable considering what is understood or interpreted by one of ordinary skill in the art from generally available information. The term “about” as used herein generally means that the approximated value is within plus or minus 10% of the accompanying value. The term “about” may be further defined by the context, and it is within the scope of the applicant's right as a lexicographer to define how “about” should be interpreted within the specific context used in the description of the invention.

[0018] As used herein, “mass %” refers to the mass percentage of the listed component relative to the total mass of the listed composition.

[0019] As used herein, “substantially free of” generally refers to 2 mass % or less. In some embodiments, “substantially free of” refers to 1.5 mass % or less, 1.0 mass % or less, 0.5 mass % or less, or 0.1 mass % or less.

[0020] As used herein, the “d10 value” means that 10% of the particles have a diameter smaller than this value.

[0021] As used herein, the “d50 value” means that 50% of the particles have a diameter smaller than this value.

[0022] As used herein, the "d90 value" means that 90% of the particles have a diameter smaller than this value.

[0023] Particle size measurement can be performed using a variety of different methods, techniques, and apparatuses. As described in this disclosure, particle size is not limited to any of the measurement methods, techniques, or apparatuses. In some embodiments, particle size is measured using techniques selected from light scattering, static light scattering, dynamic light scattering, and combinations thereof. In some embodiments, particle size is measured using a particle size analyzer. In some embodiments, particle size is measured using a particle size analyzer configured to calculate particle size using the Fraunhofer approximation of light scattering. In some embodiments, particle size is measured using a particle size analyzer selected from the Malvern Mastersizer 2000, Malvern Mastersizer 3000, HELOS / BR Sucell, and combinations thereof.

[0024] As used herein, "antifreeze" refers to a substance that can be added to water or an aqueous mixture to lower the freezing point of water or an aqueous mixture.

[0025] In the context of this disclosure, “harmful invertebrate control” means inhibiting the occurrence of harmful invertebrates (including mass deaths, reduced feeding, and / or mating disruption), and related expressions are defined similarly.

[0026] As described in this disclosure, the term “harmful invertebrates” includes arthropods, gastropods, nematodes, and parasitic helminths that are economically important as pests. The term “arthropods” includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs, and symphylans. The term “gastropods” includes snails, slugs, and other Stylommatophora. The term “nematodes” includes members of the phylum Nematoda, such as herbivorous nematodes and parasitic helminths. The term "helminths" includes all parasites, such as roundworms (Nematoda), heartworms (Nematoda, Bipolaria), trematodes (Platyhelminthes, Trematodae), acanthocephalans (Acanthocephala), and tapeworms (Platyhelminthes, Cetoidea).

[0027] The term "agricultural" refers to the production of crops for food and fiber, such as maize or corn, soybeans and other legumes, rice, grains (e.g., wheat, oats, barley, rye and rice), leafy vegetables (e.g., lettuce, cabbage and other cruciferous crops), fruit-bearing vegetables (e.g., tomatoes, peppers, eggplants, cruciferous plants and cucurbits), potatoes, sweet potatoes, grapes, cotton, fruit-bearing plants (e.g., pears, drupes and citrus fruits), small fruits (e.g., berries and cherries) and other specialty crops (e.g., canola, sunflowers and olives).

[0028] The term "non-agricultural" refers to uses other than agricultural crops, such as horticultural crops (e.g., greenhouse plants, seedlings, or ornamental plants not grown outdoors), structures for housing, agriculture, commerce, and industry, turf (e.g., lawns, pastures, golf courses, turflands, sports fields, etc.), wood products, storage products, agricultural and forestry management, and public health (i.e., human) and animal health (e.g., domesticated animals, e.g., pets, livestock, and poultry, undomesticated animals, e.g., wildlife).

[0029] The term "crop vitality" refers to the rate of crop growth or accumulation of bio-based resources. "Increased vitality" refers to the increase in crop growth or bio-based resource accumulation compared to an untreated control crop. The term "crop yield" refers to the benefit to crop material after harvest, in terms of both quantity and quality. "Increased crop yield" refers to the increase in crop yield compared to an untreated control crop.

[0030] The term "biologically effective dose" refers to the amount of a biologically active compound that, when applied (i.e., in contact with) a harmful invertebrate or its environment, or a plant, the seeds from which the plant grows, or the location of the plant (e.g., a growth medium), is sufficient to produce a desired biological effect, such as protecting the plant from damage by harmful invertebrates or for other desired effects (e.g., increasing plant vitality).

[0031] Non-agricultural uses include protecting animals from parasitic invertebrate pests by administering to animals to be protected from pests a bioactive amount of the biologically active compounds of this disclosure, usually in the form of compositions formulated for veterinary use. The terms “parasitic” and “in a bioactive manner” as used in this disclosure and claims refer to an observable effect on parasitic invertebrate pests in order to provide protection for animals from pests. Parasitic effects typically relate to reducing the presence or activity of the target pest invertebrate parasite. Such effects on pests include necrosis, death, stunted growth, reduced mobility or reduced ability to remain on or within a host animal, reduced feeding, and inhibition of reproduction. These effects on pest invertebrate parasites result in the control (including prevention, reduction, or elimination) of ectoparassis or infection of animals by the parasite.

[0032] It was surprisingly discovered that substantial improvements in controlling the volatility of pheromone compositions can be achieved using compositions containing an antifreeze and microcapsules, in which case the microcapsules are relatively large and contain co-encapsulated pheromones and solvents. The most substantial improvements were observed using microcapsules with a d90 value of at least 35 μm.

[0033] In some embodiments, compositions comprising a core containing an antifreeze, a pheromone, and a solvent, and a microcapsule containing a shell encapsulating the core, are described herein. The microcapsule has a d90 value of at least about 30 μm.

[0034] In general, compositions according to this disclosure may include microcapsules of any suitable size known in the art that facilitate the compositions described herein. The size of the microcapsules affects various properties of the encapsulant, as it indicates the amount of various carrier material on which the encapsulant is constructed. Reactivity and stability are directly related to the size of the microcapsules. Another important property affected by the size of the resulting microcapsules is sedimentation in the dispersion of the product and during application. Formulations according to this disclosure surprisingly exhibit good pheromone release rate characteristics, and the capsules do not sediment in accelerated storage stability tests.

[0035] In some embodiments, the microcapsules have a d90 value in the range of about 30 μm to about 60 μm. In some embodiments, the microcapsules have a d90 value in the range of about 35 μm to about 50 μm.

[0036] In some embodiments, the microcapsules have a d90 value of at least 30 μm, at least 31 μm, at least 32 μm, at least 33 μm, at least 34 μm, at least 35 μm, at least 36 μm, at least 37 μm, at least 38 μm, at least 39 μm, at least 40 μm, at least 41 μm, at least 42 μm, at least 43 μm, at least 44 μm, at least 45 μm, at least 46 μm, at least 47 μm, at least 48 μm, at least 49 μm, at least 50 μm, at least 51 μm, at least 52 μm, at least 53 μm, at least 54 μm, at least 55 μm, at least 56 μm, at least 57 μm, at least 58 μm, or at least 59 μm. In some embodiments, the microcapsules have a d90 value of up to 31 μm, up to 32 μm, up to 33 μm, up to 34 μm, up to 35 μm, up to 36 μm, up to 37 μm, up to 38 μm, up to 39 μm, up to 40 μm, up to 41 μm, up to 42 μm, up to 43 μm, up to 44 μm, up to 45 μm, up to 46 μm, up to 47 μm, up to 48 μm, up to 49 μm, up to 50 μm, up to 51 μm, up to 52 μm, up to 53 μm, up to 54 μm, up to 55 μm, up to 56 μm, up to 57 μm, up to 58 μm, up to 59 μm, or up to 60 μm.

[0037] In some embodiments, the microcapsules have a d50 value in the range of about 10 μm to about 30 μm. In some embodiments, the microcapsules have a d50 value in the range of about 15 μm to about 25 μm. In some embodiments, the microcapsules have a d50 value in the range of about 20 μm to about 22 μm.

[0038] In some embodiments, the microcapsules have a d10 value in the range of about 1 μm to about 7 μm.

[0039] In general, compositions relating to this disclosure may contain any suitable additives known in the art that facilitate the compositions described herein. The compositions may include encapsulated and / or unencapsulated additives. In some embodiments, the composition includes at least one additive. In some embodiments, the composition includes at least two additives. In some embodiments, the composition includes at least three additives. In some embodiments, the composition includes at least four additives.

[0040] In some embodiments, the additives are selected from dispersants, surfactants, emulsifiers, wetting agents, biocides, defoamers, antifreezes, rheological modifiers, solvents, stabilizers, UV stabilizers, UV absorbers, salts, excipients, antioxidants, and combinations thereof.

[0041] In some embodiments, the additives include xanthan gum (e.g., Rhodopol 23, Kelzan S), clay, smectite clay, bentonite clay, hectorite clay, magnesium aluminosilicate clay (e.g., Acti-Gel 208, Veegum R), organically modified hectorite clay (e.g., Bentone LF), silica (e.g., Aerosil 200), hydrophobic modified ethoxylated urethane (HEUR), hydrophobic modified anionic polyacrylate copolymer (HASE), anionic polyacrylate copolymer (ASE), rheological modifiers useful in aqueous systems (e.g., Rheovis rheological modifiers), and rheological modifiers selected from combinations thereof.

[0042] Typically, compositions conforming to this disclosure may include any suitable pheromone known in the art that facilitates the compositions described herein. In some embodiments, the pheromone is selected from aldehyde pheromones, acetate pheromones, alcohol pheromones, ketone pheromones, epoxide pheromones, hydrocarbon pheromones, ester pheromones, and combinations thereof. In some embodiments, the pheromone does not include aldehyde pheromones. Examples of pheromones include formaldehyde; 2,2-dibromoacetaldehyde; acetaldehyde; 2-methyl-2-propenal; 2-methylpropanal; 2-propenal; 3,3-dibromo-2-propenal; propanal; 2-butenal; 2-methyl-2-butenal; 2-methylbutanal; 2-methylenebutanal; 3-methyl-2-butenal; 3-methyl-3-butenal; 3-methylbutanal; butanal Naal; (E)-2-pentenal; 2-methylenepentanal; 2-pentenal; 3-methyl-1-(vinyloxy)-butane; 4-methylpentanal; 4-pentenal; 5-methylfurfural; furan-2-carbaldehyde; pentanal; (E)-2-hexenal; (E)-2-methyl-2-hexenal; (E)-3-hexenal; (E)-4-oxo-2-hexenal; (E,E)-2,4-dimethyl-2, 4-Hexadienal; (E,E)-2,4-Hexadienal; (Z)-2-Hexenal; (Z)-3-Hexenal; (Z)-4-Oxo-2-Hexenal; 1-Hexenal; 2,3-Dihydroxybenzaldehyde; 2-Hexenal; 3-((E)-2-Hexenoxy)-Hexenal; 3,5-Dimethylhexanal; 3-Ethoxyhexanal; 3-Hydroxybenzaldehyde; 3-Hydroxyhexanal; 4 -Hydroxy-3,5-dimethoxybenzaldehyde; 4-Hydroxybenzaldehyde; 5-Methylhexanal; Hexanal; (1R,2S,5R)-2-methyl-5-((R)-1-oxopropan-2-yl)-cyclopentanecarbaldehyde; (1R,2S,5S)-2-methyl-5-((R)-1-oxopropan-2-yl)-cyclopentanecarbaldehyde; (1R,5S)-6,6-dimethylbicyclo[3.1.1] Hepta-2-en-2-carbaldehyde; (1S,2S,5R)-2-methyl-5-((R)-1-oxopropan-2-yl)-cyclopentanecarbaldehyde; (3S,8R)-2-methyl-5-(1-formylethyl)-1-cyclopentene-1-carbaldehyde; (3S,8S)-2-methyl-5-(1-formylethyl)-1-cyclopentene-1-carbaldehyde; (5S,8S)-2-methyl-5-( (1-Formylethyl)-1-Cyclopentene-1-Caraldehyde; (E)-2-(2-Hydroxyethyl)-6-Methyl-2,5-Heptadienal; (E)-2-(2-Hydroxyethylidene)-6-Methyl-5-Heptenal; (E)-2-Heptenal; (E)-2-Isopropyl-5-Methyl-2-Hexanal; (E)-2-Methyl-2-Heptenal; (E,Z)-2,4-Heptadienal; (R)-2 ,6-dimethyl-5-heptenal;(S)-4-(propa-1-en-2-yl)-cyclohexa-1-encarbaldehyde;(Z)-2-isopropyl-5-methyl-2-hexenal;(Z,Z)-2,4-heptadienal;2-(3-methylcyclopentyl)-propanal;2-(3-methylcyclopentyl)-propanal;2,3,6-tribromo-4,5-dihydroxybenzaldehyde;2,3-di Bromo-4,5-dihydroxybenzaldehyde; 2,6-dimethyl-5-heptenal; 2-methoxybenzaldehyde; 2-methyl-1-cyclopentenecarboxyaldehyde; 2-methyl-2-heptenal; 2-methyl-5-(1-oxopropan-2-yl)-cyclopentanecarbaldehyde; 2-methylcyclopenta-1-encarbaldehyde; 3,3-dimethyl-5-oxo-7-oxabicyclo[4.1.0]Heptane-1-carbaldehyde; 3,4-dimethylbenzaldehyde; 3,5-dibromo-4,5-dihydroxybenzaldehyde; 3,5-dibromo-4-hydroxybenzaldehyde; 3-bromo-4,5-dihydroxybenzaldehyde; 3-bromo-4-hydroxybenzaldehyde; 3-bromo-5-hydroxy-4-methoxybenzaldehyde; 3-hydroxybenzene-1,2-dicarbaldehyde; 3- Methylbenzaldehyde; 4-(heptyloxy)-butanal; 4-methoxybenzaldehyde; 5-(1-formylethyl)-2-methyl-2-cyclopentene-1-carbaldehyde; 6-methyl-5-heptenal; 6-methylheptanal; benzaldehyde; cartilagineal; cyclohexanedial; heptanal; taxifolial D; (1R ,2S)-cis-2-isopropenyl-1-methylcyclobutaneethanal;(1S,2R,3S)-2-(1-formylvinyl)-5-methylcyclopentanecarbaldehyde;(1S,2S,3S)-2-(1-formylvinyl)-5-methylcyclopentanecarbaldehyde;(2Z,6E)-8-chloro-6-chloromethyl-2-methyl-2,6-octadienal;(4S)-(3-oxopropane-1-2- (E)-Cyclohexa-1-encarbaldehyde; (E)-(3,3-dimethyl)-cyclohexylideneacetaldehyde; (E)-2-(3,3-dimethylcyclohexylidene)-acetaldehyde; (E)-2-(4-methyl-3-pentenyl)-butanedial; (E)-2-(4-methyl-3-pentenylidene)-butanedial; (E)-2,7-octadienal; (E)-2-methyl-2-octenal; (E)-2-methyl-5-(3-furyl)-2-pentenal; (E)-2-octenal; (E)-3,7-dimethyl-2,6-octadienal; (E)-3,7-dimethyl-2,6-octadienal; (E)-3-octenal; (E)-4-oxo-2-octenal; (E)-7-methyl-2-octenal; (E,E)-2,4-octadienal; (E,E)-2,6-dimethyl-8-hydroxy-2,6-octadienal; (E,E)-2,6-octadienal; (E,E)-2,6-octadienedial; (E ,Z)-2,4-octadienal;(E,Z)-2,6-octadienal;(R)-1,2-dimethyl-3-methylenecyclopentylacetaldehyde;(R)-3,7-dimethyl-6-octenal;(Z)-(3,3-dimethyl)-cyclohexylideneacetaldehyde;(Z)-2-(3,3-dimethylcyclohexylidene)acetaldehyde;(Z)-3,7-dimethyl-2,6-octadienal;(Z,E)-3,7-dimethyl-2,6-octadienal;1-octenal;2-(1-formylvinyl)-5-me Tylcyclopentanecarbaldehyde; 2-(3,4-dihydroxyphenyl)-2-oxoacetaldehyde; 2,6,6-trimethyl-1-cyclohexene-1-carbaldehyde; 2-ethyloctanal; 2-hydroxy-6-methylbenzaldehyde; 2-methylbenzaldehyde; 2-methyl-5-(1-formylethyl)-1-cyclopentene-1-carbaldehyde; 2-octenal; 2-phenylacetaldehyde; 2-phenylpropenal; 3,4-dihydroxyphenylglyoxal; 3,7-dimethyl-6-oc Thenal; 3-Ethoxy-4-hydroxybenzaldehyde; 3-Ethylbenzaldehyde; 3-Isopropyl-6-methylbenzaldehyde; 3-Octenal; 3-Oxo-4-Isopropyridene-1-Cyclohexene-1-Carboxaldehyde; 4-Ethylbenzaldehyde; 4-Hydroxy-2-Methylbenzaldehyde; 4-Hydroxy-3-Methoxybenzaldehyde; 4-Isopropenyl-1-Cyclohexene-1-Caraldehyde; 4-Isopropenyl-3-Oxo-1-Cyclohexene-1-Carboxaldehyde;4S-4-isopropenyl-3-oxo-1-cyclohexene-1-carboxyaldehyde; 5-ethylcyclopenta-1-ene-carbaldehyde; 6,6-dimethylbicyclo[3.1.1]hepta-2-ene-2-carbaldehyde; 6-methyloctanal; 7-methyloctanal; anisomorphal; cis-2-isopropenyl-1-methylcyclobutaneethanal; octanal; peruphasmal; (1R,2S,6R)-2,6-dimethyl-3-oxabicyclo[4. 2.0] Octane-2-carbaldehyde; (E)-2-methyl-2-nonenal; (E)-2-nonenal; (E)-3-phenyl-2-propenal; (E)-4,8-nonadienal; (E)-8-methyl-2-nonenal; (E,E)-2,4-nonadienal; (E,E,E)-2,4,6-nonatrienal; (E,E,Z)-2,4,6-nonatrienal; (E,Z,Z)-2,4,6-nonatrienal; (Z)-2-methyl-2-nonenal; (Z)-3-nonenal; (Z)-4,8- Nonadienal; (Z)-4-nonenal; (Z)-8-methyl-2-nonenal; 2,6-nonadienal; 2-formyl-3-methylcyclopenteneacetaldehyde; 2-nonenal; 2-phenyl-2-butenal; 3-(4-methoxyphenyl)-2-propenal; 3,5-di-tert-butyl-4-hydroxybenzaldehyde; 3-phenyl-2-propenal; 3-phenylpropanal; 6-ethylbenzaldehyde; 7,7-dimethylbicyclo[4.1.0]hepta-3-ene-3-carbaldehyde; 7-methylnonana 7-methylnonanal; 8-methylnonanal; 9-acetyloxynonanal; Gibepyrone C; nonanal; (4R,8R)-4,8-dimethyldecanal; (4R,8S)-4,8-dimethyldecanal; (E)-17,18,19,20-Tetranorloba-8,10,13(15)-trien-16-al; (E)-2,9-decadienal; (E)-2-decenal; (E)-2-methyl-2-decenal;(E)-2-methyl-3-(2,3-dibromo-4,5-dihydroxyphenyl)-propenal; (E)-4-oxo-2-decenal; (E)-8-hydroxy-4,8-dimethyl-4,9-decadienal; (E)-9-methyl-2-decenal; (E,E)-2,4-decadienal; (E,Z)-2,4-decadienal; (Z)-4-decenal; (Z)-5-decenal; (Z)-9-methyl-2-decenal; (Z,Z)-2,4-decadienal; 1-decena 4,5-dimethyldecanal; 2-decenal; 2-ethyldecanal; 3-(2,3-dibromo-4,5-dihydroxyphenyl)-2-methylpropanal; 4,5-dimethyldecanal; 4,8-dimethyldecanal; Caraibical; decanal; Rogiolal; (2E,4E)-2,6,10-trimethylundecal-2,4,9-trienal; (2E,4E,7Z)-2,6,10-trimethylundecal-2,4,7,9-tetraenal; (5E)-2,6,10-trimethylundeca-5,9-dienal; (E)-2-undecenal; (E)-6-ethyl-2,10-dimethyl-5,9-undecadienal; (Z)-4-undecenal; 10-undecenal; 2-butyl-2-octenal; 2-undecenal; 3-isopropyl-6-methyl-10-oxoundeca-2,6-dienal; 5-methyl-2-phenyl-2-hexanal; 8-isopropyl-5-methyl-3,4,4a,5,6,7,8,8a-octahydronaphthalene-2-carbaldehyde; Austrodoral; oxytocin 1; syn-4,6-dimethylundecanal; taxifolial A; taxifolial B; taxifolial C; undecanal; (1R,6R,7S,10R)-1-hydroxy-4-cadinene-15-al; (2R,7S,11R)-7-acetoxy-2-hydroxynardosin-1(10)-en-12-al; (3 (R,5R,9R)-3,5,9-trimethyldodecanal; (3S,6E)-7-ethyl-3,11-dimethyldodeca-6,10-dienal; (9R)-3,5,9-trimethyldodecanal; (E)-10-dodecenal; (E)-2-dodecenal; (E)-3,7,11-trimethyl-6,10-dodecadienal; (E)-5-dodecenal; (E)-6-dodecenal; (E)-7-dodecenal; (E)-8-dodecenal; (E)-9,11-dodecadienal; (E)-9-dodecenal; (E,E)-3,7,11-to Rimethyl-2,6,10-dodecadienal; (E,E)-7-ethyl-3,11-dimethyl-2,6,10-dodecadienal; (E,E)-8,10-dodecadienal; (E,E,E)-3,7-dimethyl-8,11-dioxo-2,6,9-dodecadienal; (E,E,Z)-3,7-dimethyl-8,11-dioxo-2,6,9-dodecadienal; (E,Z)-2,6-dodecadienal; (E,Z)-5,7-dodecadienal; (E,Z)-7,9-dodecadienal; (E,Z)-8,10-dodecadienal;(R)-10-oxo-isodauc-3-en-15-al((R)-10-oxo-isodauc-3-en-15-al);(S,E)-3,7,11-trimethyl-6,10-dodecadienal;(Z)-2-methyl-5-((1R,5R,6S)-2,6-dimethylbicyclo[3.1.1]hepta-2-en-6-yl)-penta-2-enal;(Z)-5-dodecenal;(Z)-7-dodecenal;(Z)-9,11-dodecadienal;(Z)-9-dodecenal;(Z,E)-3,7,11-trimethyl-2, 6,10-Dodecatrienal; (Z,E)-5,7-Dodecadienal; (Z,E)-7-Ethyl-3,11-dimethyl-2,6,10-Dodecatrienal; (Z,E)-8,10-Dodecadienal; (Z,Z)-5,7-Dodecadienal; 10-Methyldodecanal; 2,10-Dibromo-3-Chloro-7-Camigren; 2-Dodecenal; 2-Ethyldodecanal; 2-Formylguaiazulene; 3,7,11-Trimethyl-(E)-6,10-Dodecadienal; 5-Hydroxy-8-Methoxycalamane-15-R (5-hydroxy-8-methoxycalamanen-15-al); 5-hydroxy-8-methoxycalamanen-15-al; Aplysinal; Debromoaplysinal; Dodecanal; Parahigginol D; Polygodial; Sclerosporal; Sinuketal; syn-4,6-dimethyldodecanal; trans-calamenene-13- R; (3R,5S,9R,7E,11E)-3,5,9,11-tetramethyl-7,11-tridecadienal; (3S,4R,6E,10Z)-3,4,7,11-tetramethyl-6,10-tridecadienal; (E,E)-3,5,9,11-tetramethyltrideca-7,11-dienal; (Z)-4-tridecenal; 13,14,15,16-tetranorclerod-3-en-12-al; 13-acetyloxytridecanal;4,6-Bis(4-methylpenta-3-en-1-yl)-6-methylcyclo-1,3-hexadienecarbaldehyde; Acanthodoral; Ancistrodial; Cespitulin F; Isoacanthodoral; Tridecanal; (E)-11,13-Tetradecadienal; (E)-11-Tetradecenal; (E,E)-8,10-Tetradecadienal; (E,Z)-4,9-Tetradecadienal; (E,Z)-8,10-Tetradecadienal; (Z)-11,13-Tetradecadienal; (Z)-11-Tetradecenal; ( Z)-5-tetradecenal; (Z)-7-tetradecenal; (Z)-8-tetradecenal; (Z)-9,13-tetradecadien-11-inal; (Z)-9-tetradecenal; (Z,E)-9,11,13-tetradecatrienal; (Z,E)-9,11-tetradecadienal; (Z,E)-9,12-tetradecadienal; (Z,Z)-5,8-tetradecadienal; (Z,Z)-8,10-tetradecadienal; (Z,Z)-9,11-tetradecadienal; 10,12-tetradecadienal; 2,4-tetradecadienal; 2-ethyltetradecanal; 3-oxo-13-tetradecenal; 3-oxo-tetradecanal; 5,8-Tetradecadienal; 5-Tetradecenal; Norasperenal A; Norasperenal B; Norasperenal C; Norasperenal D; Sargasal I; Sargasal II; Tetradecanal; (6R)-6-Acetoxidichotoma-3,14-diene-1,17-dial; (6R)-6-Hydroxydichotoma-3,14-diene-1,17-dial; (E,E)-3,7,11,15 -Tetramethyl-6,10,14-hexadecatrienal; (E,Z)-6,8-pentadecadienal; (E,Z)-9,11-pentadecadienal; (E,Z,Z)-2,6,9-pentadecadienal; (Z)-10-pentadecenal; (Z)-2-chloropentadeca-2-enal; (Z)-6,14-pentadecadienal; (Z,Z)-6,9-pentadecadienal; (Z,Z)-9,11-pentadecadienal; 2-hexyl-2-decenal; Azamial A; Azamial B; Isopaquidicthiolar ( Isopachydictyolal; Pentadecanal; Sinularial A; Umbellacin A; Xeniafaraunol A; (1R)-Pimaral; (E)-10-Hexadecenal; (E)-11-Hexadecenal; (E)-14-Hexadecenal; (E)-14-Methyl-8-Hexadecenal; (E)-3,7,11,15-Tetramethyl-2-Hexadecenal; (E,E)-10,12-Hexadecadienal; (E,E)-1 0,14-Hexadecadienal; (E,E)-11,13-Hexadecadienal; (E,E)-9,11-Hexadecadienal; (E,E,E)-10,12,14-Hexadecatrienal; (E,E,E)-3,7,11,15-Tetramethyl-2,6,10,14-Hexadecatetraenal; (E,E,Z)-10,12,14-Hexadecatetraenal; (E,E,Z)-4,6,11-Hexadecatetraenal; (E,E,Z,Z)-4,6,11,13-Hexadecatetraenal; (E,Z)-10,12-Hexadecadienal;(E,Z)-11,13-Hexadecadienal; (E,Z)-4,6-Hexadecadienal; (E,Z)-6,11-Hexadecadienal; (E,Z)-8,11-Hexadecadienal; (E,Z)-9,11-Hexadecadienal; (R)-(E)-14-Methyl-8-Hexadecenal; (R)-(Z)-14-Methyl-8-Hexadecenal; (S)-(E)-14-Methyl-8-Hexadecenal; (S)-(Z)-14-Methyl-8-Hexadecenal; (Z)-10-Hexadecenal; (Z)-11-Hexadecenal; (Z)-12-Hexadecenal; (Z)-13-Hexadecene-11-Inal; (Z)-14-Methyl-8-Hexadecenal; (Z)-3,7,11,15-Tetramethyl-2-Hexadecenal; (Z)-3-Oxo-9-Hexadecenal; (Z)-7-Hexadecenal; (Z)-9-Hexadecenal; (Z,E)-10,12-Hexadecadienal; (Z,E)-11,13-Hexadecadienal; (Z,E)-7,11-Hexadecadienal; (Z,E)-9,11-Hexadecadienal; (Z,Z)-10,12-Hexadecadienal Sadecadienal; (Z,Z)-11,13-Hexadecadienal; (Z,Z)-7,10-Hexadecadienal; (Z,Z)-7,11-Hexadecadienal; (Z,Z)-9,11-Hexadecadienal; (Z,Z,E)-7,11,13-Hexadecatrienal; 11-Hexadecenal; 11-Hexadecinal; 13(16),14-Spongiadien-19-al; 2-Methylhexadecanal; 7-Hexadecenal; 9-Hexadecenal; Deacetyl -Dihydro-nor-thuridillonal; Dictyodial A; Dihydro-nor-thuridillonal; Hexadecanal; Keikipukalide A; Keikipukalide B; Keikipukalide C; Keikipukalide D; Keikipukalide E; Nor-thuridillonal; Pseudoplexaural;Pukalide aldehyde; Sanadaol; (E)-2-tridecyl-2-heptadecenal; (Z)-9-heptadecenal; 1-heptadecenal; 2-heptadecenal; Globostelletin C; Globostelletin D; heptadecanal; (E)-11-octadecenal; (E)-13-octadecenal; (E)-14-octadecenal; (E)-2-octadecenal Lu; (E)-6-octadecenal; (E,E)-11,14-octadecadienal; (E,Z)-2,13-octadecadienal; (E,Z)-3,13-octadecadienal; (E,Z)-6,11-octadecadienal; (Z)-11-octadecenal; (Z)-13-octadecenal; (Z)-9-octadecenal; (Z,E)-13,15-octadecadienal; (Z,Z)-11,13-octadecadienal; (Z,Z )-13,15-octadecadienal; (Z,Z)-3,13-octadecadienal; (Z,Z)-9,12-octadecadienal; (Z,Z,Z)-9,12,15-octadecatrienal; 11-octadecenal; 13,15-octadecadienal; 13-octadecenal; 16-methyloctadecanal; 1-octadecenal; 3,6-dihydroxy-24-nor-9-oxo-9,11-secocholesta-7,22-diene-1 1-al; 9-octadecenal; methyloctadecanal; octadecanal; panicein B2; panicein B3; panicein C; (Z)-10-nonadecanal; (Z)-9-nonadecanal; 9(11)-Pargueren-16-al; hyrtiosal; nonadecanal; (2E,6Z,9Z)-2-methyl-2,6,9-eicosatrienal; (Z)-11-eicocenal; 11-eicocenal; 12,18-di-episcalaradial; 12b-(3'b-Hydroxybutanoyloxy)-20,24-dimethyl-24-oxo-scalara-16-en-25-al; 12b-(3'b-Hydroxypentanoyloxy)-20,24-dimethyl-24-oxo-scalara-16-en-25-al Examples include 12-deacetoxy-12-oxo-scalarradial; 12-episcalarradial; 15-eicocenal; 1-eicocenal; 3-deacetyl-22,23-dihydro-24,28-dehydrolfasterol B; 3-deacetyllfasterol B; 9-eicocenal; Anthogorgiene B; deacetylscalarradial; eicosadienal; eicosanal; Mooloolabene A; Mooloolabene B; scalarradial; and combinations thereof.

[0043] Notable pheromones include (Z)-5-decenyl acetate, dodecanyl acetate, (Z)-7-dodecenyl acetate, (E)-7-dodecenyl acetate, (Z)-8-dodecenyl acetate, (E)-8-dodecenyl acetate, (Z)-9-dodecenyl acetate, (E)-9-dodecenyl acetate, (E)-10-dodecenyl acetate, 11-dodecenyl acetate, (Z)-9,11-dodecadienyl acetate, (E)-9,11- Dodecadienyl acetate, (Z)-11-tridecenyl acetate, (E)-11-tridecenyl acetate, tetradecanyl acetate, (E)-7-tetradecenyl acetate, (Z)-8-tetradecenyl acetate, (E)-8-tetradecenyl acetate, (Z)-9-tetradecenyl acetate, (E)-9-tetradecenyl acetate, (Z)-10-tetradecenyl acetate, (E)-10-tetradecenyl acetate, (Z)-11-tetradecenyl acetate, (E)-11-tetradecenyl acetate, (Z)-12-pentadecenyl acetate, (E)-12-pentadecenyl acetate, hexadecanyl acetate, (Z)-7-hexadecenyl acetate, (Z)-11-hexadecenyl acetate, (E)-11-hexadecenyl acetate, octadecanyl acetate, (E,Z)-7,9- Dodecadienyl acetate, (Z,E)-7,9-dodecadienyl acetate, (E,E)-7,9-dodecadienyl acetate, (Z,Z)-7,9-dodecadienyl acetate, (E,E)-8,10-dodecadienyl acetate, (E,Z)-9,12-dodecadienyl acetate, (E,Z)-4,7-tridecadienyl acetate, (E,E)-9,11-tetradecadienyl acetate, (Z,Z)-9,12-tetradecadienyl acetate, (Z,Z)-7,11-hexadecadienyl acetate, (E,Z)-7,11-hexadecadienyl acetate, (Z,E)-7,11- Hexadecadienyl acetate, (E,E)-7,11-hexadecadienyl acetate, (Z,E)-3,13-octadecadienyl acetate, (E,Z)-3,13-octadecadienyl acetate, (E,E)-3,13-octadecadienyl acetate, decanol, (Z)-6-nonenol, (E)-6-nonenol, dodecanol, (Z)-5-decenol, 11-dodecenol, (Z)-7-dodecenol, (E)-7-dodecenol, (Z)-8-dodecenol, (E)-8-dodecenol, (E)-9-dodecenol, (Z)-9-dodecenol, (E)-9,11-dodecadienol, (Z)-9,11-Dodecadienol, (Z,E)-5,7-Dodecadienol, (E,E)-5,7-Dodecadienol, (E,E)-8,10-Dodecadien-1-ol, (E,Z)-8,10-Dodecadienol, (Z,Z)-8,10-Dodecadienol, (Z,E)-8,10-Dodecadienol, (E,Z)-7,9-Dodecadienol, (Z,Z)-7,9-Dodecadienol, (E)-5-Tetradecenol, (Z)-8-Tetradecenol, (Z)-9-Tetradecenol, (E)-9-Tetradecenol, (Z)-10-Tetradecenol, ( (Z)-11-tetradecenol, (E)-11-tetradecenol, (Z)-11-hexadecenol, (Z,E)-9,11-tetradecadienol, (Z,E)-9,12-tetradecadienol, (Z,Z)-9,12-tetradecadienol, (Z,Z)-10,12-tetradecadienol, (Z,Z)-7,11-hexadecadienol, (Z,E)-7,11-hexadecadienol, (E)-14-methyl-8-hexadecene-1-ol, (Z)-14-methyl-8-hexadecene-1-ol, (E,E)-10,12-hexadeca Dienol, (E,Z)-10,12-hexadecadienol, dodecanal, (Z)-9-dodecanal, tetradecenal, (Z)-7-tetradecenal, (Z)-9-tetradecenal, (Z)-11-tetradecenal, (E)-11-tetradecenal, (E)-11,13-tetradecadienal, (E,E)-8,10-tetradecadienal, (Z,E)-9,11-tetradecadienal, (Z,E)-9,12-tetradecadienal, hexadecanal, (Z)-8-hexadecenal, (Z)-9-hexadecenal, (Z) -10-Hexadecenal, (E)-10-Hexadecenal, (Z)-11-Hexadecenal, (E)-Hexadecenal, (Z)-12-Hexadecenal, (Z)-13-Hexadecenal, (Z)-14-Methyl-8-Hexadecenal, (E)-14-Methyl-8-Hexadecenal, (Z,Z)-7,11-Hexadecadienal, (Z,E)-7,11-Hexadecadienal, (Z,E)-9,11-Hexadecadienal, (E,E)-10,12-Hexadecadienal, (E,Z)-10,12-Hexadecadienal, (Z,Examples include E)-10,12-hexadecadienal, (Z,Z)-10,12-hexadecadienal, (Z,Z)-11,13-hexadecadienal, octadecenal, (Z)-11-octadecenal, (E)-13-octadecenal, (Z)-13-octadecenal, (Z)-5-decenyl 3-methylbutanoate, and (+)cis-7,8-epoxy-2-methyloctadecane.

[0044] Other notable pheromones include citral; geranial; neral; tetradecane-1-R; pentadecane-1-R; pentadecene-1-R; hexadecane-1-R; (Z)-9-hexadecene-1-R; (Z)-11-hexadecene-1-R; (7E,9E)-undeca-7,9-diene-1-R; (11Z,13Z)-hexadecadiene-1-R; (9Z,12E)-tetradecadiene-1-R; (8E,10E)-dodecadiene-1-A Examples include: (11Z)-hexadecadiene-1-arl; (9Z)-tetradecene-1-arl; 6,10-dimethyl-5,9-undecadiene-2-ol; (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene; [1S-(1a,2b,5a)]-4,6,6-trimethyl-bicyclo[3.1.1]hepta-3-en-2-ol; 10-hexadecenal; (Z)-10-hexadecenal; (E)-10-hexadecenal; and combinations thereof.

[0045] In some embodiments, the pheromone is (Z)-5-decenyl acetate, dodecanyl acetate, (Z)-7-dodecenyl acetate, (E)-7-dodecenyl acetate, (Z)-8-dodecenyl acetate, (E)-8-dodecenyl acetate, (Z)-9-dodecenyl acetate, (E)-9-dodecenyl acetate, (E)-10-dodecenyl acetate, 11-dodecenyl acetate, (Z)-9,11-dodecadienyl acetate, (E)-9,11-dodecadienyl acetate, (Z)-11-tridecenyl acetate, (E)-11-tridecenyl acetate, tetradecanyl acetate, (E) acetate -7-tetradecenyl acetate, (Z)-8-tetradecenyl acetate, (E)-8-tetradecenyl acetate, (Z)-9-tetradecenyl acetate, (E)-9-tetradecenyl acetate, (Z)-10-tetradecenyl acetate, (E)-10-tetradecenyl acetate, (Z)-11-tetradecenyl acetate, (E)-11-tetradecenyl acetate, (Z)-12-pentadecenyl acetate, (E)-12-pentadecenyl acetate, hexadecanyl acetate, (Z)-7-hexadecenyl acetate, (Z)-11-hexadecenyl acetate, (E)-11-hexadecenyl acetate, Octadecanyl acetate, (E,Z)-7,9-dodecadienyl acetate, (Z,E)-7,9-dodecadienyl acetate, (E,E)-7,9-dodecadienyl acetate, (Z,Z)-7,9-dodecadienyl acetate, (E,E)-8,10-dodecadienyl acetate, (E,Z)-9,12-dodecadienyl acetate, (E,Z)-4,7-tridecadienyl acetate, (E,E)-9,11-tetradecadienyl acetate, (Z,Z)-9,12-tetradecadienyl acetate, (Z,Z)-7,11-hexadecadienyl acetate, (E,Z)-7,11-hex Selected from sadecadienyl, (Z,E)-7,11-hexadecadienyl acetate, (E,E)-7,11-hexadecadienyl acetate, (Z,E)-3,13-octadecadienyl acetate, (E,Z)-3,13-octadecadienyl acetate, (E,E)-3,13-octadecadienyl acetate, (Z)-5-decenyl 3-methylbutanoate, (+)cis-7,8-epoxy-2-methyloctadecane, methyl(E,Z)-2,4-decadienate, methyl 2,6,10-trimethyltridecanoate, and combinations thereof.

[0046] In some embodiments, the pheromone load level relative to the entire formulation is in the range of about 5% to about 30% by mass. In some embodiments, the pheromone load level relative to the entire formulation is in the range of about 10% to about 25% by mass. In some embodiments, the pheromone load level relative to the entire formulation is in the range of about 15% to about 25% by mass. The process for achieving a desired load level includes dissolving the pheromone in an organic phase containing a solvent and an isocyanate monomer, then dispersing the organic phase in a second immiscible phase and adding an amine monomer thereto. The isocyanate monomer and the amine monomer react on the droplet surface to form a polymer film.

[0047] In some embodiments, the pheromone load level to the entire formulation is at least about 5% by mass, at least about 6% by mass, at least about 7% by mass, at least about 8% by mass, at least about 9% by mass, at least about 10% by mass, at least about 11% by mass, at least about 12% by mass, at least about 13% by mass, at least about 14% by mass, at least about 15% by mass, at least about 16% by mass, at least about 17% by mass, at least about 18% by mass, at least about 19% by mass, at least about 20% by mass, at least about 21% by mass, at least about 22% by mass, at least about 23% by mass, at least about 24% by mass, at least about 25% by mass, at least about 26% by mass, at least about 27% by mass, at least about 28% by mass, or at least about 29% by mass. In some embodiments, the pheromone load level relative to the entire formulation is up to about 6% by mass, up to about 7% by mass, up to about 8% by mass, up to about 9% by mass, up to about 10% by mass, up to about 11% by mass, up to about 12% by mass, up to about 13% by mass, up to about 14% by mass, up to about 15% by mass, up to about 16% by mass, up to about 17% by mass, up to about 18% by mass, up to about 19% by mass, up to about 20% by mass, up to about 21% by mass, up to about 22% by mass, up to about 23% by mass, up to about 24% by mass, up to about 25% by mass, up to about 26% by mass, up to about 27% by mass, up to about 28% by mass, up to about 29% by mass, or up to about 30% by mass.

[0048] In some embodiments, the percentage of pheromones in the organic phase is in the range of about 10% by mass to about 100% by mass. In some embodiments, the percentage of pheromones in the organic phase is in the range of about 50% by mass to about 100% by mass. In some embodiments, the percentage of pheromones in the organic phase is in the range of about 70% by mass to about 100% by mass.

[0049] In some embodiments, the percentage of pheromone in the organic phase is at least about 10% by mass, at least about 15% by mass, at least about 20% by mass, at least about 25% by mass, at least about 30% by mass, at least about 35% by mass, at least about 40% by mass, at least about 45% by mass, at least about 50% by mass, at least about 55% by mass, at least about 60% by mass, at least about 65% by mass, at least about 70% by mass, at least about 75% by mass, at least about 80% by mass, at least about 85% by mass, at least about 90% by mass, or at least about 95% by mass. In some embodiments, the percentage of pheromones in the organic phase is up to about 10% by mass, up to about 15% by mass, up to about 20% by mass, up to about 25% by mass, up to about 30% by mass, up to about 35% by mass, up to about 40% by mass, up to about 45% by mass, up to about 50% by mass, up to about 55% by mass, up to about 60% by mass, up to about 65% by mass, up to about 70% by mass, up to about 75% by mass, up to about 80% by mass, up to about 85% by mass, up to about 90% by mass, up to about 95% by mass, or up to about 100% by mass.

[0050] In some embodiments, the percentage of the wall material (isocyanate + amine) relative to the organic phase is in the range of about 3% by mass to about 20% by mass. In some embodiments, the percentage of the wall material (isocyanate + amine) relative to the organic phase is in the range of about 7% by mass to about 15% by mass. In some embodiments, the percentage of the wall material (isocyanate + amine) relative to the organic phase is in the range of about 10% by mass to about 16% by mass. In some embodiments, the percentage of the wall material (isocyanate + amine) relative to the organic phase is in the range of about 8% by mass to about 12% by mass.

[0051] In some embodiments, the percentage of the wall material (isocyanate + amine) relative to the organic phase is at least about 3% by mass, at least about 4% by mass, at least about 5% by mass, at least about 6% by mass, at least about 7% by mass, at least about 8% by mass, at least about 9% by mass, at least about 10% by mass, at least about 11% by mass, at least about 12% by mass, at least about 13% by mass, at least about 14% by mass, at least about 15% by mass, at least about 16% by mass, at least about 17% by mass, at least about 18% by mass, or at least about 19% by mass. In some embodiments, the percentage of the wall material (isocyanate + amine) relative to the organic phase is up to about 4% by mass, up to about 5% by mass, up to about 6% by mass, up to about 7% by mass, up to about 8% by mass, up to about 9% by mass, up to about 10% by mass, up to about 11% by mass, up to about 12% by mass, up to about 13% by mass, up to about 14% by mass, up to about 15% by mass, up to about 16% by mass, up to about 17% by mass, up to about 18% by mass, up to about 19% by mass, or up to about 20% by mass.

[0052] Typically, compositions according to this disclosure may include any suitable solvent known in the art that facilitates the compositions described herein. The solvent may be a single solvent or a mixture of solvents. In some embodiments, the solvent is selected from hydrophobic solvents including high flash point solvents, methylated seed oils, methyl methyl oleate oils, methyl methyl linoleate oils, mineral oils, paraffinic oils, tall oil fatty acid-based solvents, aromatic solvents (e.g., Aromatic 200, Aromatic 200ND), aromatic ester solvents, polybutenes, methyl esters of fatty acids, tributyl 2-acetate citrate, alkylamides (e.g., Agnique AMD10), benzyl acetate, wax esters, and combinations thereof. In some embodiments, the solvent includes methyl methyl oleate oil and methyl methyl linoleate oil. In some embodiments, the solvent includes hydrophobic solvents, methylated seed oils, mineral oils, paraffinic oils, tall oil fatty acid-based solvents, aromatic solvents, aromatic ester solvents, polybutenes, methyl esters of fatty acids, tributyl 2-acetate citrate, alkylamides, benzyl acetate, wax esters, and solvents selected from combinations thereof.

[0053] In some embodiments, the pheromone and the solvent are sealed separately. In some embodiments, the pheromone and the solvent are co-sealed. In some embodiments, the pheromone and the solvent are co-sealed together with at least one additive.

[0054] Typically, compositions conforming to this disclosure may include any suitable antifreeze known in the art that facilitates the compositions described herein. In some embodiments, the antifreeze is selected from propylene glycol, glycerin, glycol, ethylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, methanol, ethanol, propanol, butanol, and combinations thereof. In some embodiments, the antifreeze is not encapsulated. In some embodiments, a portion of the antifreeze is encapsulated.

[0055] Typically, compositions conforming to this disclosure may include any suitable microcapsule shell material known in the art that facilitates the compositions described herein. In some embodiments, the microcapsule shells include materials selected from synthetic polymers, polyureas, polyurethanes, polyacrylates, polyamides, polyvinyl alcohols, polyvinylpyrrolidones, semi-synthetic materials, modified celluloses, modified starch derivatives, natural materials, gum arabic, agar, dextrins, alginic acid, alginates, biodegradable natural polymers, collagen, polysaccharides, starches, dextrins, waxes, chitosans, arginates, celluloses, gelatins, their derivatives, and combinations thereof.

[0056] In some embodiments, when the shell contains polyurea, the polyurea is formed from amines and isocyanates. Suitable amines include diamines, hexamethylenediamine (HMDA), 1,4-diaminobutane, 1,3-diaminopropane, ethylenediamine (EDA), 1,4-cyclohexanediamine, 1,3-cyclohexanebis(methylamine), m-xylylenediamine, and combinations thereof. Suitable isocyanates include polyisocyanates and polyisocyanate prepolymers, e.g., polymethylene polyphenyl isocyanate (e.g., PAPI27), polymer diphenylmethane diisocyanate (MDI) (e.g., Rubinate M or Suprasec 5025), xylylenediisocyanate (XDI)-based isocyanates, (but not limited to Takenate) TM 500 (XDI), Takenate TM 600 (Hydrogenated XDI), Takenate TM D-110N (additive of XDI and trimethylolpropane), Takenate TM D-131N (XDI trimer), and Takenate TM Examples include D-120 (containing hydrogenated XDI and trimethylolpropane adducts), polyisocyanate-polyol adducts, and polyfunctional aliphatic isocyanates.

[0057] In some embodiments, the composition is a pesticide composition. In some embodiments, the composition is in a form selected from a premix and a tank mix. In some embodiments, the composition is a sprayable composition.

[0058] Compositions according to this disclosure may be any suitable form of compositions known in the art that facilitate the compositions described herein. Particularly preferred formulations of compositions according to this disclosure are capsule suspension concentrates (CS), mixed formulations (ZC) comprising a mixture of a flowable formulation (SC) and a capsule suspension concentrate (CS), mixed formulations (ZW) comprising a mixture of an emulsion formulation (eW) and a capsule suspension concentrate (CS), and mixed formulations (ZE) comprising a mixture of a suspension emulsion formulation (SE) and a capsule suspension concentrate (CS).

[0059] In some embodiments, the composition is in the form of a CS formulation, a ZC formulation, a ZW formulation, or a ZE formulation.

[0060] Sprayable formulations are typically diluted in a suitable medium before application. Such formulations are formulated to be easily diluted in the application medium (usually water, but sometimes another suitable medium such as aromatic or paraffinic hydrocarbons or vegetable oil). Application rates can range from approximately 1,000 to several thousand liters per hectare, but more commonly, from approximately 10 to several hundred liters per hectare. Sprayable formulations can be tank-mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of plants. The formulation may be measured directly into drip irrigation systems or measured between rows during planting. The formulation can be applied to the seeds of crops and other desired vegetation as a seed treatment before planting to prevent the growth of roots and other underground plant parts and / or branches and leaves through osmotic uptake.

[0061] Compositions relating to this disclosure may be delivered by an autonomous vehicle. The autonomous vehicle may be a ground vehicle. The autonomous vehicle may operate during the day and / or at night.

[0062] Compositions according to this disclosure may be delivered by air. Compositions according to this disclosure may be delivered by unmanned vehicles or unmanned aerial vehicles (UAVs). Compositions according to this disclosure may be delivered by helicopters or fixed-wing aircraft.

[0063] Typically, compositions relating to this disclosure can be manufactured according to any suitable method known in the art that facilitates the composition described herein.

[0064] In some embodiments, a method for producing a composition is described herein, the method comprising forming a mixture comprising: an antifreeze; a pheromone; a core containing a solvent; and a microcapsule containing a shell enclosing the core, wherein the microcapsule has a d90 value of at least about 30 μm.

[0065] In some embodiments, the method further includes encapsulating the pheromone and solvent in microcapsules before forming the mixture. In these embodiments, the microcapsules are added to the mixture.

[0066] In some embodiments, the method involves encapsulating a pheromone and a solvent in microcapsules within a mixture. In these embodiments, the microcapsules are formed in situ in the mixture by known methods of interfacial polymerization. Microencapsulated formulations produced by interfacial polymerization are beneficial for at least three reasons: i) they can be easily produced on a large scale using known techniques; ii) they can be easily applied over a wide area using conventional spraying equipment; and iii) they have a number of variables that can be manipulated to control release characteristics (e.g., capsule wall thickness, capsule wall composition, capsule size, and internal composition). Typically, compositions according to this disclosure can be used for any suitable purpose known in the art that facilitates the compositions described herein.

[0067] In some embodiments, a method for controlling a pest, comprising contacting the pest or its environment with a biologically effective amount of a composition, wherein the composition comprises: an antifreeze; a pheromone; and a core containing a solvent; and a microcapsule containing a shell enclosing the core, wherein the microcapsule has a d90 value of at least about 30 μm, is described herein.

[0068] The compositions of this disclosure are useful for controlling a wide range of harmful invertebrates. These harmful organisms include invertebrates present in various environments, such as plant branches and leaves, roots, soil, harvested crops or other foods, buildings or animal hides. Examples of these harmful organisms include invertebrates that feed on branches and leaves (including leaves, stems, flowers and fruits), seeds, wood, textile fibers or animal blood or tissue, and invertebrates that thereby cause damage or injury to, for example, growing or stored crops, forests, greenhouse crops, ornamental plants, seedling crops, stored food or textile products, or houses or structures or their contents, or are harmful to animal health or public health. As will be obvious to those skilled in the art, not all compositions are equally effective against all pests at all stages of development.

[0069] Therefore, the compositions of the present disclosure are agriculturally useful for protecting crops from phytophagous harmful invertebrates and also non-agriculturally useful for protecting other horticultural crops and plants from phytophagous harmful invertebrates. This usefulness includes protecting crops and other plants (i.e., both agricultural and non-agricultural) that contain gene materials introduced by genetic engineering (i.e., genetic transformation) or modified by mutagenesis to produce advantageous traits. Examples of such traits include herbicide tolerance, resistance to phytophagous pests (e.g., insects, mites, aphids, spiders, nematodes, slugs, phytopathogenic fungi, bacteria, and viruses), improved plant growth, tolerance to adverse growth conditions, such as high or low temperature, low or high soil moisture, and high salt concentration, increased flowering or fruiting, higher yield, faster maturation, higher quality and / or nutritional value of harvested products, or improved storage or processing characteristics of harvested products. Transgenic plants can be modified to express multiple traits. Examples of plants containing traits resulting from genetic engineering or mutagenesis include varieties of corn, cotton, soybeans, and potatoes that express insecticidal Bacillus thuringiensis toxins, such as YIELD GARD (R) , KNOCKOUT (R) , STARLINK (R) , BOLLGARD (R) , NuCOTN (R) and NEWLEAF (R) , INVICTA RR2 PRO TM , and varieties of corn, cotton, soybeans, and rapeseed with herbicide tolerance, such as, ROUNDUP READY (R) , LIBERTY LINK (R) , IMI (R) , STS (R) and CLEARFIELD (R)Furthermore, examples include crops expressing N-acetyltransferase (GAT) that confer resistance to glyphosate herbicides, or crops containing an HRA gene that confers resistance to herbicides that inhibit acetolactate synthase (ALS). The compositions of this disclosure may exhibit enhanced effects through traits introduced by genetic engineering or modified by mutagenesis, and thus may enhance phenotypic expression or trait efficacy, or enhance the efficacy of current compounds and compositions in controlling harmful invertebrates. In particular, the compositions of this disclosure may exhibit enhanced effects that result in greater control of harmful invertebrates than the sum of these pests due to the phenotypic expression of toxic proteins or other natural products.

[0070] The compositions of the present disclosure may optionally include a fertilizer composition containing plant nutrients, for example, at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnesium, iron, copper, boron, manganese, zinc, and molybdenum. Of particular note is a composition containing at least one fertilizer composition containing at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, and magnesium. The compositions of the present disclosure further containing at least one plant nutrient may be in liquid or solid form. Of particular note are solid formulations in the form of granules, small rods, or tablets. A solid formulation containing a fertilizer composition can be manufactured by mixing the compositions of the present disclosure with formulation components in a fertilizer composition, and then preparing the formulation by methods such as granulation or extrusion. Alternatively, a solid formulation can be manufactured by spraying a solution or suspension of the compositions of the present disclosure in a volatile solvent onto a dimensionally stable mixture, for example, a pre-prepared fertilizer composition in the form of granules, small rods, or tablets, and then evaporating the solvent.

[0071] Non-agricultural uses refer to the control of harmful invertebrates in areas other than crop fields. Non-agricultural uses of the compositions of this disclosure include the control of harmful invertebrates in stored grains, beans and other foodstuffs, as well as in textile products such as clothing and carpets. Non-agricultural uses of the compositions of this disclosure also include the control of harmful invertebrates in ornamental plants, forests, gardens, along roadsides and railway land, and on turf soil such as lawns, golf courses and pastures. Non-agricultural uses of the compositions of this disclosure also include the control of harmful invertebrates in houses and other structures that may be inhabited by humans and / or companions, farms, ranches, zoos or other animals. Non-agricultural uses of the compositions of this disclosure also include the control of pests such as termites that may damage wood or other structural materials used in buildings.

[0072] Non-agricultural uses of the compositions of this disclosure also include protecting human and animal health by controlling parasitic or disease-transmitting harmful invertebrates. Control of animal parasites includes controlling ectoparasites that infest the surface of the host animal's body (e.g., shoulders, armpits, abdomen, inner thighs) and endoparasites that infest the inside of the host animal's body (e.g., stomach, intestines, lungs, veins, subcutaneous tissue, lymphatic tissue). Examples of ectoparasites or disease-transmitting harmful organisms include chiggers, ticks, lice, mosquitoes, flies, mites, and fleas. Examples of endoparasites include heartworms, hookworms, and helminths. The compositions of this disclosure are suitable for systemic and / or non-systemic control of ectoparasitic and disease-transmitting harmful organisms in animals. The compositions of this disclosure are suitable for dealing with ectoparasites or disease-transmitting harmful organisms. The compositions of this disclosure are suitable for dealing with parasites that infect agricultural working animals, such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, hens, turkeys, ducks, geese, and bees; pet animals and domesticated animals, such as dogs, cats, pet birds, and ornamental fish; and so-called laboratory animals, such as hamsters, guinea pigs, rats, and mice. By dealing with these parasites, mortality rates and performance degradation (with respect to meat, milk, wool, hides, eggs, honey, etc.) are reduced, and as a result, the application of the compositions of this disclosure enables more economical and simpler animal husbandry.

[0073] Examples of agricultural and non-agricultural harmful invertebrates include the eggs, larvae, and adults of lepidopteran moths, such as cutworms, root-cutting moths, and loopers of the Noctuidae family, and tobacco moths (heliothines) such as the pink stem borer (Sesamia inferens Walker), the corn stalk borer (Sesamia nonagrioides Lefebvre), the southern armyworm (Spodoptera eridania Cramer), the fall armyworm (Spodoptera frugiperda JESmith), the white-striped armyworm (Spodoptera exigua Huebner), the cotton leafworm (Spodoptera littoralis Boisduval), and the yellowstriped armyworm (Spodoptera ornithogalli). Guenee), black cutworm (Agrotis ipsilon Hufnagel), velvetbean caterpillar (Anticarsia gemmatalis Huebner), green fruitworm (Lithophane antennata Walker), cabbage armyworm (Barathra brassicae Linnaeus), soybean looper (Pseudoplusia includens Walker), cabbage looper (trichoplusia ni Huebner), tobacco budworm (Heliothis virescens) Fabricius); borers, casebearers, webworms, coneworms, cabbageworms, and skeletonizers from the Pyralidae family (e.g., European corn borer).Corn borer (Ostrinia nubilalis Huebner), navel orange worm (Amyelois transitella Walker), corn root webworm (Crambus caliginosellus Clemens), sod webworm (Pyralidae:Crambinae), for example, sod worm (Herpetogramma licarsisalis Walker), sugarcane stem borer (Chilo infuscatellus Snellen), tomato small borer (Neoleucinodes elegantalis Guenee), green leaf roller (Cnaphalocrocis medinalis Guenee), grape leaf folder (Desmia funeralis) Huebner), pickleworm (Diaphania nitidalis Stoll), cabbage center grub (Hellula hydralis Guenee), yellow stem borer (Scirpophaga incertulas Walker), white stem borer (Scirpophaga innotata Walker), top shoot borer (Scirpophaga nivella Fabricius), dark-headed rice borer (Chilo polychrysus Meyrick), striped rice borer (Chilo suppressalis Walker), cabbage cluster caterpillar (Crocidolomia binotalis)Zeller); leafrollers, budworms, seed worms, and fruit worms of the Tortricidae family (e.g., codling moth (Cydia pomonella Linnaeus), grapeberry moth (Paralobesia viteana Clemens), pear dwarf moth (Grapholita molesta Busck), citrus false codling moth (Cryptophlebia leucotreta Meyrick), citrus borer (Gymnandrosoma aurantianum Lima), redbanded leafroller (Argyrotaenia velutinana Walker), obliquebanded leafroller (Choristoneura rosaceana Harris), and light brown leafroller (Choristoneura rosaceana Harris). Apple moth (Epiphyas postvittana Walker), European grape berry moth (Eupoecilia ambiguella Huebner), apple bud moth (Pandemis pyrusana Kearfott), omnivorous leafroller (Platynota stultana Walsingham), barred fruit-tree tortrix (Pandemis cerasana Huebner), apple brown tortrix (Pandemis heparana Denis & Schiffermueller)); as well as many other economically important lepidopterans (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora)gossypiella Saunders), gypsy moth (Lymantria dispar Linnaeus), peach fruit borer (Carposina niponensis Walsingham), peach twig borer (Anarsia lineatella Zeller), potato tuberworm (Phthorimaea operculella Zeller), spotted teniform leafminer (Phyllonorycter blancardella Fabricius), Asiatic apple leafminer (Lithocolletis ringoniella Matsumura), rice leaffolder (Lerodea eufala Edwards), apple leafminer (Leucoptera scitella Eggs, larvae, and adults of cockroaches, including those from the families Blattodeidae and Blattidae (e.g., Oriental cockroach (Blatta orientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo), German cockroach (Blattella germanica Linnaeus), brownbanded cockroach (Supella longipalpa Fabricius), American cockroach (Periplaneta americana Linnaeus), brown-banded cockroach (Periplaneta brunnea Burmeister), Madeira cockroach (Leucophaea maderae Fabricius), Oriental cockroach (Periplaneta fuliginosa Serville), American cockroach (Periplaneta australasiae Fabr.), and gray cockroach (lobster).(Cockroach) (Nauphoeta cinerea Olivier) and smooth cockroach (Symploce pallens Stephens); Eggs, leaf-eating, fruit-eating, root-eating, seed-eating, and vesicular tissue-feeding larvae and adults of the order Coleoptera, including weevils from the families Curculionidae, Fabaceae, and Curculionidae (e.g., cotton weevil (Anthonomus grandis Boheman), rice water weevil (Lissorhoptrus oryzophilus Kuschel), granaria weevil (Sitophilus granarius Linnaeus), rice grain weevil (Sitophilus oryzae Linnaeus), annual bluegrass weevil (Listronotus maculicollis Dietz), bluegrass billbug (Sphenophorus parvulus Gyllenhal), and grass weevil (Sphenophorus venatus vestitus) Chittenden), Rocky Mountain billbug (Sphenophorus cicatristriatus Fahraeus); flea beetles of the Chrysomelidae family, cucumber beetles, root-cutting beetles, leaf beetles, Colorado leaf beetles, and leaf-mining insects (e.g., Colorado leaf beetle (Leptinotarsa ​​decemlineata Say), Western corn rootworm (Diabrotica virgifera LeConte)); scarab beetles of the Scarabaeidae family and other beetles (e.g., Japanese beetle (Popillia japonica Newman), spotted beetle (Anomala orientalis Waterhouse), northern masked chafer (Cyclocephala borealis Arrow), southern masked chafer (Cyclocephala immaculata Olivier or C. lurida) Bland), dung beetles and ground insects (Aphodius spp.)Examples include the black turfgrass beetle (Ataenius spretulus Haldeman), the green June beetle (Cotinis nitida Linnaeus), the red velvet beetle (Maladera castanea Arrow), the May / June beetles (Phyllophaga spp.), and the European chafer (Rhizotrogus majalis Razoumowsky); carpet beetles from the family Dermestidae; click beetle larvae from the family Elateridae; bark beetles from the family Barkworms; and confused flour beetles from the family Tenebrionidae.

[0074] Furthermore, agricultural and non-agricultural pests include: eggs, adults, and larvae of Dermestidae, including earwigs from the family Dermestidae (e.g., European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches morio Fabricius)); eggs, immatures, adults, and larvae of Hemiptera, such as mirid bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers from the family Cicadidae (e.g., Empoasca spp.), and bed bugs from the family Cicadidae (e.g., Cimex lectularius). Linnaeus), planthoppers from the families Liviidae and Liviidae, treehoppers from the family Liviidae, psyllids from the families Liviidae, Liviidae and Liviidae, whiteflies from the family Liviidae, aphids from the family Coccidae, phylloxera from the family Neaphiidae, mealybugs from the family Coccidae, scale insects from the families Coccidae, Coccidae and Coccidae, lace bugs from the family Pentatomidae, chinch bugs (e.g., hairy chinch bug (Blissus leucopterus hirtus Montandon) and southern chinch bug (Blissus insularis)) Examples include barber bugs and other seed bugs from the family Lycanthidae, spittlebugs from the family Aesculidae, squash bugs from the family Coreidae, and red bugs and cotton stainers from the family Pentatomidae.

[0075] Agricultural and non-agricultural pests include: eggs, larvae, nymphs and adults of Acari (mites), such as spider mites and red mites of the family Miridae (e.g., apple spider mite (Panonychus ulmi Koch), two-spotted spider mite (Tetranychus urticae Koch), McDaniel spider mite (Tetranychus mcdanieli McGregor)); flat mites of the family Miridae (e.g., grape spider mite (Brevipalpus lewisi McGregor)); rust mites and bud mites of the family Miridae, as well as other leaf-eating mites and mites important to human and animal health, namely, dust mites of the family Epidermoptidae, demodectic mange (family Demodecidae mites, scouring mites; ticks commonly known as house ticks (e.g., Ixodes scapularis Say, Australian paralysis tick (Ixodes holocyclus Neumann), American dog tick (Dermacentor variabilis Say), lone star tick (Amblyomma americanum Linnaeus)); and mites commonly known as soft mites (e.g., relapsing fever tick (Ornithodoros turicata Duges), common fowl tick (Argas radiatus Raillet)); scab and itch mites of the families Cynopsidae, Liceidae, and Sarcoptes scabiei. mites); eggs, adults, and immature forms of grasshoppers, including locusts, grasshoppers, and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M.Diptera (including differentialis Thomas), American grasshoppers (e.g., Schistocerca americana Drury), desert grasshoppers (Schistocerca gregaria Forsskal), migratory locusts (Locusta migratoria Linnaeus), bush locusts (Zonocerus spp.), house crickets (Acheta domesticus Linnaeus), mole crickets (e.g., tawny mole cricket (Scapteriscus vicinus Scudder) and southern mole cricket (Scapteriscus borellii Giglio-Tos)); eggs, adults and immature forms of flies including leaf miners (e.g., Liriomyza spp., e.g., tomato leafminer (Liriomyza sativae)). Blanchard's flies, small insects, fruit flies (Tephritidae), frit flies (e.g., Oscinella frit Linnaeus), soil maggots, houseflies (e.g., Musca domestica Linnaeus), lesser house flies (e.g., Fannia canicularis Linnaeus, F. femoralis Stein), stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blowflies (e.g., Chrysomya spp., Phormia spp.), and other muscoid flies, horseflies (e.g., Tabanus spp.), botflies (e.g., Gasterophilus spp., Oestrus spp.), cattle flies (e.g., Hypoderma (spp.), blind flies (e.g., Chrysops spp.), sheep lice (e.g., Melophagus ovinus Linnaeus) and other brachycerae, mosquitoes (e.g., Aedes spp.)Eggs, adults, and immature forms of Thyriptera including onion thrips (Thrips tabaci Lindeman), flower thrips (Frankliniella spp.), and other leaf-eating thrips; Florida carpenter ant (Camponotus floridanus Buckley), red carpenter ant (Camponotus ferrugineus Fabricius), black carpenter ant (Camponotus pennsylvanicus De Geer), white-footed ant (white-footed ant) (Technomyrmex albipes F. Smith), glossy big-headed ants (Pheidole sp.)Other examples include hymenoptera pests, such as ants of the family Formicidae, including the ghost ant (Tapinoma melanocephalum Fabricius), the pharaoh ant (Monomorium pharaonis Linnaeus), the small fire ant (Wasmannia auropunctata Roger), the red imported fire ant (Solenopsis geminata Fabricius), the red imported fire ant (Solenopsis invicta Buren), the Argentine ant (Iridomyrmex humilis Mayr), the crazy ant (Paratrechina longicornis Latreille), the pavement ant (Tetramorium caespitum Linnaeus), the cornfield ant (Lasius alienus Foerster), and the odorous house ant (Tapinoma sessile Say). Other Hymenoptera, including bees (including carpenter bees), hornets, yellow jackets, wasps, and sawflies (Neodiprion spp.; Cephus spp.); and isoptera pest insects, including termites of the families Termitidae, Cryptotermes (e.g., Cryptotermes sp.), and Reticulitermes sp., Coptotermes sp., Heterotermes tenuis Hagen (e.g., Macrotermes sp.).(Odontotermes obesus Rambur), Eastern subterranean termite (Reticulitermes flavipes Kollar), Western subterranean termite (Reticulitermes hesperus Banks), Formosan subterranean termite (Coptotermes formosanus Shiraki), West Indian drywood termite (Incisitermes immigrans Snyder), Powder post termite (Cryptotermes brevis Walker), Drywood termite (Incisitermes snyderi Light), Southeastern subterranean termite (Reticulitermes virginicus Banks), American drywood termite (Western Drywood termites (Incisitermes minor Hagen), arboreal termites, such as Nasutitermes sp.and other economically important termites; silverfish, such as the European silverfish (Lepisma saccharina Linnaeus) and the spotted silverfish (Thermobia domestica Packard); head lice (Pediculus humanus capitis De Geer), human lice (Pediculus humanus Linnaeus), chicken louse (Menacanthus stramineus Nitzsch), dog louse (Trichodectes canis De Geer), chicken louse (fluff louse) (Goniocotes gallinae De Geer), cow louse (sheep body louse) (Bovicola ovis Schrank), cow louse (Haematopinus eurysternus Nitzsch), cow louse (Linognathus vituli Harmful insects of the Trichophaga and Lice orders, including Linnaeus and other blood-sucking, biting parasitic lice that attack humans and animals; harmful insects of the Siphonoptera order, including the oriental rat flea (Xenopsylla cheopis Rothschild), cat flea (Ctenocephalides felis Bouche), dog flea (Ctenocephalides canis Curtis), hen flea (Ceratophyllus gallinae Schrank), sticktight flea (Echidnophaga gallinacea Westwood), human flea (Pulex irritans Linnaeus), and other fleas that afflict mammals and birds. Further harmful arthropods targeted include: spiders of the order Araneae, such as the brown recluse spider (Loxosceles reclusa Gertsch&Mulaik) and the black widow spider (Latrodectus mactans Fabricius), and centipedes of the order Scutigera, such as the house centipede (Scutigera coleoptrata Linnaeus).

[0076] Examples of harmful invertebrates of stored grains include the larger grain borer (Prostephanus truncatus Horn), the lesser grain borer (Rhyzopertha dominica Fabricius), the grain weevil (Sitophilus oryzae Linnaeus), the grain weevil (Sitophilus zeamais Motschulsky), the four-spotted bean weevil (Callosobruchus maculatus Fabricius), the confused flour beetle (Tribolium castaneum Herbst), the granary weevil (Sitophilus granarius Linnaeus), the Indian meal moth (Plodia interpunctella Huebner), the Mediterranean flour beetle (Ephestia kuehniella Zeller), and the flat beetle (flat beetle). Examples include the rusty grain beetle (Cryptolestes ferrugineus Stephens).

[0077] The compositions of this disclosure include economically important members of the orders Cicomata, Ascarida, Pinworms, Rhabnematodes, Aniura, and Enopleida, for example, but not limited to, economically important agricultural pests (i.e., root-knot nematodes of the genus Meloidogyne, root-lesion nematodes of the genus Pratylenchus, stubby root nematodes of the genus Trichodorus, etc.), as well as organisms harmful to animal and human health (i.e., all economically important trematodes, tapeworms, and roundworms, for example, Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, and Dirofilaria immitis in dogs). It may be useful for controlling members of the Nematoda, Cetocoptera, Trematode, and Acanthocephala classes, including Leidy, Anoplocephala perfoliata in horses, and Fasciola hepatica Linnaeus in ruminants.

[0078] The compositions disclosed herein contain lepidopteran pests (e.g., Alabama argillacea Huebner (cotton leaf worm), Archips argyrospila Walker (fruit tree tortrix), A. rosana Linnaeus (European leaf roller) and other Archips species, Chilo suppressalis Walker (rice stem borer), Cnaphalocrocis medinalis Guenee (rice leaf roller), Crambus caliginosellus Clemens (corn root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoverpa armigera Huebner (Old World bollworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker (sod webworm), Lobesia botrana Denis&Schiffermueller (grape berry moth), Pectinophora gossypiella Saunders (pink bollworm), Phyllocnistis citrella Stainton (citrus leafminer), Pieris brassicae Linnaeus (large white butterfly), Pieris rapaeIt may be useful for controlling Linnaeus (cabbage white butterfly), Plutella xylostella Linnaeus (diamondback moth), Spodoptera exigua Huebner (beet armyworm), Spodoptera litura Fabricius (tobacco cutworm, cluster caterpillar), Spodoptera frugiperda JESmith (fall armyworm), Trichoplusia ni Huebner (cabbage looper), and Tuta absoluta Meyrick (tomato leafminer).

[0079] The compositions disclosed herein are: Acyrthosiphon pisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosiphon fragaefolii Cockerell (strawberry aphid), and Diuraphis noxia. Kurdjumov / Mordvilko (Russian wheat aphid), Dysaphis plantaginea Passerini (rosy apple aphid), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy (mealy plum aphid), Lipaphis pseudobrassicae Davis (turnip aphid), Metopolophium dirrhodum Walker (rose-grain aphid), Macrosiphum euphorbiae Thomas (potato aphid), Myzus persicae Sulzer (peach-potato aphid, green peach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigusspp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch (corn leaf aphid), Rhopalosiphum padi Linnaeus (bird cherry-oat aphid), Schizaphis graminum Rondani (greenbug aphid), Sitobion avenae Fabricius (English grain aphid), Therioaphis maculata Buckton (spotted alfalfa aphid), Toxoptera aurantii Boyer de Fonscolombe (black citrus aphid), and Toxoptera citricidus Kirkaldy (brown citrus aphid) Adelges spp. (aphid); Phylloxera devastatrix Pergande (pecan phylloxera); Bemisia tabaci Gennadius (tobacco whitefly, sweetpotato whitefly), Bemisia argentifolii Bellows & Perring (silverleaf whitefly), Dialeurodes citri Ashmead (citrus whitefly), and Trialeurodes vaporariorum Westwood (greenhouse whitefly); Empoasca fabae Harris (potato leafhopper), Laodelphax striatellus Fallen (smaller brown planthopper), Macrosteles quadrilineatus Forbes (aster leafhopper), Nephotettix cincticeps Uhler (Nephotettix), a type of leafhopper.Nigropictus Stal (Cross-striped black leafhopper), Nilaparvata lugens Stal (Brown planthopper), Peregrinus maidis Ashmead (Corn planthopper), Sogatella furcifera Horvath (White-backed planthopper), Tagosodes orizicolus Muir (Rice delphacid), Typhlocyba pomaria McAtee (White apple leafhopper), Erythroneura spp. (Grape leafhoppers); Magicidada septendecim Linnaeus (Periodic cicada); Icerya purchasi Maskell (Cottony cushion scale), Quadraspidiotus perniciosus Comstock (San Jose scale); Planococcus citri It may be useful for controlling members of the order Hemiptera, including Risso (citrus mealybug), Pseudococcus spp. (other mealybug complex), Cacopsylla pyricola Foerster (pear psylla), and Trioza diospyri Ashmead (persimmon psylla).

[0080] The compositions disclosed herein include Acrosternum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopterus leucopterus Say (chinch bug), Cimex lectularius Linnaeus (bed bug), Corythucha gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-Schaeffer (cotton stainer), Euschistus servus Say (brown stink bug), Euschistus variolarius Palisot de Beauvois (one-spotted stink bug), and Graptostethus It may be useful for controlling members of the order Hemiptera, including spp. (a complex of seed bugs), Halyomorpha halys Stal (brown marmorated stink bug), Leptoglossus corculus Say (leaf-footed pine seed bug), Lygus lineolaris Palisot de Beauvois (rusty blind turtle), Nezara viridula Linnaeus (southern green stink bug), Oebalus pugnax Fabricius (rice stink bug), Oncopeltus fasciatus Dallas (large milkweed bug), and Pseudatomoscelis seriatus Reuter (cotton fleahopper).Other insect orders controlled by the compositions of this disclosure include Thylemptera (e.g., Frankliniella occidentalis Pergande (western flower thrips), Scirtothrips citri Moulton (citrus thrips), Scirtothrips variabilis Beach (soybean thrips), and Thrips tabaci Lindeman (onion thrips)); and Coleoptera (e.g., Leptinotarsa ​​decemlineata Say (colored leaf beetle), Epilachna varivestis Mulsant (green beetle), and click beetle larvae of the genera Agriotes, Athous, or Limonius).

[0081] In some embodiments, the pests are selected from the group consisting of harmful invertebrates, insects, arthropods, and combinations thereof.

[0082] In some embodiments, the environment is selected from the group consisting of farmland, orchards, forests, and combinations thereof.

[0083] The compositional embodiments of this disclosure may be combined in any way with the method embodiments of this disclosure. Similarly, the method embodiments of this disclosure may be combined in any way. Accordingly, the following embodiments should be construed as merely illustrative and not as limiting the disclosure in any way.

[0084] The aspects of this disclosure are provided in accordance with the subject matter of the following clauses.

[0085] 1. Antifreeze and; Pheromones; and solvent core including; and The shell containing the core Microcapsules containing A composition comprising, Herein, the microcapsules are the composition having a d90 value of at least about 30 μm. 2. The composition according to item 1, wherein the microcapsules have a d90 value in the range of about 30 μm to about 60 μm. 3. The composition according to paragraph 1 or 2, wherein the microcapsules have a d90 value in the range of about 35 μm to about 50 μm. 4. The composition according to any one of the first to third claims, wherein the microcapsules have a d50 value in the range of approximately 5 μm to approximately 25 μm. 5. The composition according to any one of claims 1 to 4, wherein the microcapsules have a d10 value in the range of about 1 μm to about 7 μm. 6. The composition according to any one of paragraphs 1 to 5, further comprising additives selected from dispersants, surfactants, emulsifiers, wetting agents, biocides, defoamers, antifreezes, rheological modifiers, solvents, stabilizers, UV stabilizers, UV absorbers, salts, excipients, antioxidants, and combinations thereof. 7. A composition according to any one of paragraphs 1 to 6, wherein the composition is a pesticide composition. 8. The composition according to any one of paragraphs 1 to 7, wherein the composition is in a form selected from premixes and tank mixes. 9. The composition according to any one of paragraphs 1 to 8, wherein the composition is in the form of a CS formulation or a ZC formulation. 10. A composition according to any one of paragraphs 1 to 9, wherein the shell comprises a substance selected from synthetic polymers, polyureas, polyurethanes, polyacrylates, polyamides, polyvinyl alcohols, polyvinylpyrrolidones, polycarbonates, polythiocarbonates, semi-synthetic substances, modified cellulose, modified starch derivatives, natural substances, gum arabic, agar, dextrin, alginic acid, alginates, biodegradable natural polymers, collagen, polysaccharides, starch, dextrin, waxes, chitosan, arginate, cellulose, gelatin, derivatives thereof, and combinations thereof. 11. The composition according to any one of paragraphs 1 to 10, wherein the pheromone is selected from aldehyde pheromones, acetate pheromones, alcohol pheromones, ketone pheromones, epoxide pheromones, hydrocarbon pheromones, ester pheromones, and combinations thereof. 12. A composition according to any one of items 1 to 11, wherein the pheromone does not contain an aldehyde pheromone. 13. Pheromones include (Z)-5-decenyl acetate, dodecanyl acetate, (Z)-7-dodecenyl acetate, (E)-7-dodecenyl acetate, (Z)-8-dodecenyl acetate, (E)-8-dodecenyl acetate, (Z)-9-dodecenyl acetate, (E)-9-dodecenyl acetate, (E)-10-dodecenyl acetate, 11-dodecenyl acetate, (Z)-9,11-dodecadienyl acetate, (E)-9,11-dodecadienyl acetate, (Z)-11-tridecenyl acetate, (E)-11-tridecenyl acetate, tetradecanyl acetate, (E)-7-tetradecenyl acetate, (Z) )-8-tetradecenyl acetate, (E)-8-tetradecenyl acetate, (Z)-9-tetradecenyl acetate, (E)-9-tetradecenyl acetate, (Z)-10-tetradecenyl acetate, (E)-10-tetradecenyl acetate, (Z)-11-tetradecenyl acetate, (E)-11-tetradecenyl acetate, (Z)-12-pentadecenyl acetate, (E)-12-pentadecenyl acetate, hexadecanyl acetate, (Z)-7-hexadecenyl acetate, (Z)-11-hexadecenyl acetate, (E)-11-hexadecenyl acetate, octadecanyl acetate, (E,Z )-7,9-dodecadienyl acetate, (Z,E)-7,9-dodecadienyl acetate, (E,E)-7,9-dodecadienyl acetate, (Z,Z)-7,9-dodecadienyl acetate, (E,E)-8,10-dodecadienyl acetate, (E,Z)-9,12-dodecadienyl acetate, (E,Z)-4,7-tridecadienyl acetate, (E,E)-9,11-tetradecadienyl acetate, (Z,Z)-9,12-tetradecadienyl acetate, (Z,Z)-7,11-hexadecadienyl acetate, (E,Z)-7,11-hexadecadienyl acetate, (Z,E)-7 A composition according to any one of claims 1 to 12, selected from ,11-hexadecadienyl acetate, (E,E)-7,11-hexadecadienyl acetate, (Z,E)-3,13-octadecadienyl acetate, (E,Z)-3,13-octadecadienyl acetate, (E,E)-3,13-octadecadienyl acetate, (Z)-5-decenyl methylbutanoate, (+)cis-7,8-epoxy-2-methyloctadecane, (E,Z)-2,4-methyldecadienate, methyl 2,6,10-trimethyltridecanoate, and combinations thereof. 14. A composition according to any one of paragraphs 1 to 13, wherein the antifreeze is selected from propylene glycol, glycerin, glycol, ethylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, methanol, ethanol, propanol, butanol, and combinations thereof. 15. A composition according to any one of items 1 to 14, wherein the solvent is selected from hydrophobic solvents, high flash point solvents, methylated seed oils, methyl methyl oleate oils, methyl methyl linoleate oils, mineral oils, paraffinic oils, tall oil fatty acid-based solvents, aromatic solvents, aromatic ester solvents, polybutenes, methyl esters of fatty acids, tributyl 2-acetate citrate, alkylamide solvents, benzyl acetate, wax esters, and combinations thereof. 16. A method for producing a composition, the method being: Antifreeze and; Pheromones; and solvent core including; and The shell containing the core Microcapsules containing Forming a mixture containing Includes, Here, the microcapsules have a d90 value of at least about 30 μm, as described above. 17. The method according to claim 16, further comprising encapsulating the pheromone and solvent in microcapsules before forming the mixture. 18. A method for controlling a pest, comprising contacting the pest or its environment with a biologically effective amount of a composition, wherein the composition is: Antifreeze and; Pheromones; and solvent core including; and The shell containing the core Microcapsules containing Includes, Here, the microcapsules have a d90 value of at least about 30 μm, as described above. 19. The method according to paragraph 18, wherein the pest is selected from harmful invertebrates, insects, arthropods, and combinations thereof. 20. The method described in paragraph 18 or 19, wherein the environment is selected from farmland, orchards, forests, and combinations thereof.

[0086] Even without further details, those skilled in the art will likely be able to make the most of the present invention using the foregoing description. Accordingly, the following examples should be construed as merely illustrative and not as limiting the present disclosure in any way. [Examples]

[0087] Example 1. Solvent screening Solvents with different chemistry were used to prepare emulsion-in-water (EW) formulations containing the Z9-14 acetate pheromone. A solvent-free control EW formulation was also prepared and evaluated. Table 1 summarizes the volatility and chemical stability of the EW formulations, with the results sorted to list the best-performing sample at the end of the list, according to the best volatility control. EW formulations using Steposol ME (methyl oleate / methyl linoleate ester oil from Stepan) performed better than other EW formulations in this series. Solvent-free formulations exhibited the worst performance.

[0088] To measure chemical stability, the EW formulation was placed in a sealed scintillation vial, and the vial was then placed in an oven heated to 60°C for 4 hours. The amount of Z9-14 acetate pheromone remaining in each vial was quantified. Since the scintillation vial was sealed, the loss of Z9-14 acetate pheromone was due to chemical degradation. Chemical stability was measured as the percentage of remaining Z9-14 acetate pheromone by mass.

[0089] To measure volatility, the EW formulation was placed in a removed vial, and the vial was then heated in an oven at 60°C for 4 hours. The residual Z9-14 acetate pheromone in each vial was quantified. Since the scintillation vials had their lids removed, the Z9-14 acetate pheromone was able to evaporate. Volatility was measured as the residual mass percentage of Z9-14 acetate pheromone.

[0090] [Table 1]

[0091] Example 2. Volatility control of microencapsulated Z9-14 acetate formulation. Pheromone encapsulation was achieved by reacting isocyanates and amines to create a polymer wall that protects the pheromone and solvent from contact with the environment. In a stirred vessel, a solution of hydrophobic monomer (isocyanate compound), solvent, and pheromone was emulsified in water. The size of the resulting droplets was adjusted by the stirring speed. Next, water-soluble monomers were introduced into a stirred tank, and polymers were formed by chemical polymerization. This slurry was then mixed slowly at 50-60°C for several hours to achieve a complete reaction of the monomers. Finishing steps were then performed. Finishing steps included adjusting the acidity of the medium and adding post-formulation components (biocide, rheological modifier, and antifreeze compounds) to obtain the final formulation.

[0092] The table below shows the volatility control data for the CS formulation of Z9-14 acetate, where the modified parameter is the solvent. The solvents evaluated included: Steposol ME (methyl oleate / methyl linoleate from Stepan), Hallcomid M-10 (N,N-dimethyldecanamide from Stepan), Surfonic AG 1705 (benzyl acetate from Indorama), tributyl 2-acetate citrate (from Sigma Millipore), Stepan C42 (methyl laurate / methyl myristate from Stepan), Stepan C65 (methyl palmitate / methyl oleate-methyl stearate from Stepan), and Sunspray N11 (paraffinic oil from HollyFrontier Specialty Products). Steposol ME has a vapor pressure of 3.12 mmHg at 20°C, Stepan C25 has a vapor pressure of 0.36 mmHg at 20°C, Stepan C42 has a vapor pressure of 0.0163 mmHg at 25°C, and Stepan C65 has a vapor pressure of 0.01 mmHg at 20°C.

[0093] Surprisingly, Steposol ME was found to achieve the best volatility control of the pheromone, despite having the highest vapor pressure of all the solvents tested. Sunspray N11 also showed good volatility control, but Stepan C42 was not effective in this system.

[0094] [Table 2]

[0095] The volatility control of pheromones in CS formulations was measured as follows. Using the photodegradable Peach Drop method, an aqueous spray solution of the formulation was applied as droplets to glass. After a desired time (0-99 hours) under simulated sunlight, the glass was extracted with a solvent. The amount of pheromone remaining on the glass was analyzed by GC of the extract. T24hr, T44hr, T46hr, and T99hr represent 24, 44, 46, and 99 hours, respectively, of continuous light exposure in a simulated sunlight chamber. Each 24-hour simulated sunlight exposure is equivalent to 2.5 days of sunlight.

[0096] Surprisingly, the highest level of volatility control was found to be achieved with capsules having a d90 of approximately 40 μm, in which case the capsules also contained an antifreeze and a solvent. The antifreeze was added in the final step after the completion of the heating (cooking) process to improve the handling properties of the formulation at low temperatures. The antifreeze lowers the freezing point of water by inhibiting the formation of ice crystals in the continuous phase. However, the observed additional benefit that propylene glycol also improved the volatility control of the pheromone was unexpected.

[0097] Factors observed to negatively affect pheromone control include smaller capsule size, absence of solvent, and absence of antifreeze. Therefore, combinations of particle size, antifreeze, and solvent yield significant benefits.

[0098] Example 3. Effect of antifreeze The effect of the antifreeze compound (propylene glycol) was also evaluated. The loading level of Z-9-tetradecenyl acetate pheromone was set to 15% by mass in B-1 and B-2, and to 21% by mass in B-3 and B-4. The microcapsule particle size was kept constant at 37 μm. Surprisingly, the data showed that propylene glycol improved the control of the volatility of the pheromone compound.

[0099] [Table 3]

[0100] Example 4. Effect of antifreeze The effects of two antifreeze compounds, glycerin and propylene glycol, were tested and compared in a microencapsulated formulation containing Z-9-tetradecenyl acetate pheromone. The microcapsule size was kept constant at 27 μm. The data indicate that both antifreeze compounds improve the control of pheromone volatility. Propylene glycol was more effective than glycerin at the same loading level.

[0101] [Table 4]

[0102] Example 5. Effect of microcapsule particle size, solvent, and antifreeze The effects of microcapsule particle size, solvent, and antifreeze were evaluated. As shown in the table below, reducing the microcapsule particle size resulted in reduced pheromone volatility control. Furthermore, the removal of the solvent and / or antifreeze compound resulted in reduced volatility control (i.e., more pheromone was lost).

[0103] [Table 5]

[0104] Example 6. Encapsulation of Z-9-tetradecenyl acetate We evaluated the microencapsulation of Z-9-tetradecenyl acetate pheromone containing Suprasec5025 (polymer diphenylmethane diisocyanate (MDI)) as the isocyanate and Hallcomid M-10 as the solvent.

[0105] As shown in the table below, a decrease in microcapsule size resulted in reduced control of pheromone volatility.

[0106] [Table 6]

[0107] Example 7. Encapsulation of Z-11-hexadecenyl acetate using EDA amine and PAPI 27. The use of ethylenediamine (EDA) as an amine crosslinking agent was evaluated in the same manner as in the above example where hexamethylenediamine (HMDA) was used.

[0108] As shown in the table below, a decrease in microcapsule size resulted in reduced control of pheromone volatility.

[0109] [Table 7]

[0110] Example 8. Encapsulation of Z-9-tetradecenyl acetate using EDA amine and Takenate isocyanate. Takenate TM 500 (m-Xylylene diisocyanate (XDI)) and Takenate TM The use of ethylenediamine (EDA) as an amine crosslinking agent in combination with D-110N (trimethylolpropane adduct of xylylene diisocyanate) was evaluated in the same manner as in the above example using hexamethylenediamine (HMDA).

[0111] As shown in the table below, a decrease in microcapsule size resulted in reduced control of pheromone volatility.

[0112] [Table 8]

[0113] Example 9. Encapsulated Z-11-hexadecenyl acetate pheromone Microcapsule formulations were prepared using Z-11-hexadecenyl pheromone acetate. The microcapsule size, solvent, and antifreeze effect were evaluated. The control formulation without antifreeze contained water instead of antifreeze. As shown in the table below, the volatility data revealed that the inclusion of antifreeze improved the control of pheromone volatility. Furthermore, similar to formulations containing Z-9-tetradecenyl pheromone acetate, this example confirmed that a decrease in microcapsule size leads to a decrease in pheromone volatility control.

[0114] [Table 9]

[0115] Example 10. Pheromone concentration Volatility control data was evaluated for formulations using two different pheromone concentrations (150 g / L and 200 g / L). As shown in the table below, the best volatility control of the Z9-14 acetate pheromone was achieved with a D90 particle size in a capsule of approximately 40 μm.

[0116] [Table 10]

[0117] Example 11. Storage stability of microencapsulated Z9-14 acetate formulation. Accelerated storage stability tests were performed on a 200 g / L CS formulation containing an antifreeze and using Steposol ME as the solvent. This formulation was found to be fluid at both high and low temperatures (54°C for 2 weeks, 0°C for 2 weeks, and freeze-thaw cycles (30°C to -20°C) (FT) for 2 weeks). Syneresis (i.e., separation %) was observed for formulations using a small amount of rheological modifier blend containing 2% xanthan gum, 2% biocide, and 96% water. As shown in the table below, when the rheological modifier blend was used at a loading level equal to or higher than 6%, syneresis was less than 5% after storing the formulation at 54°C for 2 weeks. No syneresis was observed under other storage stability conditions. The incorporation of the antifreeze improved the control of pheromone volatility, as discussed above, and also aided in the storage stability and handling characteristics of the pheromone CS formulation.

[0118] The following table shows the effect of the rheological modifier xanthan gum (as Rhodopol 23) on syneresis of CS formulations after 2 weeks at room temperature, 40°C, and 54°C. After degrading CS formulations of different particle sizes under different conditions, formulations with good fluidity were obtained. Syneresis is mitigated by incorporating an appropriate amount of xanthan gum (Rhodopol 23) in the formulation table.

[0119] [Table 11]

[0120] Surprisingly, it was found that substantial improvements in controlling the volatility of pheromone compositions could be achieved using compositions containing an antifreeze and microcapsules, in which case the microcapsules were relatively large and contained co-encapsulated pheromones and solvents. The most substantial improvements were observed using microcapsules with a d90 value of at least 35 μm.

Claims

1. Antifreeze and; Pheromones; and solvent Cores including; and The shell containing the core Microcapsules containing A composition comprising, The composition wherein the microcapsules have a d90 value of at least about 30 μm.

2. Microcapsules: A d90 value in the range of approximately 30 μm to approximately 60 μm, preferably in the range of approximately 35 μm to approximately 50 μm; d50 values ​​in the range of approximately 15 μm to approximately 25 μm; and / or d10 values ​​in the range of approximately 2 μm to approximately 7 μm The composition according to claim 1, having the following characteristics.

3. The composition according to claim 1 or 2, further comprising additives selected from dispersants, surfactants, emulsifiers, wetting agents, biocides, defoamers, antifreezes, rheological modifiers, solvents, stabilizers, UV stabilizers, UV absorbers, salts, excipients, antioxidants, and combinations thereof.

4. The composition according to any one of claims 1 to 3, wherein the composition is a pesticide composition, preferably in a form selected from a premix and a tank mix.

5. The composition according to any one of claims 1 to 4, wherein the composition is in the form of a CS formulation or a ZC formulation.

6. The composition according to any one of claims 1 to 5, wherein the shell comprises a substance selected from synthetic polymers, polyurea, polyurethane, polyacrylate, polyamide, polyvinyl alcohol, polyvinylpyrrolidone, polycarbonate, polythiocarbonate, semi-synthetic substances, modified cellulose, modified starch derivatives, natural substances, gum arabic, agar, dextrin, alginic acid, alginate, biodegradable natural polymers, collagen, polysaccharides, starch, dextrin, wax, chitosan, arginate, cellulose, gelatin, derivatives thereof, and combinations thereof.

7. The composition according to any one of claims 1 to 6, wherein the pheromone is selected from aldehyde pheromones, acetate pheromones, alcohol pheromones, ketone pheromones, epoxide pheromones, hydrocarbon pheromones, ester pheromones, and combinations thereof.

8. The pheromone is (Z)-5-decenyl acetate, dodecanyl acetate, (Z)-7-dodecenyl acetate, (E)-7-dodecenyl acetate, (Z)-8-dodecenyl acetate, (E)-8-dodecenyl acetate, (Z)-9-dodecenyl acetate, (E)-9-dodecenyl acetate, (E)-10-dodecenyl acetate, 11-dodecenyl acetate, (Z)-9,11-dodecadienyl acetate, (E)-9,11-dodecadienyl acetate, (Z)-11-tridecenyl acetate, (E)-11-tridecenyl acetate, tetradecanyl acetate, (E)-7-tetradecenyl acetate, acetate ( (Z)-8-tetradecenyl acetate, (E)-8-tetradecenyl acetate, (Z)-9-tetradecenyl acetate, (E)-9-tetradecenyl acetate, (Z)-10-tetradecenyl acetate, (E)-10-tetradecenyl acetate, (Z)-11-tetradecenyl acetate, (E)-11-tetradecenyl acetate, (Z)-12-pentadecenyl acetate, (E)-12-pentadecenyl acetate, hexadecanyl acetate, (Z)-7-hexadecenyl acetate, (Z)-11-hexadecenyl acetate, (E)-11-hexadecenyl acetate, octadecanyl acetate, (E) acetate, Z)-7,9-dodecadienyl acetate, (Z,E)-7,9-dodecadienyl acetate, (E,E)-7,9-dodecadienyl acetate, (Z,Z)-7,9-dodecadienyl acetate, (E,E)-8,10-dodecadienyl acetate, (E,Z)-9,12-dodecadienyl acetate, (E,Z)-4,7-tridecadienyl acetate, (E,E)-9,11-tetradecadienyl acetate, (Z,Z)-9,12-tetradecadienyl acetate, (Z,Z)-7,11-hexadecadienyl acetate, (E,Z)-7,11-hexadecadienyl acetate, (Z,E) A composition according to any one of claims 1 to 7, selected from -7,11-hexadecadienyl acetate, (E,E)-7,11-hexadecadienyl acetate, (Z,E)-3,13-octadecadienyl acetate, (E,Z)-3,13-octadecadienyl acetate, (E,E)-3,13-octadecadienyl acetate, (Z)-5-decenyl 3-methylbutanoate, (+)cis-7,8-epoxy-2-methyloctadecane, (E,Z)-2,4-methyldecadienate, methyl 2,6,10-trimethyltridecanoate, and combinations thereof.

9. The composition according to any one of claims 1 to 8, wherein the antifreeze is selected from propylene glycol, glycerin, glycol, ethylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, methanol, ethanol, propanol, butanol, and combinations thereof.

10. The composition according to any one of claims 1 to 9, wherein the solvent is selected from hydrophobic solvents, high flash point solvents, methylated seed oils, methyl methyl oleate oil, methyl methyl linoleate oil, mineral oil, paraffinic oils, tall oil fatty acid-based solvents, aromatic solvents, aromatic ester solvents, polybutene, methyl esters of fatty acids, tributyl 2-acetate citrate, alkylamides, benzyl acetate, wax esters, and combinations thereof.

11. A method for producing a composition, the method being: Antifreeze and; Pheromones; and solvent Cores including; and The shell containing the core Microcapsules containing Forming a mixture containing Includes, The above method wherein the microcapsules have a d90 value of at least about 30 μm.

12. The method according to claim 11, further comprising encapsulating the pheromone and solvent in microcapsules before forming the mixture.

13. A method for controlling pests, comprising contacting a pest or its environment with a biologically effective amount of a composition, wherein the composition is: Antifreeze and; Pheromones; and solvent Cores including; and The shell containing the core Microcapsules containing Includes, The above method wherein the microcapsules have a d90 value of at least about 30 μm.

14. The method according to claim 13, wherein the harmful organism is selected from harmful invertebrates, insects, arthropods, and combinations thereof.

15. The method according to claim 13 or 14, wherein the environment is selected from farmland, orchards, forests, and combinations thereof.

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