Oil-based dispersion composition of solid particulate hygroscopic or water-soluble pesticidal agent
Patent Information
- Application Number
- CN202480018595.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2023-03-14
- Filing Date
- 2024-03-14
- Publication Date
- 2025-10-31
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Abstract
Description
Technical Field
[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 452,142, filed March 14, 2023, the contents of which are incorporated herein by reference.
[0002] This invention relates to non-aqueous suspension compositions, typically represented as oil-based dispersions of solid water-soluble and / or hygroscopic or solvent-absorbing biocidal compounds in the form of solid microparticles, most notably oil-based pymetrozine dispersions (OBPD) compositions. In particular, this invention relates to oil-based pymetrozine dispersion compositions with improved characteristics, ease of manufacture, and stability, which can be readily dispersed in water even after storage for end-use application (e.g., as tank mixes or spray mixes). Background Technology
[0003] Pymetrozine (CGA 215944) is an insecticide active and specific against sucking insect pests. Pymetrozine is representative of pyridinium benzoate (a relatively new class of insecticides). According to various reports, the mechanism of action of pymetrozine in insects may involve effects on neural regulation or neuromuscular interactions. Physiologically, it appears to work by preventing these insects from inserting their stylets into plant tissues.
[0004] The chemical name of pymetrozine is 6-methyl-4-[(E)-(pyridin-3-ylmethylene)amino]-4,5-dihydro-2H-[1,2,4]-triazine-3-one. Pymetrozine is a water-soluble and hygroscopic compound, and it has been reported to absorb certain solvents as well. Pymetrozine has the chemical formula C1. 10 H 11 N5O has a molecular weight of 217.23 g / mol. It has the structural formula (A):
[0005]
[0006] In many embodiments of the present invention, the oil-based pymetrozine dispersion compositions are non-aqueous suspension concentrates (such as oil-based dispersion concentrates (OD)). Typical features of the concentrated composition embodiments of the present invention typically include the inclusion of specific inventive ingredients or components as detailed herein, and generally limit or exclude the amount of expressly specified solvents in the composition as components of the composition. Oil-based pymetrozine dispersion concentrate compositions are typically substantially or almost entirely non-aqueous formulations or compositions, wherein substantially or almost entirely non-aqueous means a percentage content of water between greater than 0% and less than or equal to 5% w / w (excluding any water associated with pre-hydrated pymetrozine, if present). The oil-based pymetrozine dispersion concentrate compositions of the present invention are generally characterized by high dispersibility during compounding as defined herein, and high physical and chemical stability. These compositions are characterized by improved dispersibility in aqueous media (such as water).
[0007] When preparing diluted end-use compositions for application from oily dispersion concentrate compositions, the concentrated examples of the compositions of the present invention are characterized by the fact that they rapidly form a homogeneous suspension in water without clumping, and retain the aforementioned dispersibility characteristics even after these oily dispersions have been stored for a period of time at temperatures exceeding 25°C or "room temperature". As mentioned above, these compositions may contain pre-hydrated pymetrozine; however, a significant advantage of the compositions of the present invention is that they enable the advantageous manufacture of oil-based pymetrozine dispersion (concentrate) compositions containing non-hydrated pymetrozine particles, especially when a plant-based oil-based carrier is primarily used as the liquid carrier.
[0008] In several embodiments, substantially or almost entirely non-aqueous should be understood as having a water content greater than zero but not exceeding 5% by weight of the entire dispersion concentrate (excluding any water associated with pre-hydrated pymetrozine, if present). The water content mentioned is generally (but not only) water that may accompany a specific component or ingredient of the invention, as mentioned above, in a commercially available grade or brand.
[0009] To ensure the stability and efficacy of pesticide suspensions, and especially suspension concentrates (including oil-based dispersion concentrates), both during production and storage, agglomeration and particle size growth are several quality challenges that need to be overcome. The stability of the composition's dispersibility after storage remains an ongoing challenge.
[0010] The aforementioned challenges are compounded when pesticide suspension concentrates / oil dispersions contain hygroscopic pesticide active ingredients or components. Another challenge in formulating or preparing acceptable oil-based dispersions of hygroscopic water-soluble pesticides is that, in the past, it has often been found that seemingly acceptable prior art oil dispersion concentrates, which readily disperse in water during compounding, do not disperse as readily in water after being stored for a period of time (especially if stored at temperatures above 25°C or "room temperature").
[0011] Agglomeration, flocculation, and aggregation often occur during the preparation of non-aqueous pymetrozine suspension concentrates (oil dispersion concentrates), thereby reducing their stability and efficacy. Furthermore, these phenomena are even more pronounced after the storage period, and notably when the dispersion concentrate is stored above 25°C (room temperature) for more than a week (e.g., two weeks or longer at 54°C and / or at 40°C / 75% RH for at least a month).
[0012] Prior art references involve different compositions of pymetrozine. None of the prior art references disclose compositions containing pymetrozine and a specific combination of excipients used in this invention, while avoiding specific classes of harmful components (including specific solvents) and strictly controlling the water content to achieve the desired characteristics.
[0013] It has been previously reported that preparing storage-stable suspension concentrate formulations can be difficult, for example, in terms of thickening, unacceptably increased viscosity, and particle agglomeration, especially for active ingredients with high water solubility (such as pymetrozine).
[0014] Formulators looking to formulate hygroscopic, water-soluble biocides into liquid compositions face several ongoing challenges. Preparing pymetrozine liquid compositions, especially suspension compositions, and particularly oil-based dispersions of pymetrozine, is particularly challenging, especially when these oil-based dispersions are required to possess acceptable physical and stability properties as exemplified by standard practices commonly found in the field of agrochemical biocides.
[0015] Pymetrozine can absorb large amounts of liquid, notably water and solvents. Researchers often use a so-called "pre-hydration" step to ensure that pymetrozine does not undergo further changes during blending; however, the large amount of water typically used results in very little "space" left for the oil, which should be the base of the oil-based suspension, as well as other active and inactive components, and very high loadings with less-than-favorable characteristics. Furthermore, phenomena such as solidification, which previously occurred frequently, occur during blending and storage, especially at elevated temperatures. Previous attempts to formulate oil-based pymetrozine dispersion concentrates have been reported to have unacceptable appearance and problems with paste formation. Moreover, when conventional oil-based pymetrozine dispersion concentrates were diluted with water to prepare end-use tank mixes or ready-to-use spray products, these older concentrates were found to be difficult, if not impossible, to disperse in water, and this challenge was exacerbated after these prior art oil-based pymetrozine dispersion concentrates were stored for a period of time before dilution. Conventional pymetrozine dispersion products typically exhibited an unpleasant yellowing color. Unacceptably high viscosity has also been reported during manufacturing and storage.
[0016] As shown in "Manual on the development and use of FAO and WHO specifications for chemical pesticides" (https: / / www.fao.org / 3 / cb8401en / cb8401en.pdf), "OD, like SC formulations, does not spontaneously disperse when diluted in water as EC formulations. Therefore, the spray solution must be stirred to obtain a uniform dispersion before application. The most appropriate parameters to describe the performance characteristics are: - pourability (to ensure that OD can be poured from its container); - dispersion stability, wet sieving, and persistent foaming tests (to ensure the sprayability and stability of the diluted suspension); - storage at elevated temperatures (to ensure that no crystal growth occurs during storage)."
[0017] The inventors hereby disclose compositions and methods for preparing oil-based pymetrozine dispersion concentrates that overcome the aforementioned compounding challenges and achieve stable compositions that are both easily dispersible and possess the desired product quality and appearance. The oil-based pymetrozine dispersion concentrate examples of the present invention maintain a high loading concentration of pymetrozine while maintaining stability (in both dispersibility and product quality stability).
[0018] The inventors of this invention provide an insecticidal oil-based dispersion composition comprising pymetrozine and auxiliary components selected from dispersants, rheology modifiers, emulsifiers, and oil-based adjuvants and combinations thereof. This invention also provides pymetrozine oil-based dispersions produced using the methods and components of this invention, which possess advantageous physical characteristics, improved water dispersibility for end-use application, and improved chemical and physical stability. This invention provides and promotes an industrially and economically feasible method for formulating pymetrozine oily dispersions.
[0019] Purpose of the invention
[0020] The object of this invention is to provide oil-based liquid dispersion compositions of solid particulate hygroscopic and / or water-soluble biocides, particularly oil-based pymetrozine dispersions (OBPD) liquid compositions, which, compared with conventional oil dispersions of pymetrozine, have any and / or all of the following: less complex compounding, lower viscosity (maintained both during preparation and storage), easier preparation of diluted end-use suspensions in water, and improved physical characteristics (including reduced discoloration, such as yellowing). In many embodiments, these compositions are OD concentrates suitable for final dilution and dispersion in water for end-use application.
[0021] Another object of the present invention is to provide a composition of an oil-based dispersion of an insecticidal compound containing pymetrozine, wherein the active ingredient of pymetrozine (technical grade) does not require pretreatment (e.g., prehydration) before the start of compounding.
[0022] Another aspect of the invention is to provide a composition for an insecticidal oil-based dispersion comprising pymetrozine, one or more dispersants, one or more emulsifiers, one or more rheology modifiers, and one or more oil adjuvants, wherein advantageously, a significant amount of a particular solvent is minimized or absent, the particular solvent being selected from any of the following exemplified solvents: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, cyclohexanol, tetrahydrofurfuryl alcohol, ethylene glycol, glycerol, methyl acetate, ethyl acetate Esters, ethyl lactate, butyrolactone, γ-butyrolactone, ethylene carbonate, propylene carbonate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-decyl-2-pyrrolidone, acetone, butanone, methyl isobutyl ketone, methyl propyl ketone, acetophenone, cyclohexanone, dichloromethane, chloroform, trichloroethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, ethanolamine, pyridine, chlorobenzene, toluene, xylene, or tetramethylurea.
[0023] The term "minimizing a significant amount of the aforementioned solvent" typically refers herein to a content of less than 5% w / w in the composition. However, the inventors have also provided guidance on adding specific additives that can mitigate the adverse effects of higher percentages of solvent content, as described later herein.
[0024] By choosing vegetable oil-based carriers such as methyl soybean oleate instead of paraffin oil or mineral oil, the inventors were able to prepare oil-based pymetrozine dispersion compositions without needing to prehydrate the pymetrozine active ingredient before preparing the composition.
[0025] Without being bound by any theory, the inventors have deduced chemical structures that are thought to cause certain unwanted features in pymetrozine compositions containing a particular solvent, and therefore in some embodiments, the oil dispersion concentrate compositions (and / or diluted dispersions thereof) of the present invention are sometimes usefully characterized by minimizing or eliminating the content of structures labeled (B) below.
[0026]
[0027] in,
[0028] r and s are each independently between 0 and 12, but typically between greater than 0 and 12, and
[0029] L is one or more of the following: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, cyclohexanol, 2-ethylhexanol, alkylbenzene, tetrahydrofurfuryl alcohol, ethylene glycol, glycerol, methyl acetate, ethyl acetate, ethyl lactate, butyrolactone, ethylene carbonate, propylene carbonate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-decyl-2-pyrrolidone, acetone, butanone, methyl isobutyl ketone, methyl propyl ketone, acetophenone, cyclohexanone, dichloromethane, trichloromethane, trichloroethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, ethanolamine, pyridine, chlorobenzene, toluene, xylene, or tetramethylurea.
[0030] Generally, in this document, the term "minimum content" for the structures disclosed above is understood to mean an amount such that L accounts for an amount equal to or less than 5% w / w of the composition.
[0031] However, the inventors emphasize that the ability to detect or quantify the percentage content, presence or absence of any of these disclosed structures should not be used as the sole determining factor or even as an indicative basis for determining whether a particular oil-based pymetrozine dispersion composition is within or outside the scope of this invention, although such data may be used as guidance. The decisive factor will be whether the composition contains or does not contain the non-toxic bioactive formulation adjuvants of this invention as defined elsewhere herein.
[0032] Therefore, some embodiments of the present invention can be characterized as non-aqueous biocidal suspension concentrate compositions comprising compounds having structural formula (A) in the form of solid particles.
[0033]
[0034] Compounds with structural formula (B)
[0035]
[0036] The alkyl polysaccharide surfactant comprises an aqueous solution of alkyl polysaccharide glycosides, alkyl polyglucosides, or mixtures thereof; an alkoxylation auxiliaries; anionic surfactants selected from phosphate- or phosphonate-based surfactants, sulfate- or sulfonate-based surfactants, and combinations of phosphate- or phosphonate-based surfactants and sulfate- or sulfonate-based surfactants; triethylamine; methyl soybean oleate; and optionally, additional bioactive compounds (such as flonicamid), wherein...
[0037] r and s are each independently greater than 0 and 12, and L is one or more of the following: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, cyclohexanol, 2-ethylhexanol, alkylbenzene, tetrahydrofurfuryl alcohol, ethylene glycol, glycerol, methyl acetate, ethyl acetate, ethyl lactate, butyrolactone, ethylene carbonate, propylene carbonate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-decyl-2-pyrrolidone, acetone, butanone. The composition contains methyl isobutyl ketone, methyl propyl ketone, acetophenone, cyclohexanone, dichloromethane, chloroform, trichloroethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, ethanolamine, pyridine, chlorobenzene, toluene, xylene, or tetramethylurea, and the content of L is equal to or less than 5% w / w in the composition, and the amount of water constituting the aqueous solution of the alkyl polysaccharide surfactant is between greater than 0% w / w and equal to or less than 5% w / w based on the weight of the non-aqueous pest-killing suspension concentrate composition.
[0038] In some specifically mentioned embodiments, the advantage is achieved by including non-insecticide formulation adjuvants in the composition, which are alkoxylation adjuvants such as alkoxylated / ethoxylated carboxylic acid esters, ethoxylated carboxylic acids, ethoxylated primary or secondary straight-chain or branched alcohols, alkoxylated fatty alcohols, ethoxylated fatty alcohols, coconut fatty alcohol ethoxylates, C 12 / C14 Fatty alcohol ethoxylates, cetyl alcohol / oleyl alcohol ethoxylates, C 16 / C18 Fatty alcohol ethoxylates, C 12 / C18 Fatty alcohol ethoxylates, C 8 / C14 Fatty alcohol ethoxylates, C 13 / C15 Fatty alcohol ethoxylates, C 11 / C15 Fatty alcohol ethoxylates, tributylphenol ethoxylates, ethoxylated (straight-chain or branched) alkyl aryl groups (such as ethoxylated alkylphenols, nonylphenol ethoxylates and ethoxylated acetylenic diols), alkoxylated fatty alcohols / ethoxylated fatty alcohols (such as CAS No. 69011-36-5 (e.g.) U / 050), ethoxylated isotridecyl alcohol (CAS. 9043-30-5), copolymer PEG / polyisobutylene anhydride-tall fatty acid (CAS. 173717-47-0) (e.g., 4914). Also noted are ABA block copolymers having a hydrophilic portion of polyethylene oxide (PEG) and a hydrophobic portion of 12-hydroxystearic acid. A particularly mentioned example is the commercial surfactant Atlox, with an average molecular weight of approximately 5,000. TM 4912 (a trademark of Uniqema). Another example of this polymeric surfactant is the commercial surfactant Termul. TM 2510 (a trademark of Huntsman Corporation)
[0039] In some embodiments, advantages are achieved by comprising non-insectic (pesticide-killing) formulation adjuvants, which are anionic surfactants such as phosphate esters (monoesters and diesters, mixtures of free alcohols and phosphoric acid), alkylphosphonic acids, phosphate esters of fatty alcohols, phosphate esters of ethoxylated fatty alcohols, alkoxylated / ethoxylated phosphate esters, alkylphosphonic acids, and anionic / ethoxylated phosphate esters. Such formulation adjuvants that can be used in this invention can be derived from… Examples include 1306 (alkyl phosphates based on isotriadecyl alcohol ethoxylates) and olefin sulfonates containing hydrophobic alkyl chains and anionic sulfonic acid groups, as well as sulfonated sulfates derived from fatty alcohols and alcohol ethoxylates.
[0040] It should be noted that while the various solvents mentioned above can generally be harmful in binary combinations with pymetrozine, the optimized oil-based pymetrozine dispersion of the present invention can withstand equivalent amounts of these solvents, which would typically lead to mixing problems if combined with pymetrozine in the absence of excipients. Therefore, it has been unexpectedly found that, despite the inclusion of excipients (such as NINATE), the oil-based pymetrozine dispersion of the present invention can withstand these solvents. TM alkyl series (C 10-16 The calcium benzenesulfonate may contain up to about 40% solvent (including isobutanol, 2-ethylhexanol, 1-hexanol or 1-butanol), but due to the incorporation of the components of the present invention, the negative impact on the characteristics of the concentrate previously encountered is no longer apparent in the oil-based pymetrozine dispersion composition of the present invention.
[0041] In some concentrated composition embodiments of the pymetrozine oil-based dispersion composition of the present invention, it comprises triethylamine (TEA) and alkyl polyglucosides / alkyl polysaccharides (such as... 650EC 1620, ATLOX TM AL2575 / Al2579, PG8107 / Compounds exemplified by combinations of PG 8105, Tensoper APG 810, etc., improve both the quality and dispersibility of the concentrate in water when preparing diluted end-use liquids. The inventors have also found, unexpectedly, that compounds exemplified by triethylamine (TEA) achieve improved color stability of the pymetrozine oil-based dispersion concentrate compositions of the present invention during storage, exhibiting reduced yellowing compared to compositions without TEA. Alkyl polyglucosides and alkyl polysaccharides are sometimes also referred to as alkyl polysaccharides; these terms have been used interchangeably.
[0042] It has been found that the inclusion of triethylamine is advantageous in terms of the dispersibility of the concentrate even in the absence of alkyl polyglucosides, etc. However, as disclosed, some additional advantages are achieved by including alkyl polyglucosides in the concentrate composition and by including TEA in the composition.
[0043] Further unexpected effects were discovered with the inclusion of alkyl polyglucosides / alkyl polyglucosides (APGs) / alkyl polysaccharides. Typically, even small amounts of water in oil-based pymetrozine dispersion concentrates can have undesirable effects, sometimes even causing the dispersion to "cure." Compositions containing APGs were found to be tolerant of small amounts of water. As a non-limiting demonstration, it was found that introducing APG grades during blending as an approximately 50% aqueous solution actually significantly improved the composition (despite the presence of included water).
[0044] The inventors have encountered the advantages of increased and / or synergistic formulation quality and / or stability from combining different non-insecticide formulation adjuvants, which outweigh the advantages achieved by including only one, two, or three of the identified and disclosed useful non-insecticide formulation adjuvants in the absence of other adjuvants.
[0045] In some embodiments of the invention, the optimized oil-based pymetrozine dispersion composition, in addition to containing an insecticidal compound comprising pymetrozine and optionally an additional pesticide between greater than 0% w / w and equal to or less than 40% w / w, also contains all of the following non-insectic components:
[0046] a) Alkyl polysaccharide glycosides and / or alkyl polyglucosides and / or alkyl polysaccharides (including both),
[0047] b) Anionic surfactants, such as phosphonates, phosphates, sulfonates, and sulfates (branched or linear), etc.
[0048] c) One or more alkoxylation auxiliaries, such as alkoxylated / ethoxylated carboxylic acid esters, ethoxylated carboxylic acids, ethoxylated primary or secondary straight-chain or branched alcohols, alkoxylated fatty alcohols, ethoxylated fatty alcohols, etc.
[0049] d) Triethylamine (end-use dispersible stabilizer / compensator), and
[0050] e) Vegetable oils or alkylated vegetable oils, such as methyl soybean oleate, methyl palmitate, methyl oleate, methyl linoleate, methyl linolenic acid, methyl stearate, methyl palmitate, etc.
[0051] In some embodiments of the invention, the optimized oil-based pymetrozine dispersion composition, in addition to containing insecticidal compounds between greater than 0% w / w and equal to or less than 40% w / w, also contains all of the following non-insectic components.
[0052] a) Alkyl polysaccharide glycosides and / or alkyl polyglucosides and / or alkyl polysaccharides,
[0053] b) Anionic surfactants, such as phosphonates, phosphates, sulfonates, sulfates, etc.
[0054] c) Alkoxylation auxiliaries, such as alkoxylated / ethoxylated carboxylic acid esters, ethoxylated carboxylic acids, ethoxylated primary or secondary straight-chain or branched alcohols, alkoxylated fatty alcohols, ethoxylated fatty alcohols, etc.
[0055] d) Vegetable oils or their derivatives, exemplified by alkylated vegetable oils, such as methyl soybean oleate, methyl palmitate, methyl oleate, methyl linoleate, methyl linolenic acid, methyl stearate, methyl palmitate, etc.
[0056] e) Dispersible stabilizers / compensators for end-use applications, such as tertiary amines and alkyl amines (e.g., triethylamine, triethanolamine, N,N-diisopropylethylamine, butylamine, etc.).
[0057] In several embodiments, the "non-aqueous" pymetrozine oil-based dispersions of the present invention advantageously contain up to about 5% water, provided that the water is accompanied by an alkyl polysaccharide (APG) that is an ingredient of the composition. Water is typically introduced into the compositions of the present invention as a carrier for one or more non-insectic active components of the oil-based pymetrozine dispersion (particularly alkyl polysaccharides such as APG obtained as aqueous solutions). Surprisingly, this water carrier is not disadvantageous compared to introducing an equal amount of water into the composition in the absence of, for example, APG.
[0058] In the established embodiments, the concentrated oily dispersion of the present invention, prior to dilution, contains, by weight, less than 4%; less than 3%; less than 2%; less than 1%; less than 0.9%; less than 0.8%; less than 0.7%; less than 0.6%; less than 0.5%; less than 0.4%; less than 0.3%; less than 0.2%; less than 0.1%; less than 0.05% of a specified solvent selected from the group consisting of: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, cyclohexanol, 2-ethylhexanol, alkylbenzene, tetrahydrofurfuryl alcohol, ethylene glycol... Alcohols, glycerol, methyl acetate, ethyl acetate, ethyl lactate, butyrolactone, γ-butyrolactone, ethylene carbonate, propylene carbonate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-decyl-2-pyrrolidone, acetone, butanone, methyl isobutyl ketone, methyl propyl ketone, acetophenone, cyclohexanone, dichloromethane, chloroform, trichloroethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, ethanolamine, pyridine, chlorobenzene, toluene, xylene, or tetramethylurea.
[0059] However, despite the above, the inventors envision that by carefully selecting combinations of non-insecticide formulation adjuvants based on these disclosed guidelines and principles, it is possible to compensate for even greater percentage w / w content of the aforementioned solvents, and it is entirely conceivable that such compositions will likely be free of significant drawbacks as long as these instructions are followed.
[0060] Therefore, the inventors suggest that when selecting non-insecticide components for the pymetrozine oily dispersion compositions of the present invention, care must be taken not only to examine and evaluate the chemical properties of the component, but also to examine and evaluate the solvents providing that component. This is because it may be found that in some cases a particular component is beneficial to the composition when provided as a pure compound, but may perform poorly when used (included, incorporated) as a mixture or in a solution in one of the generally unfavorable solvents identified in this disclosure. Another situation is that while a solvent carrier may reduce the effectiveness of a selected excipient, the same excipient introduced into another solvent may exhibit superior advantages. Therefore, the inventors note that if the level of additional advantage resulting from including a particularly advantageous excipient in the composition is disappointing, it may not be necessary to abandon the non-insecticide formulation adjuvant as an option, but rather to choose a different commercially available grade or version provided in a different solvent or even as a compound without a carrier solvent.
[0061] As an illustrative example, the inventors have noted three different grades of alkyl (C 10-16 Calcium benzenesulfonate (alkylbenzenesulfonate) is a beneficial non-pesticide formulation adjuvant, namely NINATE. TM 60B-E; NINATE TM Both 60L and NINATE 60EPG are supplied by Stepan Company (22 West Auxiliary Drive, Northfield, Illinois, 6009). Although all these commercial products contain alkyl (C...) 10-16 ) Calcium benzenesulfonates, but they differ in the solvents that provide them:
[0062]
[0063] Clearly, based on the findings disclosed herein, some solvents are less favorable to the quality, stability, and / or ease of preparation of pymetrozine oil-based dispersions than others. The choice of which grade of alkylbenzene sulfonate to include (if chosen as an anionic surfactant) may significantly influence the quality of the concentrated oil-based pymetrozine dispersion composition and the degree of improvement in both physical and dispersion stability, even if all three grades are alkylbenzene sulfonates.
[0064] As mentioned, anionic surfactants (such as phosphonates, phosphates, sulfonates, sulfates, etc. (branched or linear)) are one type of non-insecticide formulation adjuvants of the present invention that are usefully included in the innovative concentrated oil-based pymetrozine dispersion (OBPD) compositions of the present invention. Typical examples of generally useful anionic surfactants include sulfonates, alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glyceryl ether sulfonates, α-methyl ester sulfonates, sulfonated fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glyceryl ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, glyceryl monoester (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid hydroxyethyl sulfonates, fatty acid sarcosine salts, fatty acid taurine salts, and alkyl oligoglucosides sulfates. Alkyl ether sulfates are readily available.
[0065] In some embodiments, branched alkylbenzene sulfonates are found to be superior to linear varieties of these anionic surfactant compounds and are advantageously combined in the composition with anionic surfactants such as isotracenediyl polyoxyethyl phosphate mono / dieser (acid form)
[0066] Alkyl ether sulfates (“ether sulfates”) are anionic surfactants that can be produced by sulfation and subsequent neutralization of, for example, fatty alcohols or carbonyl alcohol polyethylene glycol ethers. Some examples are sulfates of the addition products of ethylene oxide with ganol, octanol, 2-ethylhexanol, decanol, lauryl alcohol, isotrigine alcohol, myristyl alcohol, cetyl alcohol, palmitole alcohol, stearyl alcohol, isoleyl alcohol, transoleyl alcohol, phellandrene alcohol, arachidonic acid, eicosanol, betaine alcohol, gentianol, and brassinolide, as well as technical-grade mixtures thereof in the form of their sodium and / or magnesium salts. Ether sulfates can have both conventional and narrow homologue distributions.
[0067] The presence of a few moles of ethylene oxide in the form of its sodium and / or magnesium salts with technical grade C 12 / 14 Or C 12 / 18 Ether sulfates of coconut fatty alcohol fraction adducts include sodium dodecyl ethoxysulfate, fatty acid sulfates (FAS) and fatty alcohol ether sulfates (FAES), linear alkylbenzene sulfonates (LAS), secondary alkyl sulfonates (SAS), etc. Of course, there are also ether sulfates (and alkyl phosphate ethers) of adducts based on one or more moles of ethylene oxide.
[0068] Alkyl sulfates, alkyl ether sulfates, alkyl aryl ether sulfates
[0069]
[0070]
[0071] Note the salts of alkyl naphthalene sulfonic acids, salts of naphthalene sulfonic acid-formaldehyde condensation products, salts of condensation products of naphthalene sulfonic acid, phenol sulfonic acid, and formaldehyde, alkali metal salts of alkyl naphthalene sulfonic acids, salts of naphthalene sulfonic acid-formaldehyde condensation products; sulfosuccinate metal salts with branched or straight-chain alcohols as monoesters and diesters; sodium dioctyl sulfosuccinate; alkyl succinate sulfates and any and all combinations thereof.
[0072] The inventors also noted the commercial sulfate / sulfonate NIFA,
[0073] Emulsogen APS100 (allyl polyoxyethylene sulfate, ammonium salt with 4 PO and 10 EO);
[0074] EPA 073 (Sodium salt of alkyl polyethylene glycol ether sulfate with 7 EOs); EPA 078 (Sodium salt of alkyl polyethylene glycol ether sulfate with 7 EOs); EPA1954 (C12 / C14 alkyl sulfate, sodium salt); LA 033 (C12 / C14 alkyl polyethylene glycol ether sulfate with 3 EOs, ammonium salt); LA 083 (C12 / C14 alkyl polyethylene glycol ether sulfate with 8 EOs, ammonium salt); LCA 213 (ammonium salt of alcoholic polyethylene glycol ether sulfate with 21 moles of EO); PF 20S (polyalkylene glycol ether sulfate, ammonium salt); LRO (liquid C12 / C14 alkyl polyethylene glycol ether sulfate, sodium salt with 2 EOs); LRO (a paste containing two EOs, C12 / C14 alkyl polyethylene glycol ether sulfate, sodium salt); BV (concentrated tributylphenol polyethylene glycol ether sulfate, sodium salt with 7 EOs); BV (liquid tributylphenol polyethylene glycol ether sulfate, sodium salt with 7 EOs);
[0075] LP 2 (Lauryl polyethylene glycol ether sulfate with 3 EOs, ammonium salt);
[0076] SF 8 (diisooctyl sulfosuccinate, sodium salt).
[0077] Another object of the present invention is to provide one or more methods for preparing concentrated pymetrozine oil-based dispersion compositions, the method comprising the steps of adding, stirring, grinding, collecting, homogenizing, and packaging, without requiring prehydration and / or presolubilization steps for processing the pymetrozine active ingredient prior to blending, particularly when the oil-based carrier is limited to vegetable oil or its derivatives (exemplified herein by methyl soybean oleate).
[0078] Another object of the present invention is to provide concentrated pymetrozine oil-based dispersion compositions, which are typically applied as insecticides to crop plants or, where necessary, to the vicinity or location of crop plants after being diluted and / or dispersed in a large amount of water prior to application.
[0079] definition
[0080] Before detailing the subject matter of this invention, it may be helpful to provide definitions for certain terms used herein. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this subject matter pertains.
[0081] As used herein, the term “effective” when used to describe a method for controlling unwanted pests means that the method provides a good or subjectively acceptable level of control over the unwanted pests without significantly interfering with the normal growth and development of the crop plant.
[0082] As used herein, the term “effective amount” refers to the amount of a pest control agent, mixture, or composition that is sufficient to achieve a good or acceptable level of control when digested, in contact with, or sensed.
[0083] As used herein, the term “agriculturally acceptable carrier” means a carrier known and accepted in the art for forming compositions for agricultural or horticultural purposes.
[0084] As used herein, the term "adjuvant" is broadly understood to be any substance that is not itself an active ingredient but enhances or is intended to enhance the effectiveness or physical properties of a pest control agent used with it. Adjuvants can be understood to include, but are not limited to, spreading agents, penetrants, compatibilizers, and drift inhibitors.
[0085] As used herein, the term “agriculturally acceptable inert additive” (which may include adjuvants, excipients, etc.) is typically understood to be any substance that is not itself an active ingredient but is added to a composition, such as adhesives, surfactants, synergists, antioxidants, defoamers, and thickeners, provided that they are acceptable for agricultural use.
[0086] As used herein, the term "additive" is defined as any substance that is not itself a biocide but is added to a composition, such as adhesives, surfactants, synergists, buffers, acidifiers, defoamers, and thickeners.
[0087] As used herein, the term “bucket mix” when referring to a combination of pests means the mixing of two or more pests or a combination of pests, usually in diluted form and often with other non-pesticide ingredients, in a spray tank or in a suitable storage container at the time of (before) spray application.
[0088] As used in this article, the term "plant" includes references to whole plants, plant organs (such as leaves, stems, twigs, roots, trunks, limbs, buds, fruits, etc.), or plant cells and propagation material.
[0089] As used in this article, the term "plant" when referring to crops includes agricultural crops (including field crops (soybeans, corn, wheat, rice, etc.), vegetable crops (potatoes, cabbage, etc.), and fruit trees (peach trees, etc.), nuts, etc.).
[0090] As used herein, the term “propagation material” should be understood to refer to all reproductive parts of a plant, such as seeds and spores; vegetative structures, such as bulbs, corms, tubers, rhizomes, roots, basal shoots, stolons, and buds.
[0091] As used herein, the term "bioactivity" includes references to pest control, herbicidal, insecticidal and / or nematicidal activity, growth-promoting activity, and enhancement of plant growth rate and yield.
[0092] As used herein, the term "site" includes not only areas where pests may have already grown, but also areas where pests have not yet appeared, as well as cultivated areas. Pests include, but are not limited to, plant pathogenic fungi and unwanted insects or pathogens introduced by insects.
[0093] As used in this article, the term "ha" refers to a hectare.
[0094] As used herein, the terms “mixture” or “combination” refer to, but are not limited to, combinations in any physical form, such as blends, solutions, suspensions, dispersions, emulsions, alloys, etc.
[0095] Generally, unless otherwise defined, as used herein, the terms "substantially free of, for example," "solvents or adjuvants," or "substantially free of," for example, "solvents or adjuvants," generally mean that the composition is free of that ingredient or contains an amount of that ingredient that does not significantly affect the activity or quality of the pest-killing composition of the present invention. Unless the context indicates or specifies otherwise, the term "free of" should be understood as "substantially free of" or "substantially free of," in order to account for the possibility of unintentional inclusion, for example, trace amounts of commercial ingredients that may be present on the label of which may not show trace amounts.
[0096] Unless otherwise specified, the term "a / an" as used herein includes both the singular and the plural. Therefore, the terms "a / an" or "at least one" are used interchangeably in this application.
[0097] Throughout this application, the description of various embodiments uses the term "comprising"; however, those skilled in the art will understand that in certain specific circumstances, the language "substantially consisting of" or "consisting of" may be used instead to describe embodiments.
[0098] Unless otherwise defined or required by the context, numerical values and ranges herein should generally be understood to be defined or modified by the term “about” (which may be interchangeable with approximately). Unless the context requires otherwise, the term “about” as used herein specifically includes ±10% of the indicated value (e.g., within a certain range). In addition to the general rules of rounding, the endpoints of all ranges relating to the same component or property herein include endpoints that are independently combinable and include all intermediate points and ranges. It should be understood that, where a parameter range is provided, the invention also provides all integers within that range and their decimal places, as if disclosed separately. For example, “10%-50%” specifically includes 9.5%, 9.6%, 9.7%, 9.8%, 9.9%, 10%, 10.1%, 10.2%, etc., up to 50.44%, as if each had been disclosed separately. Summary of the Invention
[0099] The present invention provides a non-aqueous biocidal suspension composition comprising a biocidal compound in the form of solid particulate matter, an alkyl polysaccharide surfactant, one or more non-biocidal active formulation aids, and an oil-based carrier, wherein the biocidal compound is a hygroscopic, water-soluble, and / or solvent-absorbent compound, and wherein the non-aqueous biocidal suspension composition optionally comprises additional biocidal compounds.
[0100] Specific embodiments of the present invention provide a pourable, storage-stable concentrated pymetrozine oil-based dispersion composition, which, in addition to containing pymetrozine, also contains... 650 examples of alkyl polysaccharides (APG); triethylamine; isotridecyl polyoxyethyl phosphate monoester / diester ( 1306); branched alkylbenzene (C 11-13 Calcium sulfonate salts ( 401A);
[0101] 4912 (a copolymer having a hydrophilic portion of polyethylene oxide (PEG) and a hydrophobic portion of 12-hydroxystearic acid) or Atlox 4914 (PEG polyisobutylene anhydride tall oil fatty acid copolymer; an organic derivative of lithium montmorillonite clay (or fumed silica) and a plant-based oil (e.g., methyl soybean oleate) as a carrier).
[0102] In certain embodiments, the composition comprises an additional pest control agent exemplified by flupyradifurone.
[0103] In particular, the present invention provides a pourable, storage-stable concentrated pymetrozine oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage (dilution), characterized by low viscosity, physical quality and stability, and especially water dispersibility stability as defined herein or by recognized compounding standards, having the following percentage content of the concentrate by mass (weight):
[0104] A formulation adjuvant comprising, but not limited to, greater than 0% and equal to or less than 40%, sometimes 10%-35% w / w pymetrozine and optionally an additional pest-killing compound, and comprising, between 0.2% and equal to or less than 30% w / w, a non-insecticide formulation adjuvant selected from the group consisting of,
[0105] a. Emulsifiers / surfactants in concentrations between greater than 1% and approximately 10%, which are composed of... 1306 (alkyl phosphate based on isotracene alcohol ethoxylate), 401A (branched alkylbenzene (C 11-13 ) sulfonates), and advantageously both are exemplified;
[0106] b. A dispersant comprising greater than 1% to about 10%, which is composed of 4914 (PEG polyisobutylene anhydride-talc fatty acid copolymer) and / or Example 4912 (a block copolymer having a hydrophilic portion of polyethylene oxide (PEG) and a hydrophobic portion of 12-hydroxystearic acid);
[0107] c. 0.1%-3% of thickeners and / or rheology modifiers, such as magnesium aluminum silicate, organobentonite, organic derivatives of lithium montmorillonite clay, silica, fumed or colloidal silica, or one or more of these.
[0108] d. End-use dispersible stabilizers / compensators and modifiers, greater than 0% to about 20%, typically comprising components selected from: 1% to about 10% alkyl polysaccharides (alkyl polyglycosides) such as 650; approximately 1% to approximately 7% of phosphate esters, such as 1306, about 0.1%-1% of triethylamine, and preferably a combination of two or more thereof; and
[0109] Any and all combinations of two or more of ea-d;
[0110] The oil-based liquid carrier is added up to 100%. In many embodiments, the water content in the concentrated pymetrozine oil-based dispersion is less than or equal to 5% by weight of the total dispersion concentrate, typically greater than 0% to less than or equal to 5%, excluding any water pre-hydrated and associated with pymetrozine (if present).
[0111] Therefore, in several embodiments, the present invention provides an insecticidal oil dispersion (OD) composition comprising pymetrozine and vegetable oils and / or derivatives thereof (exemplified by methyl soybean oleate, methylated seed oils, etc.) in the absence of solvents (as defined herein) that would adversely affect the efficacy of the composition. This composition exhibits excellent ease of manufacture (including aspects of pymetrozine curing, dispersibility, and / or curing) and / or improved viscosity, physical stability (including aspects of viscosity and yellowing), and dispersibility in water when diluted to form an end-use liquid for application.
[0112] In several embodiments, the present invention provides an insecticidal oil dispersion (OD) composition comprising pymetrozine and vegetable oils and / or derivatives thereof (exemplified by methyl soybean oleate and methylated seed oil), the composition of which can be prepared without pretreatment or prehydration of the pymetrozine active ingredient (ai) prior to blending.
[0113] The inventors have noted the results achieved in which the carrier in the pymetrozine oil dispersion is a plant-based oil, exemplified by alkylated vegetable oils (e.g., methyl soybean oleate), rather than a carrier (such as mineral oil and paraffin oil).
[0114] In noteworthy embodiments, the present invention provides an insecticidal oil dispersion composition containing pymetrozine and other agricultural chemical adjuvants in the absence of destabilizing and degrading amounts of destructive solvents as previously detailed, or when compensated by selecting non-insectic formulation adjuvants as agricultural chemical adjuvants as disclosed herein.
[0115] In several embodiments, the present invention provides an insecticidal oil dispersion composition comprising pymetrozine and other agrochemical adjuvants in the absence (or substantially absence) of specific destabilizing and degrading antifreeze agents (exemplified by glycol ether compounds, notably propylene glycol). However, the inventors note that several commercially available non-pesticide agricultural ingredients can be provided with undisclosed minimum amounts of a carrier (such as propylene glycol), and the unintentional inclusion of these minimum amounts does not cause compositions containing them to fall outside the scope of the invention, provided that the advantages of the composition are not compromised.
[0116] Generally speaking, it should be mentioned that the unintentional (or even intentional) addition or inclusion of trace amounts of ingredients indicated herein as “absent” (in amounts so small as to have no harmful or even noticeable effect on the composition) should not be considered beyond the scope of this invention (e.g., when a commercial additive with a particular grade of an undesirable ingredient as a minor component is obtained unknowingly). This is especially true when such unwanted ingredients are added in such minute amounts for design purposes while utilizing this invention. These negligible amounts are considered “substantially absent” (as mentioned, defined as being contained in such small amounts that they have no visible harmful or even noticeable effect on the composition) or completely absent.
[0117] In some embodiments, the present invention generally relates to concentrated compositions of insecticidal oil-based dispersions comprising pymetrozine, and, in addition to any water (if present) associated with the pymetrozine active ingredient due to pre-hydration prior to introduction into the formulation, containing up to 5% by weight (preferably less). Thus, limiting the water content improves the ease of mixing, physical and / or chemical stability, and quality of the concentrated oil-based dispersion, and also improves the ease with which the oil-based dispersion can be subsequently diluted in water to form a uniform end-use insecticide spray mixture for application (this characteristic is maintained even after the storage period). However, as detailed herein, it is precisely the non-insectic formulation adjuvants of the present invention that enable the safe inclusion of small amounts of water (and unfavorable solvents as defined above) in the oil-based pymetrozine dispersion compositions of the present invention without impairing the physical properties, stability, or ease of manufacture of the OBPD. In other words, the disclosed additives of the present invention can, to some extent, compensate for the “harm” that might otherwise result from the inclusion of less advantageous components.
[0118] Many embodiments of the present invention specifically relate to oil-based pymetrozine dispersions (OBPD) compositions comprising pymetrozine and specific agrochemical adjuvants that avoid compatibility and stability challenges. These compositions are characterized by containing, or not containing, specific solvents in reduced amounts. As defined above, “not containing” generally includes substantially no or “largely no” solvents.
[0119] In some concentrated embodiments, the present invention specifically relates to oil-based pymetrozine dispersion (OBPD) compositions containing no more than 5% water (excluding any water associated with pymetrozine through prehydration, if present), thereby improving the quality of the dispersion and the ease with which it can subsequently be diluted and dispersed in water to form an end-use biocide for application.
[0120] In many embodiments, the oil-based pymetrozine dispersion (OBPD) compositions of the present invention are intended to be diluted with water prior to their pesticidal application, and those diluted end-use liquids prepared by adding the compositions of the present invention to water are clearly within the scope of the present invention. Therefore, the aforementioned limitation on water content refers to the water content (excluding any water associated with the pymetrozine active ingredient) of the stable concentrate embodiments of the present invention, and not to diluted ready-to-use liquids (which are prepared immediately prior to their application as a pesticidal agent and do not require stable storage for, for example, several hours).
[0121] In many notable embodiments, the present invention more specifically relates to oil-based pymetrozine dispersions (OBPDs) comprising pymetrozine, one or more dispersants, one or more emulsifiers / surfactants, one or more rheology modifiers, and one or more oil adjuvants, these OBPD compositions being characterized by ease of compounding and / or improved stability. The pymetrozine oil-based dispersion compositions of the present invention allow for high loadings of pymetrozine in the concentrate examples of the present invention and significantly improve stability and ease of dispersion in water.
[0122] In some typical embodiments, the present invention more specifically relates to packaged oil-based pymetrozine dispersions (OBPD) compositions comprising pymetrozine, one or more dispersants, one or more emulsifiers / surfactants, one or more rheology modifiers, and one or more oil adjuvants. These OBPD compositions are characterized by ease of compounding and / or improved stability, contained in packaging exemplified by containers that do not negatively affect the stability of their contents. The packaging containers for the compositions must be equipped with a closure system and made of a material such that, when the composition is packaged therein, the composition contained therein is not allowed to be adversely affected, for example, during storage, by the ingress of water or water vapor exceeding the limits defined herein.
[0123] The present invention also relates to a method for preparing an oil-based pymetrozine dispersion (OBPD) composition, the method comprising the steps of: adding, stirring, grinding, collecting, homogenizing, and packaging (typically packaged into a container, as described below, that will not negatively affect the stability of its contents).
[0124] According to reports, pymetrozine undergoes significantly faster photodegradation in water compared to non-aqueous systems. See Ximei Liang et al., “Pivotal role of water molecules in the photodegradation of Pymetrozine: New insights for developing green pesticides”, Journal of Hazardous Materials, (2021): https: / / doi.org / 10.1016 / j.jhazmat.2021.127197. Clearly, in addition to the innovative improvements in ease of manufacture, quality, dispersibility stability, and physical properties of the oil-based pymetrozine dispersion (OBPD) compositions of the present invention disclosed herein, additional advantages are anticipated by limiting the water content when or if the OBPD compositions are exposed to light (especially sunlight), particularly during storage. Therefore, it is envisioned that when the packaging container containing the composition is made of a light-shielding material (opaque) or is contained within an external opaque container (e.g., a box), such that these packages do not allow the composition contained therein to be exposed to light (especially sunlight) at photodegradation levels, further chemical stability can be achieved during storage under sunlight exposure conditions. Similarly, it is envisioned that after application in a pest-killing manner under field conditions, a greater proportion of pymetrozine will remain undegraded for a longer period compared to compositions with a water content higher than defined herein.
[0125] Furthermore, in several concentrate examples, the stability of the oil-based pymetrozine dispersion composition and the stability of the concentrate's dispersibility in water for end-use after storage are susceptible to impairment by the presence of more than a small amount of water.
[0126] As mentioned above, it is generally important that the containers packaging these oil-based pymetrozine dispersions (OBPD) compositions are sufficiently impermeable to moisture, sunlight, and often both, so that the quality of the dispersion is maintained during storage and its dispersibility is not affected by storage at elevated temperatures.
[0127] Typically, suitable containers for many embodiments of the oil-based pymetrozine dispersion concentrate compositions of the present invention are formed of a material that provides a barrier to moisture and / or light (such as sunlight) with wavelengths between 250 and 400 nm. These containers are constructed and sealed to maintain the stability of the oil-based pymetrozine dispersion composition contained within the container through closures that do not impair the level of moisture and / or light impermeability provided by the material forming the container.
[0128] Typically, a container is considered suitable for use in packaging (OBPD) compositions if, after a period of storage at temperatures and humidity exemplified by 54°C and / or 40°C / 75%RH, the percentage of water content in the contained OBPD does not increase to more than 5% w / w.
[0129] In some specifically mentioned embodiments, the container used to package the OBPD composition will be impermeable to moisture such that after a storage period of more than one week in the container at temperatures and humidity exceeding 25°C (exemplified by two weeks at 54°C with 75% relative humidity (RH) and one month at 40°C), the water content % of the contained OBPD will not increase to more than 1% w / w.
[0130] For numerous embodiments, containers suitable for packaging the oil-based pymetrozine dispersion concentrate of the present invention should be sufficiently opaque to light such that when exposed to sunlight or artificial light with wavelengths between 250 and 400 nm during storage, the pymetrozine content degrades by no more than 5% w / w compared to the pymetrozine content at the beginning of the storage period.
[0131] In several specifically mentioned embodiments, once the oil-based pymetrozine dispersion concentrate compositions are compounded, they are packaged in containers that ensure that the percentage moisture content (water content) of the oil-based pymetrozine dispersion compositions remains substantially at the level at the time of compounding and / or at the start of storage during storage at temperatures and relative humidity above room temperature (above 25°C or above ambient temperature), and that the pymetrozine content does not significantly (understood to be greater than 5%) degrade due to photodegradation during the storage period.
[0132] At a minimum, the packaging container is constructed to be impermeable to moisture and light (e.g., sunlight), such that the packaging ensures that: after a period of storage in the container at the appropriate temperature and humidity (exemplified by two weeks at 54°C and / or at least one month at 40°C / 75% RH), the percentage of water content of the contained OBPD does not increase by more than 5% w / w compared to when it was formulated and / or at the start of storage, and ensures to be impermeable to light such that when stored exposed to sunlight or artificial light with wavelengths between 250 and 400 nm, the photodegradation of the pymetrozine content does not exceed 5% w / w compared to the start of storage.
[0133] Clearly, when the formulation of the oil-based pymetrozine dispersion (OBPD) composition is completed, it is advantageous to package the OBPD in a container that is impermeable to moisture and light (e.g., sunlight), such that the packaging ensures that the percentage of water content of the contained OBPD does not increase by more than 1% w / w compared to when it was formulated and / or at the start of storage during the expected storage period exemplified above, and ensures that the container is impermeable to light, such that when stored exposed to sunlight or artificial light with wavelengths between 250 and 400 nm, the photodegradation of the pymetrozine content does not exceed 5% w / w.
[0134] Several embodiments of the present invention also relate to oil-based pymetrozine dispersions (OBPD) compositions having a minimum or no (substantially or substantially no) content of any of the following solvents: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, cyclohexanol, 2-ethylhexanol, alkylbenzene, tetrahydrofurfuryl alcohol, ethylene glycol, glycerol, methyl acetate, ethyl acetate, ethyl lactate, butyrolactone, γ-butyrolactone, ethylene carbonate, propylene carbonate, etc. Acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-decyl-2-pyrrolidone, acetone, butanone, methyl isobutyl ketone, methyl propyl ketone, acetophenone, cyclohexanone, dichloromethane, chloroform, trichloroethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, ethanolamine, pyridine, chlorobenzene, toluene, xylene, or tetramethylurea.
[0135] In some embodiments, the invention also relates to oil-based pymetrozine dispersion compositions comprising at least one of the following, although typically a combination of alkoxylation auxiliaries (alkyl polyglucosides / alkyl polysaccharides / alkyl polysaccharides), triethylamine, phosphate esters / ethoxylated phosphate esters, sulfate / sulfonate-based surfactants, and up to but not exceeding about 5% water (in addition to pre-hydrated water associated with pymetrozine, if present).
[0136] Several optimized embodiments of the present invention also relate to oil-based pymetrozine dispersion (OBPD) compositions, wherein the oily carrier is selected from the group consisting of: vegetable oil-based carriers (exemplified by, but not limited to, methyl soybean oleate).
[0137] Many embodiments of the present invention provide oil-based pymetrozine dispersion (OBPD) compositions comprising pymetrozine and agriculturally acceptable non-insecticide components selected from ingredients such as dispersants, emulsifiers / surfactants, rheology modifiers, and vegetable oil adjuvants or derivatives thereof.
[0138] The embodiments specifically mentioned in this invention are characterized by the absence, in minimum quantity or in general, of solvents exemplified by: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, cyclohexanol, 2-ethylhexanol, alkylbenzene, tetrahydrofurfuryl alcohol, ethylene glycol, glycerol, methyl acetate, ethyl acetate, ethyl lactate, butyrolactone, γ-butyrolactone, ethylene carbonate, propylene carbonate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-decyl-2-pyrrolidone, acetone, butanone, methyl isobutyl ketone, methyl propyl ketone, acetophenone, cyclohexanone, dichloromethane, trichloromethane, trichloroethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, ethanolamine, pyridine, chlorobenzene, toluene, xylene, or tetramethylurea. However, these solvents are sometimes carriers of the formulation adjuvants that provide the non-insecticides of the present invention. Usually, these small amounts of solvent will not cause harm. However, as mentioned earlier, further advantages can be achieved by carefully selecting the carriers / solvents used to obtain these components.
[0139] It is worth mentioning that those OBPD examples, in addition to other components of pymetrozine and oil-based pymetrozine dispersion concentrate, also contain one, some, or all of the following:
[0140] Alkyl polyglucosides and / or alkyl polysaccharides;
[0141] Alkoxylated acids / alcohols, such as alkoxylated / ethoxylated carboxylic acid esters, ethoxylated carboxylic acids, ethoxylated primary or secondary straight-chain or branched alcohols, alkoxylated fatty alcohols, and ethoxylated fatty alcohols.
[0142] End-use dispersible stabilizers / compensators tertiary amines (such as triethylamine or triethanolamine); and
[0143] Anionic surfactants, alkyl (alkylaryl) phosphate esters / sulfates / ethoxylated phosphate esters, and / or ethoxylated sulfate (sulfonate) esters. Vegetable oil derivatives (such as methyl soy ester) are more preferred in the oil-based pymetrozine dispersion concentrates of the present invention compared to hydrocarbon (paraffin) and oil-based carriers, especially because, as the inventors have unexpectedly discovered, pymetrozine can be easily mixed without prehydration when vegetable oil derivatives are selected.
[0144] In some embodiments, the oil-based pymetrozine dispersion concentrate may further contain additional pest-killing (insect-killing) ingredients (exemplified herein by flonicamid).
[0145] In some embodiments, the concentrated oil-based pymetrozine dispersion composition contains the following inactive components as well as non-insecticide formulation aids and carriers.
[0146]
[0147]
[0148] Several notable embodiments of the concentrated oil-based pymetrozine dispersion compositions of the present invention (wherein pymetrozine is in a solid particulate, non-hydrated form) advantageously use a vegetable oil-based carrier or a derivative thereof in place of mineral oil or aromatic paraffin oil. In particular, the inventors have found that when a vegetable oil-based carrier or a derivative thereof (such as methyl soybean oleate) is used in place of mineral oil or aromatic paraffin oil, compositions can be readily formulated without pre-hydrating pymetrozine prior to blending the oil-based dispersion. This unexpected discovery allows for the inclusion of one or more active pest-killing compounds in higher percentages (which would otherwise be water content). This advantage gained through the use of a carrier (such as methyl soybean oleate) allows for higher pymetrozine loadings and / or the inclusion of additional pest-killing compounds (exemplified herein by, but not limited to, flonicamid).
[0149] Exemplary non-insecticide components that can be used in the pymetrozine oil-based dispersion (OD) compositions of the present invention include (but are by no means limited to) alkoxylation auxiliaries containing one or more C1-C4 alkoxy groups, such as one or more propoxy or ethoxy groups or mixtures thereof. Alkoxylated non-insecticide components may contain 3 to 50 alkoxy groups, such as 6 to 50 alkoxy groups, for example 7 to 20 alkoxy groups. Suitable alkoxylated nonionic auxiliaries may include ethoxylated primary or secondary straight-chain or branched alcohols, which often contain an average of 8 to 22 carbon atoms in the (straight-chain or branched) alkyl moiety; ethoxylated carboxylic acids, which often contain an average of 8 to 22 carbon atoms in the (straight-chain or branched) alkyl moiety; ethoxylated alkyl arylates (such as ethoxylated alkylphenols), wherein the (straight-chain or branched) alkyl moiety often contains an average of 5 to 20 carbon atoms; ethoxylated alkynyl glycols, typically containing 8 to 22 carbon atoms in the (straight-chain or branched) alkyl moiety; and propoxylated or ethoxylated and propoxylated analogs of all the aforementioned ethoxylated nonionic auxiliaries. As used herein, the term "alkoxylated auxiliaries" includes block copolymers containing alkoxy groups, such as block copolymers of ethylene oxide and propylene oxide, and block copolymers obtained by polycondensation of ethylene oxide and propylene oxide over ethylenediamine. Block copolymers are known to contain 30% to 80% ethylene oxide by weight.
[0150] Alkoxylated nonionic adjuvants can be water-miscible or water-immiscible liquids or water-soluble or water-insoluble solids. Typically, alkoxylated nonionic adjuvants are liquids.
[0151] Many suitable ethoxylated alcohols are commercially available, including, for example... PE or A series, which have a certain range of ethylene oxide content (indicated by the number after PE or "A") and are based on C containing approximately 50% by weight straight-chain alcohols (the remainder being mainly monobranched) 13 -C 15 Alcohols; BRIJ 96 and 98, which are based on unsaturated C 18 Straight-chain alcohols and having average ethylene oxide contents of 10 and 20, respectively; LM 11, which is based on C8-C having an average ethylene oxide content of 11. 14 alcohol; LM 17, which is based on C with an average ethylene oxide content of 17. 10 -C 14 alcohols; and TR / 15, which is based on branched C with an average degree of ethoxylation of 15. 13 Alcohols. Suitable examples of secondary alcohol ethoxylates are... 15-S-9, which is based on C having an average ethylene oxide content of 9. 11 -C 15 A mixture of straight-chain secondary alcohols. A suitable example of an ethoxylated carboxylic acid is Cithrol 6ML, which is an ethoxylated laurate with an average ethylene oxide content of 12. A suitable example of an ethoxylated alkylphenol is... NP13, which is based on nonylphenol having an average ethylene oxide content of 13. A suitable example of an ethoxylated acetylene diol is... 465, which is based on tetramethyldecynyl glycol having an average ethylene oxide content of 10. An example of a suitable block copolymer of ethylene oxide and propylene oxide is... PE L44 and PEP85. PE L44 has a molecular weight of 2200 and contains 40% by weight of ethylene oxides; Synperonic PE P85 has a molecular weight of 4650 and contains 50% by weight of ethylene oxides.
[0152] U / 050 127036-24-2 (Polyoxylated (POE)(5) isoundecaneol), Alkoxylated fatty alcohol / ethoxylated fatty alcohol CAS 69011-36-5, Ethoxylated isotridecaneol (CAS 9043-30-5).
[0153] (Branched C with 8 mol EO ethoxylated) 13 Carbonyl alcohol (tridecyl alcohol polyether-8)).
[0154] This article uses examples to illustrate " 4914 (ICI / CRODA) is a polymeric surfactant for agricultural use, in which the hydrophilic part is PEG and the hydrophobic part is an alkyd resin.
[0155] According to the report (see EP 2326169), 4914 (Croy Corporation, Uniquema) is CAS number 173717-47-0 and has been identified as a copolymer PEG poly-isobutylene anhydride-tall fatty acid.
[0156] For example, one could mention polyethylene glycol / polypropylene glycol / polyethylene glycol triblock polymers sold by Croda Corporation (formerly Leykama Corporation) under the name "Synperonic," such as... PE / L 64 (Poloxamer 184) sells ethyleneoxy, propyleneoxy, and ethyleneoxy condensates (13OE / 30OP / 13OE) (MW: 2900), which are classified as ethoxylated fatty alcohols and specifically as ethyleneoxy / propyleneoxy block copolymers.
[0157] Some non-restrictive examples
[0158] Composed of the following: branched C atoms ethoxylated with 5 mol EO 11 Carbonyl alcohol (undecyl alcohol polyether-5), ethoxylated C 11 Alcohol, CAS 127036-24-2,
[0159] T / 300: 70% branched C with 30 mol EO 13 Carbonyl alcohols, ethoxylated isocarbonyl alcohols 13 Alcohol (ethoxylated isotridecyl alcohol) (tridecyl alcohol polyether-30) CAS 69011-36-5, 9043-30-5,
[0160] E / 100 / 060: C with 6 mol EO 10 Alcohol (Decanol Polyether-6) CAS78330-20-8
[0161] T / 060: Branched C ethoxylated with 6 mol EO 13 Carbonyl alcohol (tetranol polyether-6)
[0162] CAS 9043-30-5
[0163] T / 030: Branched C ethoxylated with 3 mol EO 13Carbonyl alcohol (tridecyl alcohol polyether-3)
[0164] CAS 9043-30-5
[0165] E / 100 / 050: C ethoxylated with 5 mol EO 10 Alcohol (Isodecyl alcohol polyether-5)
[0166] CAS 78330-20-8
[0167] U / 060: Branched C ethoxylated with 6 mol EO 11 Carbonyl alcohol (undecyl alcohol polyether-6)
[0168] CAS127036-24-2
[0169] T / 090: Branched C atoms ethoxylated with 9 mol EO 13 Carbonyl alcohol (tetranol polyether-9)
[0170] CAS 9043-30-5
[0171] T / 080: Branched C ethoxylated with 8 mol EO 13 Carbonyl alcohol (tridecyl alcohol polyether-8)
[0172] CAS 9043-30-5
[0173] C 10 carbonyl alcohol + 7EO
[0174] 2-Propyl-2-heptanol + 8EO. Liquid at room temperature. HLB 15
[0175] C9-C 11 Carbonyl alcohol + 6EO. Liquid at room temperature. HLB value 12.5.
[0176] C 10 Carbonyl alcohol + 9EO. Liquid (paste-like) at room temperature. HLB 15.5
[0177] In addition, it is worth noting alkyl-polyoxyethylene alkanoates (where the alkyl group is C10) 12 -C 18) and rosin acid ethoxylates (Rhodia's products "Scurol C" and "Soprophor 64 / C").
[0178] The example given here is Hostaphart. TM 1306 isotridecyl polyoxyethyl (6EO) phosphate monoester / diester, in acid form; approximately 96% liquid emulsifier, which is a model for various phosphate-related compounds, particularly anionic phosphates / ethoxylated phosphates, that can be used in this invention. Hostaphat TM 1306 is a phosphate ester based on isotriadecyl alcohol ethoxylate and is used as an anionic emulsifier and dispersant.
[0179] Some other non-insecticide formulation adjuvants are,
[0180] CC 100: Cetyl phosphate, acid form, monoester / dieser, approximately 98%.
[0181] CK 100: Cetyl phosphate, potassium salt, monoester / dieser, approximately 98%; MDAH: Mono- / Di-2-ethylhexyl phosphate, acidic form, approximately 98%.
[0182] 145: Oleyl-based polyoxyethyl (5EO) phosphate monoester / diester, acidic form, approximately 98%.
[0183] 1306: Isotridecyl polyoxyethyl (6EO) phosphate monoester / diester, acid form, approximately 96%.
[0184] KL 340D: Lauryl polyethoxylated (4EO) phosphate, sodium salt, monoester / diester / triester, approximately 90%.
[0185] KW 340D: Stearyl polyethoxylated (4EO) phosphate, sodium salt, monoester / diester / triester, approximately 90%.
[0186] MIT 080: Tridecyl polyethylene glycol ether phosphate (8EO), acidic form, approximately 80% monoester, approximately 98%
[0187] OPS 30: Octanephosphonic acid dissolved in water, approximately 30%.
[0188] OPS 75E: n-Octanphosphonic acid + ethanol / water, approximately 75%
[0189] OPS100: n-Octanphosphonic acid, approximately 100%
[0190] Some commercially available ingredients in non-insecticide formulations include (but are not limited to) phosphate esters, such as organophosphate esters derived from ethoxylated alcohols, alkylphenols, or phenols, and consisting of a mixture of monoesters and diesters. Most of these surfactants are provided as free acids, which can be converted into salts by adding a base.
[0191] Alcohol ethoxylated phosphate esters
[0192]
[0193] Alkylphenol ethoxylated phosphate esters
[0194]
[0195] Alkylamine phosphate
[0196]
[0197] SERVOXYL VPDZ 3 / 100 Tridecyl Polyethylene Glycol Ether (3EO) Phosphate
[0198] SERVOXYL VPDZ 6 / 100 Tridecyl Polyethylene Glycol Ether (6EO) Phosphate
[0199] SERVOXYL VPDZ 20 / 100 Tridecyl Polyethylene Glycol Ether (20EO) Phosphate
[0200] SERVOXYL VPEZ 100 Isobutyl Phosphate
[0201] SERVOXYL VPFZ 5 / 100 Oleyl Alkenyl Polyethylene Glycol Ether (5EO) Phosphate
[0202] SERVOXYL VPFZ 7 / 100 Oleyl Alkenyl Polyethylene Glycol Ether (7EO) Phosphate
[0203] SERVOXYL VPGZ 6 / 100 Phenolic Polyethylene Glycol Ether (6EO) Phosphate
[0204] SERVOXYL VPHZ 100 Octyl Phosphate
[0205] SERVOXYL VPI 55 n-Butyl Phosphate, Na Salt
[0206] SERVOXYL VPIZ 100 n-Butyl Phosphate
[0207] SERVOXYL VPIZ 4 / 100 n-Butyl polyethylene glycol ether (4EO) phosphate
[0208] SERVOXYL VPKZ 100 Oleyl Alkenyl Phosphate
[0209] SERVOXYL VPKZ 5 / 100 Nonylphenyl polyethylene glycol ether (5EO) phosphate
[0210] SERVOXYL VPNZ 6 / 100 Nonylphenol Polyethylene Glycol Ether (6EO) Phosphate
[0211] SERVOXYL VPNZ 7 / 100 Nonylphenol Polyethylene Glycol Ether (7EO) Phosphate
[0212] SERVOXYL VPNZ 9 / 100 Nonylphenol Polyethylene Glycol Ether (9EO) Phosphate
[0213] SERVOXYL VPNZ 14 / 100 Nonylphenol Polyethylene Glycol Ether (14EO) Phosphate
[0214] SERVOXYL VPNZ 20 / 100 Nonylphenol Polyethylene Glycol Ether (20EO) Phosphate
[0215] SERVOXYL VPPZ 100 Isopropyl Phosphate
[0216] SERVOXYL VPRZ 100 Cetyl / Stearyl Phosphate
[0217] SERVOXYL VPRZ 6 / 100 Cetyl / Stearyl Propylene Glycol Ether (6EO) Phosphate
[0218] SERVOXYL VPRZ 11 / 100 Cetyl / Stearyl Polyethylene Glycol Ether (11EO) Phosphate
[0219] PROTE-PON P-TD-06-Z Alkyl Ether Phosphate
[0220] PROTE-PON P-TD-09-Z Alkyl ether phosphoric acid
[0221] PROTE-PON P-TD-12-Z Alkyl Ether Phosphate
[0222] PROTE-PON TD-09-K30 Alkyl Ether Potassium Phosphate
[0223] LUBRHOPHOS LP 700 is a phosphate ester containing aromatic bases.
[0224] RHODAFAC BG 510 is a phosphate ester containing an aliphatic base.
[0225] RHODAFAC PA 15 is a phosphate ester containing an aliphatic base.
[0226] RHODAFAC PA / 17 Alkylphenoxy polyethyl ester of phosphoric acid
[0227] RHODAFAC PA / 19 Alkylphenoxy polyethyl ester of phosphoric acid
[0228] RHODAFAC PE / 610 Alkylphenoxy polyethyl ester of phosphonic acid
[0229] RHODAFAC PE / 960 Alkylphenoxy polyethyl ester of phosphoric acid
[0230] RHODAFAC RA 600 is a phosphate ester containing an aliphatic base.
[0231] DERMALIX C Alkyl Phosphate in Water / Organic Media
[0232] ELFUG1N AKT 300% Aqueous Solution Phosphate
[0233] SANDOCLEAN SKBB Alkyl Phosphate
[0234] SANDOCORIN 8160 Phosphate
[0235] Phosphate esters in SANDOCORIN LF10 aqueous solution
[0236] Phosphate and triazole in SANDOCORIN LF20 aqueous solution
[0237] SANDOCORIN LF30: Phosphate, Triazole, and Multivalent Chelating Agent
[0238] SANDOPAN BFN phosphate ester mixture
[0239] SANDOPAN SF Phosphate
[0240] SANDOZIN EH Phosphate Esters in Water-Organic Solutions
[0241] SERVOXYL VPAZ 100 Lauryl Phosphate
[0242] SERVOXYL VPAZ 3 / 100 Lauryl Polyethylene Glycol Ether (3EO) Phosphate
[0243] SERVOXYL VPBZ 5 / 100 C 12 -C 18 Fatty alcohol (5EO) phosphate
[0244] SERVOXYL VPDZ 100 Tridecyl Phosphate
[0245] PROTE-PON P-TD-06-Z Alkyl Ether Phosphate
[0246] PROTE-PON P-TD-09-Z Alkyl ether phosphoric acid
[0247] PROTE-PON P-TD-12-Z Alkyl Ether Phosphate
[0248] PROTE-PON TD-09-K30 Alkyl Ether Potassium Phosphate
[0249] LUBRHOPHOS LP 700 is a phosphate ester containing aromatic bases.
[0250] RHODAFAC BC 510 is a phosphate ester containing an aliphatic base.
[0251] RHODAFAC PA 15 is a phosphate ester containing an aliphatic base.
[0252] RHODAFAC PA / 17 Alkylphenoxy polyethyl ester of phosphoric acid
[0253] RHODAFAC PA / 19 Alkylphenoxy polyethyl ester of phosphonic acid
[0254] RHODAFAC PE / 610 Alkylphenoxy polyethyl ester of phosphonic acid
[0255] RHODAFAC PE 960 Alkylphenoxy polyethyl ester of phosphonic acid
[0256] RHODAFAC RA 600 is a phosphate ester containing an aliphatic base.
[0257] DERMALIX C Alkyl Phosphate in Aqueous / Organic Media
[0258] Phosphate esters in ELFUG1N AKT 300% aqueous solution
[0259] SANDOCLEAN SKBB Alkyl Phosphate
[0260] SANDOCORIN 8160 Phosphate
[0261] Phosphate esters in SANDOCORIN LF10 aqueous solution
[0262] Phosphate and triazole in SANDOCORIN LF 20 aqueous solution
[0263] SANDOCORIN LF 30: Phosphate, Triazole, and Multivalent Chelating Agent
[0264] SANDOPAN BFN phosphate ester mixture
[0265] SANDOPAN SF Phosphate
[0266] SANDOZ1N EH Phosphate Ester in Water-Organic Solution
[0267] SERVOXYL VPAZ 100 Lauryl Phosphate
[0268] SERVOXYL VPAZ 3 / 100 Lauryl Polyethylene Glycol Ether (3EO) Phosphate
[0269] SERVOXYL VPBZ 5 / 100 C 12 -C 18 Fatty alcohol (5EO) phosphate
[0270] SERVOXYL VPDZ 100 Tridecyl Phosphate
[0271] PAE 147 Phosphorylated alcohol ethoxylate
[0272] PAE 1780 Phosphorylated Alcohol Ethoxylate
[0273] PPE 156 Phosphorylated phenol ethoxylate
[0274] PPE 159 Phosphorylated phenol ethoxylate
[0275] PPE 604 Phosphorylated Phenol Ethoxylate
[0276] Sodium salt of LIBRAPHOS AD Libraphos EP 120
[0277] LIBRAPHOS EP 120 Ethoxyalkylaryl phosphate, acid form
[0278] LIBRAPHOS EP Alkyl phosphate, acid form
[0279] LIBRAPHOS ER 150 Ethoxyalkylaryl phosphate, acid form
[0280] LIBRAPHOS HC 2A Ethoxyalkyl phosphate, acid form
[0281] LIBRAPHOS HC 2K, a potassium salt of Libraphos HC 2A
[0282] LIBRAPHOS HC3A Alkyl phosphate, acid form
[0283] Potassium salt of LIBRAPHOS L66 Libraphos P4 ester
[0284] LIBRAPHOS MR 100 Phosphate, Acid Form
[0285] LIBRAPHOS P4ESTER (phosphate ester, acid form)
[0286] LIBRAPHOS TL 100P4 Ethoxyalkyl phosphate, acid form
[0287] ALKAWET N Mixed Phosphate
[0288] NIKKOL DDP-2 diPOE(2) alkyl ether phosphate; free acid form
[0289] NIKKOL DDP-4 diPOE(4) alkyl ether phosphate; free acid form
[0290] NIKKOL DDP-6 diPOE(6) alkyl ether phosphate; free acid form
[0291] NIKKOL DDP-8 diPOE(8) alkyl ether phosphate; free acid form
[0292] NIKKOL DDP-10 diPOE(10) alkyl ether phosphate; free acid form
[0293] NIKKOL DLP 10 Dilauryl Alcohol Polyether-10 Phosphate
[0294] NIKKOL DNPP-4 dinonylphenol polyether-4 phosphate
[0295] NIKKOL DOP 8N Dioleoyl Alcohol Polyether-8 Phosphate
[0296] NIKKOL PHOSTEN HLP-N Sodium Lauryl Phosphate
[0297] MARLOPHOR NP7-ACID Nonylphenol polyethylene glycol ether phosphate metaester
[0298] MARLOPHOR OC5-Acid Trioleic Acid Glyceryl Trioleate Polyethylene Glycol Ether Phosphonate Metaester
[0299] MARLOPHOR ON 3-acid (Isotridecyl polyethylene glycol ether phosphate metaester)
[0300] MARLOPHOR ON 5-Acid (Isotridecyl polyethylene glycol ether phosphate)
[0301] MARLOPHOR ON 7-ACID Isotridecyl polyethylene glycol ether phosphate metaester
[0302] MARLOPHOR T6-Acid tallow polyethylene glycol ether phosphonate metaester
[0303] MARLOPHOR T10-Acid Tallow polyglycol ether phosphonate partial ester
[0304] MARLOPHOR UW 12-ACID Alkyl Polyethylene Glycol Ether Phosphate
[0305] MARLOWET 5301 Coconut Polyethylene Glycol Ether Phosphate
[0306] MARLOWET 5311 Isononyl phosphate metaester
[0307] MARLOWET 5320 Nonylphenol Polyethylene Glycol Ether Phosphate
[0308] MARLOWET 5324 Phenolic Polyethylene Glycol Ether Phosphate
[0309] MARLOWET 5361 Alkyl Polyethylene Glycol Ether Phosphate
[0310] ATLAS G-2203 Potassium salt of phosphate ester
[0311] ATLAS G-2207 Potassium Salt of Phosphate
[0312] FOSFODET 1214N / 16 Ethoxylated Fatty Alcohol Phosphate
[0313] FOSFODET 20D Fatty Alcohols, Phosphate Esters
[0314] FOSFODET 9Q / 22 Ethoxylated Alkyl-Aryl Phosphates
[0315] FOSFODET T-17 Ethoxylated Fatty Alcohols, Phosphate Esters
[0316] PA 100 Phosphorylated alcohol
[0317] PA800 Phosphorylated alcohol ethoxylate
[0318] PAE 106 Phosphorylated alcohol ethoxylate
[0319] PAE 126 Phosphorylated alcohol ethoxylate
[0320] PAE 136 Phosphorylated alcohol ethoxylate
[0321] DlSPONIL AEP 5300 Alkyl Aryl Ether Phosphate, Acid Ester
[0322] DISPONIL AEP 5302 Alkyl aryl ether phosphate, acid ester
[0323] DISPONIL AEP 8100 Alkyl Aryl Ether Phosphate, Acid Ester
[0324] DISPONIL AEP 9525 Alkyl Aryl Ether Phosphate, Sodium Salt
[0325] FORLANIT E Hydroxycetin Phosphate
[0326] FORLANIT P Fatty alcohol ether phosphate, sodium salt
[0327] KATAX AL Phosphate
[0328] OSIMOL 728 modified phosphate ester
[0329] OSIMOL LVP modified phosphate ester
[0330] H OSTAPHAT KL340 Laureth-4 Phosphate
[0331] HOSTAPHAT KL340N Laureth-4 Phosphate
[0332] HOSTAPHAT KW340 Laureth-4 Phosphate
[0333] HOSTAPHAT KW340N Laureth-4 Phosphate
[0334] MARLOPHOR CS ACID Isopropyl Phosphate
[0335] MAELOFHOR DS-ACID n-Butyl Phosphate
[0336] MARLOPHOR F 1-ACID n-Hexyl polyethylene glycol ether phosphate metaester
[0337] MARLOPHOR FC NA-SALT 2-Ethylhexyl polyethylene glycol ether phosphate, sodium salt
[0338] MARLOPHOR FC ACID 2-Ethylhexyl polyethylene glycol ether phosphate metaester
[0339] MARLOPHOR HS-ACID n-Ocylphosphate metaester
[0340] MARLOPHORIH-ACID 2-Ethylhexylphosphate metaester
[0341] MARLOPHOR MO3-ACID Lauryl Polyethylene Glycol Ether Phosphate
[0342] MARLOPHOR N5-ACID Isononyl polyethylene glycol ether phosphate metaester
[0343] MARLOPHOR ND-ACID isoalkyl phosphate metaester and alkylphenol polyethylene glycol ether blend
[0344] MARLOPHOR ND DE A SALT: A blend of isoalkyl phosphate metaesters and alkylphenol polyethylene glycol ethers
[0345] MARLOPHOR NP 5-ACID Nonylphenol polyethylene glycol ether phosphate
[0346] SERVOXYL VPT 3 / 85 2-Ethylhexyl polyethylene glycol ether (3EO) phosphate, sodium salt
[0347] SERVOXYL VPTZ 100 2-Ethylhexyl Phosphate
[0348] SERVOXYL VPTZ 3 / 100 2-Ethylhexyl polyethylene glycol ether (3EO) phosphate
[0349] SERVOXYL VPUZ 100 Methyl Phosphate
[0350] SERVOXYL VPXZ 100 Isononyl Phosphate
[0351] SERVOXYL VPXZ 5 / 100 Isononyl polyethylene glycol ether (5EO) phosphate
[0352] POLYSTEP PN 209 Alkylphenol Ethoxylated Phosphate
[0353] STEPFAC PN SERIES Phosphate
[0354] TRITON H-55 Phosphate
[0355] TRITON H-66 Phosphate
[0356] TRITON QS-44 Phosphate
[0357] MYKON 8402 Phosphorylated Nonylphenol Ethoxylate
[0358] Phospholan PS-131 Tridecyl alcohol (6EO) ethoxylated phosphate
[0359] Phospholan PS-220 C 10-14 Alcohol (30EO) ethoxylated phosphate ester
[0360] Phospholan PS-222 C 12-15 Alcohol (3EO) ethoxylated phosphate ester
[0361] Phospholan PS-236 C 10-14 Alcohol (3EO) ethoxylated phosphate ester
[0362] Alkylphenol ethoxylated phosphate esters
[0363] Phospholan CS-1361 Nonylphenol (6EO) ethoxylated phosphate, sodium salt; Phosphholan CS-141 Nonylphenol (10EO) ethoxylated phosphate.
[0364] Phospholan CS-147 Nonylphenol (8EO) Ethoxylated Phosphate Phenol
[0365] ethoxylated phosphate esters
[0366] Phospholan TS-211 Phenol (3EO) Ethoxylated Phosphate Alkylamine Phosphate
[0367] Phospholan TEAP (Triethylammonium Phosphate)
[0368] REWOPHAT E 1027 Alkylphenol Polyethylene Glycol Ether Phosphate
[0369] REWOPHAT EAK 8190 Lauryl alcohol polyethylene glycol ether phosphate
[0370] REWOPHAT NP 90 Alkylphenol Polyethylene Glycol Ether Phosphate
[0371] SYNTOPHOS 06N Based on Ethoxylated Alcohols
[0372] ULTRAPHOS 59 is based on ethoxylated phenol.
[0373] WTTCOR SI-3065 Complex Phosphate
[0374] COLLASTAT AP Phosphate
[0375] ELACTIV K phosphate
[0376] ELACTIV PS Phosphate
[0377] ELACTIV PV Phosphate
[0378] FLEROL TP 3000 modified phosphate ester
[0379] PHOSFETAL 201K Alkyl Polyethylene Glycol Ether Potassium Phosphate
[0380] PHOSFETAL 201 Alkyl polyethylene glycol ether phosphate, acid
[0381] PHOSFETAL 205 Alkyl polyethylene glycol ether phosphate, acid
[0382] PHOSFETAL 600 Alkyl aryl polyethylene glycol ether phosphate, acid
[0383] PHOSFETAL 601 Alkyl aryl polyethylene glycol ether phosphate, acid
[0384] PHOSFETAL 602 Alkyl aryl polyethylene glycol ether phosphate, acid
[0385] PHOSFETAL 603 Alkyl aryl polyethylene glycol ether phosphate, acid
[0386] One class of useful non-pesticide ingredients is dispersants, exemplary products of which are compounds in which the hydrophobic portion is formed of poly-12-hydroxystearic acid (APHS / EO) and the hydrophilic portion is formed of polyethylene oxide. A representative example is the commercial product of Leikema Corporation. 4914 or Hypermer B261. An alternative ingredient could be branched C atoms ethoxylated with 5 mol EO. 11 Carbonyl alcohols are exemplified by compounds (alcohol C). 11 +5EO), such as commercial products U / 050 is reported to be ethoxylated undecanoyl alcohol / branched ethoxylated C 9-11 alcohol.
[0387] Another notable category of components is ethoxylated fatty alcohol phosphates, alkyl phosphates, ethoxylated phosphates, etc. These components have been found to be extremely useful in the oil-based pymetrozine dispersion compositions of the present invention.
[0388] In some embodiments of the invention, compositions of insecticidal oil dispersions are provided, comprising pymetrozine, calcium alkylbenzene sulfonate, castor oil ethoxylate, alkyl polyglucosides, organic derivatives of lithium montmorillonite clay (or fumed silica), and plant-based oils (e.g., methyl soybean oleate).
[0389] In some embodiments of the invention, compositions of insecticidal oil dispersions are provided, the compositions comprising pymetrozine, isotridecyl polyoxyalkyl (e.g., 6 EO) phosphate monoester / diester (e.g., acid form), calcium alkylbenzene sulfonate such as branched alkylbenzene (C 11-13 Calcium sulfonate salts, castor oil ethoxylates, alkyl polyglucosides (alkyl polyglucosides / alkyl polysaccharides), organic derivatives of lithium montmorillonite clay (or fumed silica), and plant-based oil carriers (such as soybean methyl oleate).
[0390] Additional advantages are achieved by adding end-use dispersible stabilizer / compensator compounds such as tertiary amines and alkylamines (e.g., triethylamine, triethanolamine, n,n-diisopropylethylamine, butylamine, etc.), as exemplified by the addition of triethylamine to concentrated oil-based pymetrozine dispersion compositions. The inclusion of these types of end-use dispersible stabilizer / compensator compounds provides the compositions of the invention with good dispersibility characteristics in water after dilution and can be used to prevent noticeable color changes by visual inspection during storage periods exceeding one week at temperatures above 25°C (room temperature) (e.g., two weeks or longer at 54°C and / or at 40°C / 75% RH for at least one month).
[0391] Another embodiment of the present invention provides a method for preparing a pymetrozine oil dispersion composition by selecting an oily carrier from vegetable oils and their alkylated derivatives (such as methylated seed oil, methyl soybean oleate, etc.), the method comprising the steps of adding, stirring, grinding, collecting, homogenizing, and packaging, without the need for prehydration or presolubilization of pymetrozine before mixing.
[0392] In some specifically mentioned embodiments, the container used to package the OBPD composition will be impermeable to moisture, such that after a period of storage in the container at elevated temperatures and humidity (exemplified by 54°C and 40°C / 75%RH), the water content % of the contained OBPD will not increase by more than 1% w / w.
[0393] For many embodiments, containers suitable for packaging the oil-based pymetrozine dispersion concentrate of the present invention should be sufficiently opaque to light such that when stored exposed to sunlight or artificial light with wavelengths between 250 and 400 nm, the pymetrozine content degrades by no more than 5% w / w.
[0394] The inventors have noted that they have discovered that replacing commonly used oily carriers (such as paraffin, mineral oil, etc.) with plant-based oils (exemplified by methyl soybean oleate) in pymetrozine oil-based dispersions eliminates the need for prehydration or presolubilization of pymetrozine before blending with other advantageously selected ingredients, and can reduce the necessity or amount of emulsifying components.
[0395] Another embodiment of the present invention provides a composition of pymetrozine oil dispersion that, compared with previous attempts to formulate such products, saves operating costs and production steps and enables high dosage loading.
[0396] The particularly mentioned embodiments of the OBPD compositions of the present invention are concentrates that are generally suitable for easy dispersion in excess aqueous media after an extended shelf life and just before use. Stability of dispersibility is a major advantage achieved through many of these embodiments.
[0397] Another embodiment of the present invention provides a composition of an insecticidal oil dispersion comprising:
[0398] (a) A pest-killing ingredient comprising solid particulate pymetrozine in the range of 0.1% to 50% (w / w), typically up to 35% ± 5%.
[0399] (b) Stabilizing dispersants in the range of 0.03% to 10% (w / w),
[0400] (c) Enhanced emulsifiers in the range of 0.01% to 20% (w / w), typically up to 10%,
[0401] (d) Rheology modifiers in the range of 0.01% to 5% (w / w), and
[0402] (e) Vegetable oil-based carriers / adjuvants in the range of 0.4% to 90% (w / w), more typically up to 65% ± 5%,
[0403] The pest-killing ingredient may optionally include additional pest-killing compounds (such as flonicamid).
[0404] In some concentrated embodiments, the present invention provides a composition of an insecticidal oil dispersion comprising:
[0405] (a) Pesticides containing solid microparticles of pymetrozine in the range of greater than 0% to 40% (w / w), typically up to 35%.
[0406] (b) Stabilizing dispersants in the range of 3% to 10% (w / w),
[0407] (c) Enhanced emulsifiers in the range of 1% to 20% (w / w), typically up to 10%,
[0408] (d) Rheology modifiers in the range of 1% to 5% (w / w), and
[0409] (e) Vegetable oil-based carriers / adjuvants in the range of 30% to 80% (w / w), more typically up to 65% ± 5%,
[0410] The pest-killing ingredient may optionally include additional pest-killing compounds (such as flonicamid).
[0411] Another embodiment of the present invention provides a concentrated composition of an insecticidal oil dispersion, the composition comprising:
[0412] (a) Pesticides containing solid microparticles of pymetrozine in the range of 5% to 35% (w / w).
[0413] (b) Alkyl phosphates / ethoxylated phosphates in the range of 1% to 10% (w / w),
[0414] (c) Ethoxylated alcohols in the range of 1% to 10% (w / w),
[0415] (d) Copolymers of α-olefins and ethylene glycol ethers in the range of 1% to 10% (w / w),
[0416] (e) an organic derivative of lithium montmorillonite clay in the range of 0.1% to 3%, and optionally fumed silica in the range of 0.1% to 3% (w / w), and
[0417] (f) Vegetable oils or alkyl vegetable oils in the range of 30% to 80% (w / w), more typically up to 65% ± 5%,
[0418] The pest-killing ingredient may optionally include additional pest-killing compounds (such as flonicamid).
[0419] Another embodiment of the present invention provides a composition of an insecticidal oil dispersion comprising:
[0420] (a) A pest-killing component comprising solid particulate pymetrozine in the range of 20% to 50% (w / w), typically up to 32% ± 10%.
[0421] (b) Alkyl phosphates / ethoxylated phosphates in the range of 3% to 10% (w / w),
[0422] (c) Tri-sec-butylphenol polyethylene glycol ether in the range of 1% to 10% (w / w),
[0423] (d) Alkyl polyglucosides / polysaccharides in the range of 1% to 10% (w / w),
[0424] (e) An organic derivative of lithium montmorillonite clay in the range of 0.1% to 3% optionally combined with fumed silica in the range of 0.1% to 3% (w / w), and
[0425] (f) Methyl soybean oleate in the range of 30% to 72% (w / w), more typically up to 65% ± 5%,
[0426] The pest-killing ingredient may optionally include additional pest-killing compounds (such as flonicamid).
[0427] Another embodiment of the present invention provides a composition of an insecticidal oil dispersion comprising:
[0428] (a) Pesticides containing solid microparticles of pymetrozine in the range of 20% to 50% (w / w),
[0429] (b) Anionic alkyl ether sulfate surfactants, such as calcium alkylbenzene sulfonate, in the range of 3% to 10% (w / w).
[0430] (c) Alkoxylated alcohols such as tri-sec-butylphenol polyethylene glycol ether in the range of 1% to 10% (w / w),
[0431] (d) Alkyl polyglucosides / polysaccharides in the range of 1% to 10% (w / w),
[0432] (e) An organic derivative of lithium montmorillonite clay in the range of 0.1% to 3% optionally combined with fumed silica in the range of 0.1% to 3% (w / w), and
[0433] (f) Methyl soybean oleate in the range of 30% to 72% (w / w), more typically up to 65% ± 5%.
[0434] The pest-killing ingredient may optionally include additional pest-killing compounds (such as flonicamid).
[0435] Several embodiments of the present invention provide pymetrozine oil-based dispersion compositions, comprising (but not limited to) some or all of the following, in addition to pymetrozine:
[0436] Copolymers of α-olefins and ethylene glycol (e.g., 4914)
[0437] • Ethoxylated fatty alcohol phosphate esters (e.g., 1306)
[0438] Organic derivatives of lithium montmorillonite clay ( SD 3)
[0439] Triethylamine (TEA)
[0440] Alkyl polyglucosides / alkyl polysaccharides / alkyl polysaccharides (e.g., 650EC / PG 8107-BL / 8105-G AL-2575 / Al-2579)
[0441] Alkylated vegetable oils, such as methyl soybean oleate
[0442] Alkyl polyglucosides (Formula 1) are a group of surface-active compounds that are alkyl polyglucosides derived from glucose.
[0443] Structure of alkyl polyglucosides (APG)
[0444]
[0445] Their hydrophilic and hydrophobic portions are clearly separated. The hydrophilic group in an APG molecule typically consists of one to five condensed glucosinolate moieties (DP = 1-5). The hydrophobic group in an APG molecule is typically an alkyl chain containing six to eighteen carbon atoms. Surface activity depends on both the hydrophilic and hydrophobic portions, albeit to varying degrees. The surface activity of a surfactant is primarily determined by chain length. According to Traube's rule, surface activity at the water / air interface increases threefold with increasing chain length via the CH2 group (at 20°C).
[0446] The hydrophilic portion influences adsorption to a lesser extent. However, it affects solubility in polar solvents. Depending on the molecular structure, alkyl polyglucosides exhibit varying solubilities in a variety of solvents. Compounds with a degree of polymerization (DP) of 1 to 5 containing alkyl chains of 6 to 14 carbons are soluble in water. Molecules with 16 to 22 carbon atoms are oil-soluble. Generally, increasing the degree of polymerization increases solubility in polar media, while elongation of the alkyl chain increases solubility in nonpolar media. Alkyl polyglucosides exist as monomers at low concentrations and form micelles above the critical micelle concentration (CMC, typically on the order of a few percent). Aqueous solutions of alkyl polyglucosides can appear as lyotropic liquid crystals at concentrations above 30%.
[0447] Alkyl polysaccharide glycosides / alkyl polyglucosides are part of the alkyl polysaccharide surfactant group. Surfactant components contain one or more alkyl polysaccharide surfactants.
[0448] Examples of alkyl polysaccharide surfactants include compounds having Formula 2:
[0449] R 11 -O-(SUG) u Equation (2)
[0450] Where R 11 It is a straight-chain or branched substituted or unsubstituted hydrocarbon group selected from alkyl, alkenyl, alkylphenyl, alkenylphenyl groups having about 4 to about 22 carbon atoms or about 4 to 18 carbon atoms. The SUG moiety is a sugar residue and can be open-ended or cyclic (i.e., pyranose) in structure.
[0451] The sugar can be a monosaccharide, disaccharide, oligosaccharide, or polysaccharide having 5 or 6 carbon atoms. Examples of suitable sugar moieties (including their corresponding pyranose forms) include ribose, xylose, arabinose, glucose, galactose, mannose, taloose, gulose, allose, adroose, idole, lysolose, ribulose, sorbitol, fructose, and mixtures thereof.
[0452] Suitable examples of disaccharides include maltose, lactose, and sucrose. Disaccharides, oligosaccharides, and polysaccharides can be combinations of two or more identical sugars, such as maltose (two glucose molecules), or combinations of two or more different sugars, such as sucrose (a combination of glucose and fructose). The degree of polymerization u is an average of 1 to approximately 10, 1 to approximately 8, 1 to approximately 5, 1 to approximately 3, and 1 to approximately 2.
[0453] In various embodiments, the alkyl polysaccharide surfactant may be an alkyl polyglucoside (APG) surfactant having formula (2), wherein: R 11It is typically a branched or straight-chain alkyl group having 4 to 22 carbon atoms or 8 to 18 carbon atoms, or a mixture of alkyl groups having an average value within a given range; SUG is a sugar residue, such as a glucose residue (e.g., a glucoside); and u is 1 to about 5, and more typically 1 to about 3. In various embodiments, the surfactant component comprises an APG having formula (2), wherein R 11 It is a mixture of branched or straight-chain alkyl groups having 8 to 10 carbon atoms or having an average value of alkyl groups within a given range, and u is 1 to about 3.
[0454] Alkyl polysaccharides include, but are not limited to,
[0455] 325 (Cognis), alkyl polysaccharides containing 9 to 11 carbon atoms and having an average degree of polymerization of 1.6. 2000 (Corning), alkyl polysaccharides containing 8 to 16 carbon atoms and having an average degree of polymerization of 1.4, 1300 (Corning), alkyl polysaccharides containing 12 to 16 carbon atoms and having an average degree of polymerization of 1.6. PG 2067 (Corning), an alkyl polysaccharide containing 8 to 10 carbon atoms and having an average degree of polymerization of 1.7. PG 2069 (Corning), an alkyl polysaccharide containing 9 to 11 carbon atoms and having an average degree of polymerization of 1.6. PG 2076 (Corning), an alkyl polysaccharide containing 8 to 10 carbon atoms and having an average degree of polymerization of 1.5. 438 (Yelekhem Corporation, Wilmington, Delaware) (where the alkyl group contains 9 to 11 carbon atoms in an alkyl polysaccharide) and 452 (Yelekhem Corporation, Wilmington, Delaware) (where the alkyl group contains 8 to 10 carbon atoms in the alkyl polysaccharide),
[0456] PG 8105-G C8 / C 10 Alkyl polysaccharide (DP=1.5) 68515-73-1
[0457] PG 8107-G C8 / C 10 Alkyl polysaccharide (DP=1.7) 68515-73-1
[0458] PG 8107-BL Low-Foaming Alkyl Polysaccharide (DP=1.7) 68515-73-1
[0459] PG8107-G
[0460] PG 2067
[0461]
[0462] In some embodiments, the alkyl glycosides used in this invention can be obtained by reacting an alkanol with glucose or other monosaccharides, disaccharides, or polysaccharides. As used herein, the term "alkyl glycoside" includes alkyl glucosides, alkyl monosaccharides, and alkyl polysaccharides (sometimes commonly referred to as alkyl polysaccharides). Typically, the alkyl glycosides used in this invention are alkyl polysaccharides, comprising alkyl polyglucosides obtained by reacting glucose with a straight-chain or branched alkanol or a mixture of alkanols (e.g., a mixture containing 7 to 18, typically 7 to 16, e.g., 8 to 10 carbon atoms of alkanols). The number of sugar groups in each alkyl group in the molecule can vary, and alkyl monoglucose, alkyl disaccharide, or alkyl polyglucose, or alkyl monosaccharide, alkyl disaccharide, or alkyl polysaccharide derivatives are possible. Commercial alkyl polyglucosides typically contain mixtures of derivatives in which each alkyl group has an average number of monosaccharide groups. Thus, alkyl glycosides have the general formula (III).
[0463]
[0464] Where n is the degree of aggregation and is typically in the range of 1 to 3, for example, 1 to 2, and R 5 It is a mixture of branched or straight-chain alkyl groups having 4 to 18 carbon atoms, or alkyl groups having an average value within a given range. Typical alkyl glycosides are marketed under the trade names AL2042 (Imperial Chemical Industries PLC) and... PG2067 (a commercially available product of Henkel Corp.), where n is the average of 1.7 and R... 5 It is a mixture of octyl (45%) and decyl (55%); by trade name PG2069 (Henkel) is a commercially available product, where n is the average value of 1.6, and R... 5 It is a mixture of nonyl (20%), decyl (40%) and undecyl (40%); and under the trade name AG6202 (now owned by Nouryon, formerly Akzo Nobel) is a commercially available product, which is 2-ethyl-1-hexyl glycoside.
[0465] Exemplary APG ( 650EC) is clearly based on natural fatty alcohol C8-C 16 An aqueous solution of an alkyl polyglucoside, specifically comprising the following aqueous solution:
[0466] D-glucopyranose, oligo-C 10-16 -Alkyl glycosides 25%-<50%
[0467] D-glucopyranose, oligodecyl octyl glycoside 20%-<25%
[0468] NaOH 0.3%-1%,
[0469] Water content is approximately 48%.
[0470] Typically, it is based on aqueous solutions containing, for example, D-glucopyranose, oligomeric C... 10-16 -alkylpyranose, oligo C 8-10 -alkyl glycoside.
[0471] Example PG 8107-BL is reported to contain approximately 70% active ingredient content. 8-10 APG products containing alkyl polysaccharide glycosides (DP=1.7).
[0472] In several experiments, the alkyl polyglucosides / alkyl polysaccharides were found to play a noteworthy and useful additional role. While it was found that reasonably acceptable concentrated oil-based pymetrozine dispersion compositions could be prepared without this component class, it was noted that these compositions were difficult to disperse in water, especially after a period of storage. Furthermore, experimental samples that did not contain alkyl polyglucosides / alkyl polysaccharides were found to be particularly sensitive to water content during compounding, and adding more than a minimum amount of water resulted in solidification. In contrast, samples containing alkyl polyglucosides / alkyl polysaccharides were more easily dispersed in water. Even more surprisingly, the use of alkyl polyglucosides (APG) in aqueous solution form in compounding the oil-based pymetrozine dispersion (OBPD) of the present invention did not result in the destructive effects seen in experiments involving the introduction of equal or even lower amounts of water.
[0473] Perhaps most surprisingly, in addition to the “protective” effect of APG on the compatibility issues with water content that have been encountered to date in OBPD concentrate compositions observed in this experiment, a real positive effect was also found when the oil-based pymetrozine dispersion concentrate was subsequently dispersed in water to form a diluted end-use biocidal application liquid.
[0474] In any case, surprisingly, despite the doubts researchers in the field have encountered so far, the inventors have noted that it is likely that choosing APG in the form of an aqueous liquid or aqueous solution will not only not “impair” the properties and manufacturability of OBPD concentrate, but may also bring considerable benefits in terms of stability during manufacturing and storage, as well as the ease with which OBPD can be diluted and dispersed after the storage period.
[0475] In addition, the inventors have found that, in some embodiments, the combination of APG with anionic co-surfactants, derived from phosphate esters / phosphonates (alkylphosphonic acids (RPO(OH)2) or their esters) and sulfate / sulfonate surfactants, has the most significant (to date) further positive effect when compounding OBPD concentrates.
[0476] It is even possible that the interaction between exemplary APGs and specific anionic surfactants modulates their combined advantages by influencing the “free state” of water molecules in OBPDs. The combination of Hostaphant 1306 and Ninate401A has been found to be significantly advantageous.
[0477] In any case, it is useful to minimize or completely exclude solvents exemplified by any of the following: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, cyclohexanol, 2-ethylhexanol, alkylbenzene, tetrahydrofurfuryl alcohol, ethylene glycol, glycerol, methyl acetate, ethyl acetate, ethyl lactate, butyrolactone, γ-butyrolactone, ethylene carbonate, propylene carbonate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-decyl-2-pyrrolidone, acetone, butanone, methyl isobutyl ketone, methyl propyl ketone, acetophenone, cyclohexanone, dichloromethane, chloroform, trichloroethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, ethanolamine, pyridine, chlorobenzene, toluene, xylene, or tetramethylurea.
[0478] The inventors emphasize that, in some compositional embodiments, excluding the aforementioned solvents may be more important than other approaches in order to prepare a useful oil-based pymetrozine dispersion composition, and that a useful composition may be prepared in the absence of one or more of the components of the disclosed class in this embodiment.
[0479] In fact, once the improvement is achieved by eliminating undesirable solvents, further improvements can be achieved by selecting components of various categories that are identified as useful, and improvements can be optimized by a combination of these categories of components.
[0480] Alternatively, as discussed herein, certain components comprising the compositions of the present invention can make OBPD concentrates less sensitive to the presence of typically destructive solvents than they would be in the absence of such components.
[0481] The inventors have determined that when the oil-based pymetrozine dispersion composition of the present invention comprises a subset of components represented by combinations of alkyl polyglucosides / alkyl polysaccharides with triethylamine and alkyl phosphates / ethoxylated phosphates, a specific set of enhancing advantages is achieved.
[0482] Based on experiments, a plant-based oil carrier was advantageously chosen over mineral oil, paraffin, aromatic oils, etc. Therefore, the inventors have demonstrated the significant advantage of choosing a plant-based carrier component in the oil-based pymetrozine dispersion (OBPD) compositions of the present invention.
[0483] While it may be feasible to produce reasonably acceptable OBPD compositions using mineral oil or paraffin oil, the inventors have found that by choosing vegetable oil-based carrier components, exemplified by methyl soy oleate, the emulsifiers previously required for emulsifying mineral oil or paraffin oil can be reduced or even eliminated. More importantly, as discussed herein, the use of carriers such as methyl soy oleate has the unexpected benefit of allowing pymetrozine compounds to be formulated into oil-based pymetrozine dispersion concentrates without the need for prehydration of pymetrozine prior to formulation.
[0484] In the embodiments of the pymetrozine oil-based dispersion of the present invention, the above materials provide non-limiting specific examples of each class of advantageous non-insecticide components (excipients).
[0485] However, the inventors emphasize that each of the specific ingredients mentioned above is merely an example. Researchers skilled in formulating agricultural pesticide dispersions, and especially pymetrozine oil-based dispersions, will immediately recognize that each component can be replaced with an alternative that will perform the same function.
[0486] The inventors also emphasized that they did not claim any instances of the aforementioned non-insecticide formulation adjuvants, namely... 4914; 1306; SD 3, TEA, 650EC and soybean oleate methyl ester are not the best substances or optimal specific ingredients, but rather they provide clear guidance for skilled researchers in these fields on favorable ingredient categories.
[0487] As a (non-restrictive) instance only, as VPDZ 3 / 100 sells tridecyl polyethylene glycol ether (3EO) phosphate, which in some cases may be the above-mentioned. Alternatives to 1306. Whether one instance of an ingredient is superior to another instance of the same class of ingredients will generally depend on the identity of other selected excipients and / or additional biocidal ingredients, and the preferred choice is entirely within the skill of the formulator.
[0488] In another instance, under specific circumstances, the aforementioned organic derivatives of lithium montmorillonite clay are known to be useful rheological additives, and researchers may clearly discover that this component can be used with... R972 illustrates the replacement or enhancement of fumed silica products.
[0489] Researchers are likely to discover that anionic tristyrylphenol sulfate surfactants, such as those derived from ammonium salts, can... The anionic tristyrylphenol sulfate surfactant exemplified in 4D / 384 can be a useful dispersing additive to replace one of the exemplified ones or simply to supplement the dispersing ability.
[0490] Several embodiments of the present invention provide pymetrozine oil-based dispersion compositions comprising additional pest control agents that do not depart from the scope of the invention, notably but not limited to insecticides. The illustrated model additional pest control molecules may include flonicamid.
[0491] In yet another embodiment, the present invention provides a (non-limiting) exemplary method for preparing an insecticidal plant oil-based pymetrozine dispersion composition, wherein the method comprises the following steps:
[0492] (a) The vegetable oil-based adjuvant is loaded into a container equipped with, for example, a high-shear disperser, and stirred, then heated to, for example, 45°C-50°C.
[0493] (b) Add dispersant and emulsifier.
[0494] (c) The rheology modifier is added under stirring for, for example, 30 minutes, and a high shear force is applied.
[0495] (d) Pymetrozine (and optionally one or more other biocides) is added to the resulting homogeneous solution under continuous stirring, and a high shear force is applied.
[0496] (e) Milling the resulting mixture until the desired particle size distribution is achieved, and optionally cooling the contents to room temperature (if necessary), and
[0497] (f) Package the obtained oil dispersion into a suitable container.
[0498] A suitable storage container will typically be impermeable to light and moisture.
[0499] In yet another embodiment, the present invention provides an exemplary (though not limiting) method for preparing an insecticidal pymetrozine oil-based dispersion composition, wherein the method comprises the following steps:
[0500] (a) The vegetable-based oil is loaded into a container equipped with a stirring device and stirring is started, optionally followed by heating to, for example, 40°C-45°C. The container is advantageously equipped with a high-shear disperser as a stirring device.
[0501] (b) Add alkyl phosphate / alkoxylated phosphate, emulsifier, and stir the mixture for homogenization.
[0502] (c) Optionally, an organic derivative (rheology modifier) of fumed silica and / or lithium montmorillonite clay is introduced under stirring, for example, for 30 min, and a high shear force is applied.
[0503] (d) Pymetrozine was added to the obtained homogeneous solution under continuous stirring, and a high shear force was applied.
[0504] (e) Mill the resulting mixture until the desired particle size distribution is achieved, and cool the contents to room temperature (if necessary).
[0505] (f) For example, continue stirring at room temperature for a period of 2 hours, and
[0506] (g) Package the obtained oil dispersion into one or more suitable storage containers, such as into rollers or into commercial retail containers (e.g., bottles, cans, etc.).
[0507] A suitable storage container will typically be impermeable to light and moisture.
[0508] In yet another embodiment, the present invention provides a method for preparing an insecticidal oil dispersion composition, wherein the method comprises the following steps:
[0509] (a) Load the vegetable oil-based carrier into a high-shear disperser and start stirring, then heat to, for example, 40°C-45°C.
[0510] (b) A copolymer of alkyl phosphate ester / ethoxylated phosphate ester, ethoxylated alcohol / α-olefin and ethylene glycol is loaded and the mixture is stirred to homogenize.
[0511] (c) Optionally, an organic derivative of fumed silica and / or lithium montmorillonite clay is introduced under stirring and a high shear force is applied.
[0512] (d) Pymetrozine was added to the obtained homogeneous solution under continuous stirring, and a high shear force was applied.
[0513] (e) Mill the resulting mixture until the desired particle size distribution is achieved, and cool the contents to room temperature (if necessary).
[0514] (f) Continue stirring at room temperature for a period of time, for example, 2 hours, and
[0515] (h) Package the obtained oil dispersion into one or more suitable storage containers, such as into rollers or into commercial retail containers (e.g., bottles, cans, etc.).
[0516] A suitable storage container will typically be impermeable to light and moisture.
[0517] In some specifically mentioned embodiments, suitable containers for packaging OBPD compositions will be impermeable to moisture such that, after a period of storage in the container at elevated temperatures and humidity (exemplified by 54°C and 40°C / 75%RH), the water content % of the contained OBPD will not increase by more than 1% w / w.
[0518] For many embodiments, containers suitable for packaging the oil-based pymetrozine dispersion concentrate of the present invention should be sufficiently opaque to light such that when stored exposed to sunlight or artificial light with wavelengths between 250 and 400 nm, the pymetrozine content degrades by no more than 5% w / w. Detailed Implementation
[0519] The term “comprising” is synonymous with “including,” “containing,” or “characterized by,” and is defined herein as inclusive or open-ended, and does not exclude additional unlisted elements or method steps unless the context clearly requires otherwise.
[0520] The present invention provides a composition of an insecticidal oil dispersion comprising pymetrozine, one or more dispersants, one or more emulsifiers, one or more rheology modifiers, and one or more advantageously plant-based oil adjuvants.
[0521] One embodiment of the present invention provides an insecticidal oil-based dispersion composition comprising pymetrozine, alkyl phosphate / ethoxylated phosphate, triethylamine, alkyl polyglucosides / alkyl polysaccharides, an organic derivative of lithium montmorillonite clay, and soybean methyl oleate oil.
[0522] One embodiment of the present invention provides an insecticidal oil dispersion composition comprising pymetrozine, alkyl phosphate / ethoxylated phosphate, triethylamine, alkyl polyglucoside / alkyl polysaccharide, an organic derivative of lithium montmorillonite clay, and methyl soybean oleate, as well as a polymeric surfactant for agricultural use (wherein the hydrophilic portion is PEG and the hydrophobic portion is an alkyd resin).
[0523] One embodiment of the present invention provides an insecticidal oil dispersion composition comprising pymetrozine, alkyl phosphate / ethoxylated phosphate, triethylamine, alkyl polyglucosides / polysaccharides, an organic derivative of lithium montmorillonite clay, and methyl soybean oleate, as well as an ethoxylated carbonyl alcohol-based polymeric surfactant for agricultural use.
[0524] In many embodiments, the present invention also relates to numerous embodiments of pymetrozine oil-based dispersion compositions having a minimized amount of any of the following solvents exemplified, or having none of these solvents: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, cyclohexanol, 2-ethylhexanol, alkylbenzene, tetrahydrofurfuryl alcohol, ethylene glycol, glycerol, methyl acetate, ethyl acetate, ethyl lactate, butyrolactone, γ-butyrolactone, ethylene carbonate, propylene carbonate, Acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-decyl-2-pyrrolidone, acetone, butanone, methyl isobutyl ketone, methyl propyl ketone, acetophenone, cyclohexanone, dichloromethane, chloroform, trichloroethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, ethanolamine, pyridine, chlorobenzene, toluene, xylene, or tetramethylurea.
[0525] The present invention also relates to pymetrozine oil-based dispersion compositions comprising, in addition to pymetrozine insecticides, at least one of the following (but typically in combination): alkyl phosphate esters / ethoxylated phosphate esters, triethylamine, alkyl polyglucosides / alkyl polysaccharides, ethoxylated carbonyl alcohols / PEG-alkyd resin copolymers; organic derivatives of lithium montmorillonite clay and / or fumed silica; and soybean methyl oleate oil.
[0526] Typically, oil dispersions (OD) formulations are solid active ingredients dispersed in an oil. This oil can vary from paraffinic solvent type to aromatic solvent type, and can be vegetable oil or methylated seed oil. Ideally, the active ingredient is uniformly suspended in the oil phase. In this invention, vegetable oils or methylated seed oils have been found to have significant advantages over paraffinic and aromatic carrier types.
[0527] The insecticides used in the compositions of this invention include pymetrozine. The addition of another bioactive component is clearly conceived by the inventors and is entirely within the scope of this invention. It is evident that adding additional excipients to increase the compatibility of all components of the oil-based pymetrozine dispersion compositions of this invention does not diminish the conceived scope.
[0528] The concentration of pymetrozine used in oil-based pymetrozine dispersions is greater than 0% and equal to or less than 40% (w / w), often it is 5% to 35% (w / w), and notably 10% to 32% (w / w). Typically, the pymetrozine concentration used is 15% to 26% (w / w) of the total weight of the composition. The inventors have exemplified numerous compositions of the invention containing high levels of pest-loading agents (including about 20% and above of pymetrozine), which are non-limiting and clearly represent the full breadth of the scope of the disclosure, rather than any indication that the invention should be so limited in any way.
[0529] The dispersants used in the compositions of the present invention include, but are not limited to, ethyleneoxy-propyleneoxy block polymers, alkylphenol polyethylene glycol ethers, phosphorylated or sulfated derivatives of tristyrylphenol polyethylene glycol ethers, and calcium alkylbenzene sulfonates. nC 12 α-alkylbenzene sulfonate calcium salt phosphate ester ( FLR), nC 12 Alkylbenzene sulfonate calcium salt, nC 12 Calcium alkylbenzene sulfonate salts ( CAL) and calcium dodecylbenzenesulfonate ( 60BER), alkyl phosphates, alkoxylated phosphates.
[0530] In some embodiments, the concentration of the dispersant used in the oil-based pymetrozine dispersion is 1% to 10% (w / w). In some examples of use, the concentration of the dispersant is 3% to 8% of the total weight of the composition.
[0531] In some embodiments, the emulsifiers used in the compositions of the present invention include, but are not limited to, nonionic, anionic, cationic, and amphoteric emulsifiers, or blends of two or more emulsifiers. In some embodiments, the emulsifiers used include aliphatic amine alkoxylates, polyoxyethylene glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty acid polydiethanolamides, lanolin ethoxylates, fatty acid polyethylene glycol esters, isoform tridecyl alcohol, alkyl polysaccharides, and castor oil ethoxylates having 36 moles of EO ( 360), castor oil ethoxylate with 36 moles of EO ( 4853B), tri-sec-butylphenol polyethylene glycol ether with 4EO ( T 040), ethoxylated compounds of alkyl polyethylene glycol ethers (( TO 5), or combinations thereof.
[0532] In some embodiments, the concentration of the emulsifier used in the oil-based pymetrozine dispersion is 1% to 20% (w / w). Typically, the emulsifier concentration used is 1% to 10% (w / w).
[0533] Rheology modifiers that can be used in the compositions of the present invention include, but are not limited to, organic derivatives of lithium montmorillonite clay (such as... 38. 27. 1000 SD-3), blends of vegetable oil derivatives such as vegetable oil bases ( ESP 8105), and fumed (or colloidal) silica, such as R974 200 972, R816 300, etc. Rheology modifiers specifically mentioned include, but are not limited to, those mentioned above. SD-3 38. 27. 1000 R-816 200 300 R-816 and R-972.
[0534] The inventors have envisioned other rheology modifiers, and they have devised a simple scheme for selecting rheology modifiers tailored to specific embodiments of the oil-based pymetrozine dispersion concentrate compositions of the present invention.
[0535] Typically, the choice of oil-based carrier (or solvent) for OBPD concentrates will be crucial for the initial screening of candidate rheology modifier types / grades; therefore, pure solvents / carriers can be used for initial screening. Furthermore, the amount and method of incorporating candidate rheology modifiers into OBPD can be usefully determined using examples of OBPD compositions of the present invention that will benefit from further optimization.
[0536] Solution / Method:
[0537] 1: Identify relevant rheology modifier candidates
[0538] 2: Select a carrier model system for each solvent for initial screening and to determine the useful percentage content.
[0539] 3: Select one or more OBPD composition models whose stability needs to be optimized through rheology.
[0540] 4: For each screened rheology modifier, based on the desired viscosity and rheological properties, the optimal method for incorporation into the model OBPD composition was determined experimentally using the percentage content determined during the screening of the carrier model system.
[0541] 5: Optimize the % content of the selected rheology modifier in the actual OBPD concentrate by comparing the stability results from each experiment with the desired specifications.
[0542] See below for various examples of rheological candidates, their chemical categories, and incorporation methods.
[0543]
[0544]
[0545] The concentration of rheology modifier used in insecticidal oil dispersions is 0.1% to 5% (w / w), and typically the concentration of rheology modifier used is 0.1% to 1% of the total weight of the composition.
[0546] Oil adjuvants used in the compositions of this invention include, but are not limited to, soybean methyl oleate oil, rapeseed oil, olive oil, castor oil, canola oil, corn oil, cottonseed oil, sunflower oil, and palm methyl ester oil. While the selection of oil adjuvants is broad and theoretically can include mineral oil or paraffin oil, the inventors have noted that the use of soybean methyl oleate, alkyl esters of rapeseed oil, sunflower oil, and palm methyl ester oil allows for efficient incorporation of the pymetrozine active ingredient into OBPD without the conventional pre-hydration. This can be advantageous in some high-loading embodiments, and formulators can make choices to avoid using mineral oil or paraffin oil in the preparation of these compositions.
[0547] The concentration of the oil adjuvant (oil-based carrier) used in insecticidal oil dispersions (OBPDs) is 15% to 90%, more typically 40% to 80% (w / w). More typically, the concentration of the oily carrier used is about 45% to 70% (w / w) of the total weight of the composition, although several exemplary embodiments contain an oily carrier between 50% and 65% w / w.
[0548] The present invention provides a composition of pymetrozine oil dispersions that saves operating costs through an industrially and economically feasible method of simple compounding of a stable, non-viscous OD concentrate, which exhibits and maintains high dispersibility in water and retains this level of dispersibility even after prolonged storage at elevated temperatures.
[0549] This invention provides a method for preparing an oil-based pymetrozine dispersion composition, the method comprising the steps of: addition, stirring, grinding, collecting, homogenizing, and packaging. However, further optimization of the order in which some non-insecticidal formulation adjuvants (NIFAs) are incorporated into the OBPD can have significant effects.
[0550] In the specifically mentioned embodiments, unexpected additional advantages were achieved when a sulfate / sulfonate-based NIFA, exemplified by branched alkylbenzene sulfonates (calcium salts), was added to an OBPD embodiment already optimized with phosphate / phosphonate NIFAs, and incorporated after all other components had been milled and homogenized. Although the dispersibility in water was previously simple and physically stable, it was now found to be similar to that of the emulsifiable concentrate, and the OBPD itself was further stabilized in terms of separation, exceeding previously acceptable levels.
[0551] The following non-exhaustive examples illustrate the nature of the invention and are given only for the purpose of illustrating the invention in more detail, and are not restrictive, and relate to solutions that are particularly effective on a laboratory scale for solving one or more challenges.
[0552] As previously mentioned, there are several challenges in the formulation of oil-based pymetrozine dispersions (OBPD) compositions during the compounding stage; in quality evaluation, in storage stability characteristics; and when the composition is an oil-based dispersion, there are even more challenges, and when such an oil-based dispersion is a concentrate intended to be dispersed in an aqueous medium (water) prior to its end-use application (which requires it to remain easily dispersible after storage), there are even more challenges.
[0553] In the following non-limiting examples, various compositions are presented and are frequently compared and contrasted with other sample compositions presented herein.
[0554] The inventors wish to emphasize that, apart from a limited number of comparative examples, the illustrated compositions are neither “superior” nor “inferior”, but rather establish a progressive spectrum: some of the compositions overcome a limited number of formulation challenges, while others of the illustrated compositions perform better and overcome a large number of challenges.
[0555] The inventors do not limit the scope of their invention to the best of the illustrated compositions, but rather wish to emphasize the success of each individual solution in addressing each of the aforementioned challenges, while recognizing that those compositions that overcome many or all the difficulties associated with the formulation of pymetrozine oil-based dispersions are clearly considered more optimized than the inventive compositions, which are less successful.
[0556] Preparation A - General
[0557]
[0558]
[0559] Preparation A1 - Hydrogenated light-chain alkane petroleum distillate carrier
[0560]
[0561]
[0562] When using a less preferred paraffin-based carrier, pymetrozine must be prehydrated before compounding can begin. From a production standpoint, prehydrating pymetrozine before incorporation is neither ideal nor preferred, as it is found that approximately 16% water is required, leaving a small amount of oil that can be incorporated into the dispersion. The dispersion composition is also undesirable from the perspective of appearance and physical properties (including sedimentation, paste formation, and water dispersibility for end-use), both during the compounding stage and during the stabilization period (even with prehydration).
[0563] Formulation A2-Soybean Oleate Carrier
[0564] When using vegetable oil derivatives as a carrier, pymetrozine must be prehydrated before mixing can begin. However, even if this problem is solved, the composition can be further improved, for example, by selecting non-insecticide formulation adjuvants that are more compatible with methyl soybean oleate than with alternative paraffin-based carriers.
[0565]
[0566]
[0567] Formulation A3-Soybean Oleate Carrier & Combination with Flupyradifurone
[0568]
[0569] Preparation B - General
[0570]
[0571]
[0572] Formulation B1 - Hydrotreated light-chain alkane petroleum distillate carrier
[0573]
[0574]
[0575] When using a paraffin-based carrier, pymetrozine must be prehydrated before compounding can begin. From a production standpoint, prehydrating pymetrozine before incorporation is neither ideal nor preferred, as it is found that approximately 16% water is required, leaving a small amount of oil that can be incorporated into the dispersion. The dispersion composition is also undesirable from the perspective of appearance and physical properties (including precipitation and paste formation), both during the compounding stage and during stabilization (even with prehydration).
[0576] Formulation B2-Soybean Oleate Carrier
[0577] When using vegetable oil derivatives as a carrier, pymetrozine must be prehydrated before mixing can begin. However, even if this problem is solved, the composition can be further improved, for example, by selecting non-insecticide formulation adjuvants that are more compatible with methyl soybean oleate than with alternative paraffin-based carriers.
[0578]
[0579]
[0580] Formulation B3-Soybean Oleate Carrier & Combination with Flupyradifurone
[0581]
[0582] Preparation D - General
[0583]
[0584]
[0585] Formulation D1 - Hydrogenated light-chain alkane petroleum distillate carrier
[0586]
[0587] When using a paraffin-based carrier, pymetrozine must be prehydrated before compounding can begin. From a production standpoint, prehydrating pymetrozine before incorporation is neither ideal nor preferred, as it is found that approximately 16% water is required, leaving a small amount of oil that can be incorporated into the dispersion. The dispersion composition is also undesirable from the perspective of appearance and physical properties (including precipitation and paste formation), both during the compounding stage and during stabilization (even with prehydration).
[0588] Formulation D2-Soybean Oleate Carrier
[0589] When using vegetable oil derivatives (such as methyl soybean oleate) as a carrier, pymetrozine must be prehydrated before mixing can begin. However, even if this problem is solved, the composition can be further improved, for example, by selecting non-insecticide formulation adjuvants that are more compatible with methyl soybean oleate than with alternative paraffin-based carriers.
[0590]
[0591] Formulation D3-Soybean Oleate Carrier & Combination with Flupyradifurone
[0592]
[0593]
[0594] E-General Preparations
[0595]
[0596]
[0597] Preparation E1 - Hydrogenated light distillate (petroleum),
[0598] When using a paraffin-based carrier, pymetrozine must be prehydrated before compounding can begin. From a production standpoint, prehydrating pymetrozine before incorporation is neither ideal nor preferred, as it is found that approximately 16% water is required, leaving a small amount of oil that can be incorporated into the dispersion. The dispersion composition is also undesirable from the perspective of appearance and physical properties (including precipitation and paste formation), both during the compounding stage and during stabilization (even with prehydration).
[0599]
[0600] E2-Soybean Oleate (Formulation)
[0601] When using vegetable oil derivatives as a carrier, pymetrozine must be prehydrated before mixing can begin. However, even if this problem is solved, the composition can be further improved, for example, by selecting non-insecticide formulation adjuvants that are more compatible with methyl soybean oleate than with alternative paraffin-based carriers.
[0602]
[0603] Formula E3-methyl soybean oleate & combination with flonicamid
[0604]
[0605]
[0606] Preparation F-General
[0607]
[0608] Formulation F1 - Hydrotreated intermediate distillate (petroleum)
[0609]
[0610]
[0611] Formula F2-methyl soybean oleate
[0612]
[0613] Formula F3-methyl soybean oleate & combination with flonicamid
[0614]
[0615] Following testing, replacing paraffin solvents with methylated seed oil (methyl soybean oleate) is reasonable, at least because pre-hydration of pymetrozine is unnecessary before blending. Further experiments to optimize oil-based dispersions include the following non-limiting examples.
[0616] The formulations include AA-ethoxylated alkyl phosphates and alkoxylated fatty alcohols / acids.
[0617] The viscosity increases when stored at 54°C. Although the composition does not solidify and is acceptable (good) after shaking, its dispersibility in water needs further optimization.
[0618] Preparation AA1 - Pymetrozine alone
[0619]
[0620]
[0621] Formulas AA2-pymetrozine and flonicamid
[0622]
[0623] Formula AA3 - Prehydrated pymetrozine + Mineral / paraffinic oil - Unoptimized
[0624]
[0625] Formulations BB ethoxylated alkyl phosphates / alkoxylated fatty alcohols or acids / APG
[0626] Better stability. After storage at 54°C, the dispersion still requires inversion 3-4 times to achieve complete suspension.
[0627] BB1 formulation - pymetrozine alone
[0628]
[0629] Formulas BB2-pymetrozine and flonicamid
[0630]
[0631]
[0632] Formula BB3 - Prehydrated pymetrozine + Mineral / paraffinic oil - Unoptimized
[0633]
[0634] The formulation contains CC-ethoxylated alkyl phosphates / APG / triethylamine (TEA).
[0635] Adding TEA (triethylamine) to the system improved its performance in water and
[0636] Dispersibility after two weeks of storage at 54°C. Furthermore, the oil-based dispersion is color-stable (not yellow) compared to some other examples that do not contain TEA.
[0637] Exemplary APG ( 650EC)
[0638] formulation CC1 - pymetrozine alone
[0639]
[0640]
[0641] The formulations CC2-pymetrozine and flonicamid
[0642]
[0643] Formula CC3 - Prehydrated pymetrozine + Mineral / paraffinic oil - Unoptimized
[0644]
[0645]
[0646] Formulation DD-General Purpose-Alkoxylated Alkyl Phosphate / APG / TEA / Surfactant
[0647]
[0648] Formulation DD1-alkoxylated alkyl phosphate esters / 650EC / TEA / surfactant
[0649]
[0650]
[0651] Formulation DD2-alkoxylated alkyl phosphate / Agnique PG 8107-BL / TEA / Surfactant
[0652]
[0653]
[0654] It was found that replacing APG (Glucopon) with Agnique PG resulted in acceptable stability in terms of viscosity, sedimentation, and dispersibility in water after stabilization (dispersibility stability).
[0655] Formulation DD3-alkoxylated alkyl phosphate esters / PG 8107-BL / TEA / surfactant
[0656] Combined with flonicamid
[0657]
[0658] Formulation DD4-alkoxylated alkyl phosphate esters / 650EC / TEA / Combination of Surfactant and Flupyradifurone
[0659]
[0660] Formulations: EE-anionic phosphate / APG / TEA / surfactant
[0661] [20g formulation CC2 + 1g added surfactant used for compatibility testing after 2W storage at 54°C]
[0662]
[0663]
[0664] Some exemplary, more refined embodiments of the compositions of the present invention
[0665] a. Anionic phosphate esters + sulfonates
[0666] 1. Add soybean methyl oleate to the container.
[0667] 2. Add materials: 4914, Agnique PG 8107-BL / Glucopon 650EC, TEA, 1306, Ninate 401A.
[0668] 3. Mix to obtain a homogeneous mixture.
[0669] 4. Add one or more active ingredients – pymetrozine (and flonicamid) – under stirring and high shear stress.
[0670] 5. Add SD-3 and apply high shear force.
[0671] 6. Grind the dispersion to obtain the desired particle size.
[0672]
[0673]
[0674] 1306-ethoxylated fatty alcohol phosphate esters
[0675] 401 Branched Alkylbenzene (C 11-13 Calcium sulfonate salts
[0676]
[0677] b. Anionic phosphates without sulfonates
[0678] 1. Add soybean methyl oleate to the container.
[0679] 2. Add materials: 4914, Agnique PG 8107-BL / Glucopon 650EC, TEA, 1306.
[0680] 3. Mix to obtain a homogeneous mixture.
[0681] 4. Add the active ingredients – pymetrozine (and flonicamid) – under stirring and high shear stress.
[0682] 5. Add SD-3 and apply high shear force.
[0683] 6. Grind the dispersion to obtain the desired particle size.
[0684] 7. Pack in a suitable container (typically impermeable to light and moisture, see above).
[0685]
[0686] 1306-ethoxylated fatty alcohol phosphate esters
[0687]
[0688]
[0689] The results showed that compositions 3 and 4 contained, in addition to pymetrozine (and flonicamid) 4914; Hostaphalt 1306; SD-3; TEA; Glucopon 650EC or Agnique PG 8107-BL and methyl soybean oleate, these compositions performed well and showed good dispersibility in water. However, the inventors found that the addition of Ninate 401A to compositions 1 and 2 above improved the ease of dilution in water after storage at the temperature illustrated at 54°C. Furthermore, after one week of dispersion in water, minimal precipitation was observed, and no precipitation was observed after inverting the diluted sample 2-3 times.
[0690] c. According to process optimization
[0691] Although it contains 1306 and The combination of 401A and the other two [1 and 2 above] is very good, but the inventors have managed to add branched alkylbenzene (C) after grinding all other ingredients. 11-13 These compositions were further optimized when sulfonate salts (NINATE 401A) were used.
[0692] Therefore, using Example 2 above and the following preparation method, further optimized features are provided.
[0693] 1. Add soybean methyl oleate to the container.
[0694] 2. Add materials: 4914、 PG 8107-BL / 650EC, TEA, 1306.
[0695] 3. Mix to obtain a homogeneous mixture.
[0696] 4. Add SD-3 and apply high shear force
[0697] 5. Add one or more active ingredients, pymetrozine (and flonicamid), while applying stirring and high shear force.
[0698] 6. Grind the dispersion to obtain the desired particle size.
[0699] 7. After grinding, add materials. 401A and mix to obtain a uniform dispersion.
[0700] 8. Pack in a suitable container (typically impermeable to light and moisture, see above).
[0701] Pymetrozine + Flupyradifurone
[0702]
[0703] stability
[0704] Dispersion stability - Effects of alkyl polysaccharides / alkyl polyglucosides and TEA
[0705] Contains methyl soybean oleate, 1306 4914、 Oil-based dispersion samples of SD-3 and additional co-formulated formulations are indicated in the table below:
[0706] 650EC - Based on natural fatty alcohols C8-C 14 Aqueous solutions of alkyl polyglucosides
[0707] PG 8107-BL-C 8-10 Alkyl polysaccharide glycoside (DP=1.7) contains approximately 70% active ingredient.
[0708] TEA-Triethylamine
[0709]
[0710]
[0711] CC2-Stability Data of Formulations ( 650EC+triethylamine)
[0712]
[0713] Compositions with space for optimization
[0714] Having provided guidelines for the easy production of pourable, storage-stable, concentrated pymetrozine oil-based dispersions, several compositions that can now be further optimized are illustrated. A prototype composition profile for optimizing high pesticide loadings is provided, comprising pymetrozine and flonicamid as model compound mixing partners.
[0715]
[0716]
[0717] The composition did not solidify during compounding and after storage at elevated temperatures. However, the high viscosity and the challenge of dispersing the concentrate in water present challenges. The low solvent / carrier content in the system also poses an issue.
[0718] The following formulations have high levels of biocides, and while these compositions have addressed some challenges, they will benefit from further optimization using the guidance provided above, particularly in terms of physical stability, which exhibits unacceptable levels of curing after storage at 54°C. In particular, it is now clear from the foregoing description that the addition of any one or both of alkyl polyglucosides / alkyl polysaccharides and / or triethylamine will improve these compositions.
[0719]
[0720] Some envisioned compositions serve as an initial basis for optimization.
[0721]
[0722]
[0723]
[0724]
[0725] Comparison of two anionic components used alone in a non-optimized process
[0726] As previously mentioned, when the composition contains anionic surfactants, additional advantages may be obtained in some embodiments by combining phosphate / phosphonate surfactants and sulfate / sulfonate surfactants. However, each should be visualized as enabling potentially different process optimizations.
[0727] The following are non-limiting examples of combined products of pymetrozine and flonicamid, in which different product characteristics were achieved using the same method for two compositions of different anionic surfactants, each with a high loading.
[0728] When optimizing product combinations, it is recommended to always consider all active ingredients.
[0729]
[0730]
[0731] When each of the combined compositions 1 and 2 in the table above was treated with the same method at high loadings (6% w / w) of anionic surfactants from different classes, the results were different. When the anionic surfactants were added at the same time point early in the preparation process before the addition of the two active ingredients, the composition containing only sulfate / sulfonate anionic surfactants was found to be less optimized than the composition based on phosphate / phosphonate surfactants. Concentrate 1 was flowable and the milling process was acceptable, while Concentrate 2 was difficult to manufacture and had suboptimal curing effects.
Claims
1. A non-aqueous biocidal suspension composition comprising: a) Biocidal compounds in the form of solid particulate matter b) Alkyl polysaccharide surfactants, c) Non-toxic biological active formulation aids, and d) Oil-based carrier The biocidal compound is a hygroscopic, water-soluble, and / or solvent-absorbent compound, and the non-aqueous biocidal suspension composition may optionally contain additional biocidal compounds.
2. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is an insecticidal oil-based dispersion composition, the insecticidal oil-based dispersion composition comprising, a) Pymetrozine, a compound used as a pesticide, exists in solid particulate form. b) An aqueous solution of alkyl polysaccharide as an alkyl polysaccharide surfactant, which contains Alkyl polysaccharide glycosides, alkyl polyglucosides, or mixtures thereof, c) Non-insecticide formulation adjuvants used as formulation adjuvants for non-toxic pest control. d) Oil-based carrier, and optionally e) Other insecticide compounds, The pymetrozine, which is in solid particulate form, is unhydrated or prehydrated before being included in the composition.
3. The non-aqueous biocidal suspension composition as described in claim 2, wherein, The composition is an insecticidal oil-based dispersion concentrate composition, the insecticidal oil-based dispersion concentrate composition comprising, a) Pymetrozine in solid particulate form b) An aqueous solution of an alkyl polysaccharide surfactant, comprising, Alkyl polysaccharide glycosides, alkyl polyglucosides, or mixtures thereof, c) At least one non-insecticide formulation adjuvant. d) Dispersible stabilizer / compensator compounds for end-use applications, and e) Oil-based carrier. The amount of water constituting the aqueous solution of the alkyl polysaccharide surfactant is between greater than 0% w / w and equal to or less than 5% w / w, based on the weight of the insecticidal oil-based dispersion concentrate composition.
4. The non-aqueous biocidal suspension composition as described in claim 2 or claim 3, wherein, The pymetrozine is in the form of non-hydrated solid particles, and the oil-based carrier includes vegetable oil, vegetable oil derivatives such as alkylated vegetable oil, or combinations thereof.
5. The non-aqueous biocidal suspension composition according to any one of claims 2-4, wherein, The end-use dispersible stabilizer / compensator compound is one or more of the following: tertiary amines, alkylamines, triethylamine, tributylamine mixed alkylamines, triethanolamine, N,N-diisopropylethylamine, butylamine, especially triethylamine, and the oil-based carrier includes one or more of the following: vegetable oils, vegetable oil derivatives—such as alkylated vegetable oils exemplified by vegetable oil methyl esters such as soybean oleate methyl ester, palm methyl ester oil, methyl oleate, methyl linoleate, methyl linoleate, methyl stearate, methyl palmitate, and rapeseed oil methyl ester.
6. The non-aqueous biocidal suspension composition according to any one of claims 1-5, wherein, The formulation adjuvants for non-toxic pest control and / or non-toxic insect control are one or more of dispersants, emulsifiers, surfactants, rheology modifiers, oil additives, and combinations thereof.
7. The non-aqueous biocidal suspension composition according to any one of claims 1-6, wherein, The non-toxic bioactive formulation aids include one or more alkoxylation aids, anionic surfactants, dispersants, end-use dispersible stabilizers or compatibilizers, thickeners and / or rheology modifiers, and combinations of two or more thereof.
8. The non-aqueous biocidal suspension composition as described in claim 7, wherein, The alkoxylation auxiliary is one or more of the following: alkoxylated (e.g., ethoxylated) carboxylic acid esters, alkoxylated (e.g., ethoxylated) carboxylic acids, alkoxylated (e.g., ethoxylated) primary or secondary straight-chain or branched alcohols, alkoxylated fatty alcohols, ethoxylated fatty alcohols, coconut fatty alcohol ethoxylates, C 12 / C14 Fatty alcohol ethoxylates, cetyl alcohol / oleyl alcohol ethoxylates, C 16 / C18 Fatty alcohol ethoxylates, C 12 / C18 Fatty alcohol ethoxylates, C 8 / C14 Fatty alcohol ethoxylates, C 13 / C15 Fatty alcohol ethoxylates, C 11 / C15 Fatty alcohol ethoxylates, tributylphenol ethoxylates, alkoxylated (such as ethoxylated linear or branched) alkyl arylates such as ethoxylated alkylphenols, nonylphenol ethoxylates and ethoxylated acetylacetic alcohols, alkoxylated fatty alcohols / ethoxylated fatty alcohols, ethoxylated isotridecyl alcohols, copolymers PEG polyisobutylene anhydride-tall fatty acids, ABA block copolymers having a hydrophilic portion of polyethylene oxide (PEG) and a hydrophobic portion of 12-hydroxystearic acid.
9. The non-aqueous biocidal suspension composition as described in claim 7, wherein, The anionic surfactant is one or more of the following: phosphonates, phosphates, sulfonates, sulfates such as alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl aryl ether sulfates, alkylbenzene sulfonates, alkylbenzene sulfonates (branched or linear) salts of alkylnaphthalene sulfonic acids, salts of naphthalene sulfonic acid formaldehyde condensation products, salts of condensation products of naphthalene sulfonic acid, phenol sulfonic acid, and formaldehyde, alkali metal salts of alkylnaphthalene sulfonic acids, salts of naphthalene sulfonic acid-formaldehyde condensation products; sulfosuccinate metal salts with branched or linear alcohols as monoesters and diesters; sodium dioctyl sulfosuccinate; alkyl succinate sulfates, alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glyceryl ether sulfonates, α-methyl ester sulfonates, sulfonated fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glyceryl ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, glyceryl monoester (ether) sulfates, fatty acid amide (ether) sulfates. Salts, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamide salts, sulfoglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid hydroxyethanesulfonates, fatty acid sarcosine salts, fatty acid taurine salts, alkyl oligoglucosides sulfates, alkylbenzene sulfonates, alkylbenzene sulfonates (branched / straight-chain), phosphates such as monoesters and diesters, mixtures of free alcohols and phosphoric acids, alkylphosphonic acids, phosphates of fatty alcohols, phosphates of ethoxylated fatty alcohols, alkoxylated / ethoxylated phosphates, alkylphosphonic acids, anionic phosphates, ethoxylated phosphates such as alkyl phosphates based on isotriadecyl alcohol ethoxylates, and olefin sulfonates containing hydrophobic alkyl chains and anionic sulfonic acid groups, sulfonated sulfates from fatty alcohols and alcohol ethoxylates, alkoxylated (e.g., ethoxylated) phosphates of alcohols, alkylphenol alkoxylated (e.g., ethoxylated) phosphates, alkylamine phosphates and combinations thereof.
10. The non-aqueous biocidal suspension composition of claim 7, comprising pymetrozine, triethylamine, ethoxylated fatty alcohol phosphates such as isotridecyl polyoxyalkyl (e.g., 6EO) phosphate monoester / diesel acid; calcium alkylbenzene sulfonate, such as branched alkylbenzene (C 11-13 Calcium sulfonate salts; castor oil ethoxylates; alkyl polysaccharides (alkyl polyglucosides / alkyl polyglucosides) such as C-based 8-16 Aqueous solutions of alkyl polyglucosides of fatty alcohols; organic derivatives of lithium montmorillonite clay and / or fumed silica; and plant-based oil carriers such as methyl soybean oleate; and optionally, additional pest-killing compounds.
11. The non-aqueous biocidal suspension composition of claim 7, comprising pymetrozine, flonicamid, triethylamine, isothiazine polyoxyethyl phosphate monoester / diesel acid; branched alkylbenzene C 11-13 Sulfonates, calcium salts; castor oil ethoxylates, based on fatty acid C 8-16 Aqueous solutions of alkyl polyglucosides of alcohols; organic derivatives of lithium montmorillonite clay; and methyl soybean oleate.
12. The non-aqueous biocidal suspension composition according to any one of claims 2-11, wherein, The non-aqueous pest control suspension composition is packaged in a container that is sufficiently impermeable to moisture, sunlight, or both, such that the quality of the dispersion is maintained during storage and the end-use dispersibility is not affected by storage at temperatures above 25°C for more than one week. The container is characterized by being formed of a material that provides a barrier to moisture and / or light with wavelengths between 250 and 400 nm, and the container is sealed by a closure system that does not impair the level of impermeability to moisture and / or light provided by the material forming the container. The sufficient impermeability to moisture, sunlight, or both ensures that the percentage of water content in the contained non-aqueous pest control suspension composition does not increase to more than 5% w / w after a storage period of two weeks at 54°C and / or one month at 40°C / 75% RH. Furthermore, the non-aqueous pest control suspension composition is characterized by a degradation of no more than 5% w / w in the pymetrozine content when stored in the container exposed to sunlight or artificial light with wavelengths between 250 and 400 nm during the storage period.
13. A non-aqueous biocidal suspension concentrate composition comprising: a) A compound with structural formula (A) that exists in the form of solid particles. Compounds with structural formula (B) b) An aqueous solution of an alkyl polysaccharide surfactant, comprising, Alkyl polysaccharide glycosides, alkyl polyglucosides, or mixtures thereof, c) Alkoxylation auxiliaries, d) Selected from the following anionic surfactants, i) Surfactants based on phosphate esters or phosphonates; ii) Surfactants based on sulfates or sulfonates; and iii) A combination of surfactants based on phosphate esters or phosphonates and surfactants based on sulfates or sulfonates. e) Triethylamine, f) Methyl soybean oleate, and optionally g) Additional bioactive compounds, such as flonicamid in, r and s are each independently between 0 and 12, and L is one or more of the following: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, cyclohexanol, 2-ethylhexanol, alkylbenzene, tetrahydrofurfuryl alcohol, ethylene glycol, glycerol, methyl acetate, ethyl acetate, ethyl lactate, butyrolactone, ethylene carbonate, propylene carbonate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-decyl-2-pyrrolidone, acetone, butanone, methyl isobutyl ketone, methyl propyl ketone, acetophenone, cyclohexanone, dichloromethane, trichloroethane, etc. The composition contains chloromethane, trichloroethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, ethanolamine, pyridine, chlorobenzene, toluene, xylene, or tetramethylurea, and the content of L is equal to or less than 5% w / w of the composition, wherein the amount of water constituting the aqueous solution of the alkyl polysaccharide surfactant is between greater than 0% w / w and equal to or less than 5% w / w based on the weight of the non-aqueous pest control suspension concentrate composition, and the non-aqueous pest control suspension concentrate composition is characterized by the substantial absence of propylene glycol.
14. The non-aqueous biocidal suspension composition of claim 13, wherein, The non-aqueous pest control suspension composition is packaged in a container that is sufficiently impermeable to moisture, sunlight, or both, such that the quality of the dispersion is maintained during storage and the end-use dispersibility is not affected by storage at temperatures above 25°C for more than one week. The container is characterized by being formed of a material that provides a barrier to moisture and / or light with wavelengths between 250 and 400 nm, and the container is sealed by a closure system that does not impair the level of impermeability to moisture and / or light provided by the material forming the container. The sufficient impermeability to moisture, sunlight, or both ensures that the percentage of water content in the contained non-aqueous pest control suspension composition does not increase to more than 5% w / w after a storage period of two weeks at 54°C and / or one month at 40°C / 75% RH. Furthermore, the non-aqueous pest control suspension composition is characterized by a degradation of no more than 5% w / w in the pymetrozine content when stored in the container exposed to sunlight or artificial light with wavelengths between 250 and 400 nm during the storage period.
15. A pourable, storage-stable concentrated pymetrozine oil-based dispersion composition, characterized in that... Low viscosity and stable water dispersibility, having the following percentage content based on the total weight of the dispersion composition, (a) Pesticide components containing solid particulate pymetrozine or solid particulate prehydrated pymetrozine at a concentration between 0% and 40% w / w. (b) Non-insecticide formulation adjuvants at 0.2% to 30% w / w or less, wherein the non-insecticide formulation adjuvant is selected from the group consisting of: i. Emulsifiers / surfactants at a concentration between approximately 1% and approximately 10% w / w ii. Dispersants of greater than 1%-10%, iii. 0.1%-3% thickener and / or rheology modifier, iv. 2%-20% as an end-use dispersible stabilizer / compensator / modifier v. Water between 0% w / w and 5% w / w, excluding any water associated with the pre-hydrated pymetrozine—if present—and vi. Any and all of two or more of them. (c) Added to 100% oil-based liquid carrier, The biocidal ingredient may optionally include additional biocidal compounds such as flonicamid, and the composition may optionally be packaged in a container.
16. The pymetrozine oil dispersion of claim 15, wherein, The non-insecticide formulation adjuvant comprises alkyl polysaccharides and / or alkyl polyglucosides at a weight of about 1% to 10% w / w based on the total weight of the dispersion composition.
17. The pymetrozine oil dispersion of claim 15, wherein, The non-insecticide formulation adjuvant comprises an aqueous solution of alkyl polysaccharide and / or alkyl polyglucoside.
18. The pymetrozine oil dispersion of claim 15, wherein, The non-insecticide formulation adjuvant comprises, by weight of the total dispersion composition, between about 1% and 10% w / w, anionic surfactants such as phosphate esters (monoesters and diesters, mixtures of free alcohols and phosphoric acid), alkylphosphonic acids, phosphate esters of fatty alcohols, phosphate esters of ethoxylated fatty alcohols, alkoxylated / ethoxylated phosphate esters, alkylphosphonic acids, branched or linear alkylaryl sulfonates, branched or linear alkylbenzene sulfonates, alkyl sulfonates and olefin sulfonates comprising hydrophobic alkyl or olefin chains and anionic sulfonic acid groups, and sulfonated sulfates derived from fatty alcohols and alcohol ethoxylates.
19. The pymetrozine oil dispersion of claim 15, wherein, The non-insecticide formulation adjuvant comprises an alkoxylation adjuvant, such as alkoxylated / ethoxylated carboxylic acid esters, ethoxylated carboxylic acids, ethoxylated primary or secondary straight-chain or branched alcohols, alkoxylated fatty alcohols, ethoxylated fatty alcohols, coconut fatty alcohol ethoxylates, C 12 / C 14 Fatty alcohol ethoxylates, cetyl alcohol / oleyl alcohol ethoxylates, C 16 / C 18 Fatty alcohol ethoxylates, C 12 / C 18 Fatty alcohol ethoxylates, C8 / C 14 Fatty alcohol ethoxylates, C 13 / C 15 Fatty alcohol ethoxylates, C 11 / C 15 Fatty alcohol ethoxylates, tributylphenol ethoxylates, ethoxylated (straight-chain or branched) alkyl arylates such as ethoxylated alkylphenols, nonylphenol ethoxylates and ethoxylated acetylacetic diols, alkoxylated fatty alcohols / ethoxylated fatty alcohols CAS No. 69011-36-5 ( U / 050), ethoxylated isotridecyl alcohol (CAS. 9043-30-5), copolymer PEG / polyisobutylene anhydride-tall fatty acid CAS. 173717-47-0 ( Atlox 4914) block copolymers of EO-12-hydroxystearic acid (Atlox 4912) and all combinations thereof.
20. The pymetrozine oil-based dispersion of claim 18, wherein, The anionic surfactant is a sulfate / sulfonate such as fatty alcohol sulfate, fatty alcohol ether sulfate, α-olefin sulfonate, alkylbenzene sulfonate (…). 60, Ninate 70BE, Nansa EVM 70 / 2E), branched alkylbenzene C 11-13 Sulfonates and their salts ( 401A), alkyl phosphates, or ethoxylated phosphates in acid or salt form such as isotridecyl polyoxyethyl (6EO) phosphate monoester / diester acid form ( 1306), tridecyl polyethylene glycol ether phosphate ( VPDZ 3 / 100), alkylphenoxy polyethyl ester of phosphoric acid ( PA), tridecyl alcohol polyether-5 phosphate ( T5A) and combinations of two or more of them.
21. The pymetrozine oil-based dispersion of claim 15, wherein, The non-insecticide formulation adjuvant contains alkyl glycosides such as alkyl polysaccharides and / or alkyl polyglucosides (alkyl polysaccharides), such as those based on natural fatty alcohols C8-C. 14 Aqueous solutions of alkyl polyglucosides ( 650EC), C 8-10 Alkyl polysaccharide (DP = 1.7) approximately 70% PG 8107-BL), alkyl polyglucosides and phosphate esters, in water 50% (TRITON) TM CG-50 and its combinations.
22. The pymetrozine oil dispersion of claim 15, wherein, The end-use dispersible stabilizers / compensators include tertiary amines and alkyl amines such as triethylamine, triethanolamine, N,N-diisopropylethylamine, and butylamine.
23. The pymetrozine oil dispersion according to any one of claims 16-22, wherein, The end-use dispersible stabilizer / compensator contains between about 0.01% and about 1% of tertiary amines such as triethylamine, triethanolamine, N,N-diisopropylethylamine, butylamine, and combinations thereof.
24. The pymetrozine oil-based dispersion concentrate as described in claim 15, wherein, The pymetrozine is not prehydrated, and the oil-based liquid carrier is a vegetable oil or its derivative, such as alkyl esters exemplified by soybean oleate, rapeseed oil or its alkyl esters, olive oil, castor oil, rapeseed oil, corn oil, cottonseed oil, sunflower oil, palm methyl ester oil, methyl oleate, methyl linoleate, methyl linolenate, methyl stearate, methyl palmitate, and mixtures thereof, wherein the oil-based liquid carrier is characterized by a content of mineral oil and / or paraffinic oil selected from the group consisting of, based on the weight of the entire dispersion composition: a) Less than 5% w / w; b) Less than 4% w / w; c) Less than 3% w / w; d) Less than 2% w / w; e) Less than 1% w / w; f) less than 0.5% w / w; and g)0% w / w.
25. The pymetrozine oil-based dispersion concentrate as described in claim 15, wherein, The oil-based liquid carrier is a vegetable oil or a derivative thereof, characterized by a content of less than 5% w / w of mineral oil and / or paraffinic oil based on the weight of the dispersion, wherein the pymetrozine is not prehydrated, and wherein the pymetrozine oil-based dispersion concentrate is characterized by a total water content selected from the group consisting of the following, based on the weight of the dispersion concentrate: a) Less than 4% w / w; b) Less than 3% w / w; c) Less than 2% w / w; d) Less than 1% w / w; e) less than 0.5% w / w; and f) greater than 0% w / w.
26. The pymetrozine oil dispersion of claim 15, wherein, The non-insecticide formulation adjuvant comprises a mixture of the following anionic surfactants. a) Anionic surfactants based on phosphate esters / phosphonates, such as phosphate esters (monoesters and diesters, mixtures of free alcohols and phosphoric acid), alkylphosphonic acids, phosphate esters of fatty alcohols, phosphate esters of ethoxylated fatty alcohols and alkoxylated / ethoxylated phosphate esters, alkylphosphonic acids, and b) Sulfate / sulfonate-based anionic surfactants, such as alkyl sulfonates and olefin sulfonates containing hydrophobic alkyl chains and anionic sulfonic acid groups, sulfonated sulfate esters from fatty alcohols and alcohol ethoxylates, branched alkylbenzenes (C 11-13 Calcium sulfonate salts.
27. The pymetrozine oil dispersion according to claim 15, characterized in that, The emulsifier includes one or more of the following: oleic acid, oleic acid polyoxyethylene ether, alkylphenol polyoxyethylene ether, castor oil polyoxyethylene ether or fatty alcohol polyoxyethylene ether, copolymer PEG poly-isobutylene anhydride-tall fatty acid, alkoxylated fatty alcohol, ethoxylated fatty alcohol.
28. The pymetrozine oil dispersion as described in claim 15 or 16, characterized in that, The thickener includes one or more of the following: magnesium aluminum silicate, organobentonite, organic derivatives of lithium montmorillonite clay, silica, fumed or colloidal silica.
29. The pymetrozine oil dispersion according to claim 15 or 16, characterized in that, The end-use dispersible stabilizers / compensators include one or more of triethylamine, triethanolamine, acetic acid, or phosphoric acid.
30. The pymetrozine oil dispersion according to claim 15, characterized in that, The oil-based liquid carrier includes vegetable oils or their derivatives, such as corn oil, soybean oil, alkyl esters of fatty acids such as alkyl oleate, methyl oleate, methyl soybean oleate, methyl linoleate, methyl linoleate, methyl stearate, methyl palmitate, cottonseed oil, and alkyl esters of vegetable oils.
31. The pymetrozine oil dispersion of claim 15, comprising pymetrozine, alkyl polysaccharide glycoside, anionic surfactant, and vegetable oil or its derivatives, characterized in that... Water content selected from the group selected based on the weight of the dispersion concentrate: a) Less than approximately 4% w / w; b) Less than approximately 3% w / w; c) Less than approximately 2% w / w; d) Less than approximately 1% w / w; e) less than about 0.5% w / w; and f) Between 0% and approximately 0.4% w / w.
32. The pourable, storage-stable concentrated pymetrozine oil dispersion composition of claim 15, comprising: a) Pymetrozine, b) At least one non-insecticide formulation adjuvant selected from the following i) Alkyl polysaccharides; ii) Emulsifiers; iii) Alkoxylation auxiliaries; Combinations of iv)i) and ii); Combinations of v)i) and iii); Combinations of vi), ii), and iii); and vii)i) and ii) and iii); c) At least one non-insecticide formulation adjuvant selected from anionic surfactants. d) At least one non-insecticide formulation adjuvant selected from tertiary amines. e) At least one oil-based liquid carrier selected from vegetable oils or their derivatives.
33. The pourable, storage-stable concentrated pymetrozine oil dispersion composition of claim 15, comprising: a) Solid microparticles of pymetrozine, b) At least one non-insecticide formulation adjuvant selected from alkyl polysaccharide glycosides and / or alkyl polyglucosides; c) Triethylamine d) At least one non-insecticide formulation adjuvant selected from anionic surfactants. e) At least one oil-based liquid carrier.
34. The pourable, storage-stable concentrated pymetrozine oil dispersion composition of claim 15, comprising: a) Anionic surfactants in the form of salts or acids, selected from... i) Straight-chain or branched alkyl phosphates; ii) Ethoxylated phosphate esters; iii) Phosphate esters containing aromatic bases; iv) Alkylphenoxy polyethyl esters of phosphoric acid; v) Fatty alcohol polyethylene glycol ether phosphate; vi) Straight-chain or branched alkyl aryl sulfonates; vii) Straight-chain or branched alkylbenzene sulfonates; viii) Alkyl sulfonates; ix) Olefin sulfonates; x) Alkyl ether sulfonate xi) sulfonyl fatty acids; xii) Alkyl sulfates; xiii) Fatty alcohol ether sulfates; xiv) Calcium alkylbenzene sulfonate phosphate, and xv) its combination, b) Alkyl polysaccharides, such as alkyl polysaccharide glycosides and / or alkyl polyglucosides, c) Alcohols or esters or alkylphenol alkoxylates selected from the group below i) Alkoxylation of C6-C 24 alcohol; ii) Alkoxylation of C6-C 24 Alkylphenol; iii) Alkoxylation of C6-C 24 carboxylic acid; iv) Alkyl-polyoxyethylene alkyl esters; d) At least 0.5% w / w of water, and e) Vegetable oil-based carriers, The composition thereof contains less than 5% w / w of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, cyclohexanol, 2-ethylhexanol, alkylbenzene, tetrahydrofurfuryl alcohol, ethylene glycol, glycerol, methyl acetate, ethyl acetate, ethyl lactate, butyrolactone, γ-butyrolactone, ethylene carbonate, propylene carbonate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrole, based on the total weight of the oil dispersion. Alkyl ketones, N-octyl-2-pyrrolidone, N-decyl-2-pyrrolidone, acetone, butanone, methyl isobutyl ketone, methyl propyl ketone, acetophenone, cyclohexanone, dichloromethane, chloroform, trichloroethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, ethanolamine, pyridine, chlorobenzene, toluene, xylene, or tetramethylurea, wherein less than 5% w / w is substantially absent or less than 5% w / w.
35. The pourable, storage-stable concentrated pymetrozine oil dispersion composition of claim 32, comprising, as an end-use dispersibility stabilizer / compensator, in the range of about 0.01% to about 1% of a tertiary amine such as triethylamine, triethanolamine, N,N-diisopropylethylamine, butylamine, or a combination thereof.
36. The pourable, storage-stable concentrated pymetrozine oil dispersion composition according to any one of claims 15-35, comprising one or more of the following: magnesium aluminum silicate, organobentonite, an organic derivative of lithium montmorillonite clay, silica, fumed or colloidal silica.
37. The pourable, storage-stable concentrated pymetrozine oil dispersion composition according to any one of claims 15-36, comprising additional pest-killing compounds.
38. The pourable, storage-stable concentrated pymetrozine oil dispersion composition as described in claim 37, wherein, The combined percentage content of pymetrozine and the aforementioned biocidal compound is not greater than 45% w / w of the concentrated pymetrozine oil-based dispersion composition.
39. The pourable, storage-stable concentrated pymetrozine oil-based dispersion composition of claim 15, comprising... a) At least one alkyl polysaccharide or alkyl polyglucan (APG) b) At least one alkoxylated aliphatic, branched, or straight-chain alcohol. c) At least one anionic surfactant selected from phosphate esters, phosphonates, sulfates, sulfonates, sulfosuccinates, or combinations thereof. d) At least one tertiary amine, such as triethylamine, e) Water greater than 0% and less than 3% w / w.
40. The pourable, storage-stable concentrated pymetrozine oil-based dispersion composition of claim 15, comprising pymetrozine at 2% to 35% w / w or less.
41. The pourable, storage-stable concentrated pymetrozine oil-based dispersion composition according to any one of claims 15-40, wherein it is packaged in a container, said container being characterized in that... Suitable containers are provided that are sufficiently impermeable to moisture, sunlight, or both, such that the quality of the pourable, storage-stable concentrated pymetrozine oil-based dispersion composition contained within the container is maintained during storage, and the end-use dispersibility of the concentrated pymetrozine oil-based dispersion composition is not significantly affected by storing the packaged, pourable, storage-stable concentrated pymetrozine oil-based dispersion composition at temperatures above 25°C for more than one week. The containers are characterized by being formed of a material that provides a barrier to moisture and / or light with wavelengths between 250 and 400 nm, and the containers are sealed by a closed system. The closed system does not impair the level of impermeability to moisture and / or light provided by the material forming the container, wherein sufficient impermeability to moisture, sunlight, or both ensures that the percentage of water content in the contained non-aqueous pest control suspension composition does not increase to more than 5% w / w during a two-week storage period at 54°C and / or a one-month storage period at 40°C / 75% RH, and is characterized in that when stored in sunlight or artificial light with wavelengths between 250 and 400 nm during said storage period, the pymetrozine content of the non-aqueous pest control suspension composition packaged in the container degrades by no more than 5% w / w.
42. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion suitable for end-use dispersion in excess aqueous media after storage. The concentrated biocidal oil-based dispersion is characterized by low viscosity and stable water dispersibility, and contains a biocidal compound at a weight of greater than 0% to up to about 46% w / w, and is characterized by a compositional content at a weight of greater than 0% and equal to or less than 32% for pymetrozine. Non-insecticide formulation adjuvants in combination with oil-based liquid carriers, preferably vegetable oil-based liquid carriers, at concentrations between 0.2% and 30%, wherein the non-insecticide formulation adjuvants are selected from the group consisting of: a) Alkoxylation auxiliaries ranging from 1% to approximately 10%; b) Anionic surfactants between 1% and approximately 10%; c) Alkyl glycosides (sugars) between 1% and 7%; d) Thickeners and / or rheology modifiers between 0.1% and about 4%; e) Dispersible stabilizer / compensator for end-use applications at concentrations between 0.01% and approximately 0.5%; f) any combination of a), b), c), d), and e); and All combinations of g)a), b), c), d), and e). The concentrated biocidal oil-based dispersion is characterized in that the total water content in the concentrated biocidal oil-based dispersion is formulated and packaged to be less than about 5% by weight of the entire concentrated dispersion, wherein the concentrated biocidal oil-based dispersion composition is optionally packaged in a suitable container characterized in that the container is capable of maintaining the ease of dispersing the concentrated biocidal oil-based dispersion composition for end use during the storage period.
43. The pourable, storage-stable, concentrated insecticidal oil-based dispersion composition as described in claim 42, wherein, The alkoxylation auxiliary is selected from, i) Alkoxylated carboxylic acid esters; ii) Ethoxylated carboxylic acid esters; iii) Alkoxylated primary or secondary straight-chain or branched alcohols; iv) Ethoxylated primary or secondary straight-chain or branched alcohols; v) Alkoxylated fatty acids; vi) Ethoxylated fatty acids; vii) Alkoxylated fatty alcohols; viii) Ethoxylated fatty alcohols; and ix) any and all of two or more of them.
44. The pourable, storage-stable, concentrated insecticidal oil-based dispersion composition as described in claim 42, wherein, The anionic surfactant is selected from, a) Surfactants based on phosphate esters or phosphonates; b) Surfactants based on sulfates or sulfonates; and c) A combination of surfactants based on phosphate esters or phosphonates and surfactants based on sulfates or sulfonates.
45. The pourable, storage-stable, concentrated insecticidal oil-based dispersion composition as described in claim 44, wherein, The surfactant based on phosphate esters or phosphonates is selected from, a) Anionic phosphate esters; b) A mixture of monoesters and diesters, free alcohols and phosphoric acid; c) Alkyl and / or arylphosphonic acids; d) Alkyl arylphosphonic acids; e) Phosphate esters of fatty alcohols; f) Ethoxylated fatty alcohol phosphate esters; g) Alkoxylated phosphate esters; h) Surfactants selected from the following phosphate ester or phosphonate-based surfactants. i) Ethoxylated phosphate esters; alkyl aryl phosphate esters; j) Alcohol ethoxylated phosphate esters; k) Alkylphenol ethoxylated phosphate esters; l) Alkylamine phosphates; and m) any and all of its combinations.
46. The pourable, storage-stable, concentrated insecticidal oil-based dispersion composition as described in claim 45, wherein, The surfactant based on phosphate esters or phosphonates is selected from, a) Isotridecyl polyoxyethyl phosphate mono / dieser; b) Tridecyl polyethylene glycol ether phosphate; c) Alkylphenoxy polyethyl esters of phosphoric acid.
47. The pourable, storage-stable, concentrated insecticidal oil-based dispersion composition as described in claim 44, wherein, The sulfate- or sulfonate-based surfactants are selected from, a) Branched or straight-chain alkylbenzene sulfonates; b) Alkyl sulfonates; c) Olefin sulfonates; d) Alkyl ether sulfonates; e) Glyceryl ether sulfonate, f) Methyl ester sulfonate; g) Alkyl ester sulfonate; h) Sulfonated fatty acids; i) Alkyl sulfates; j) Fatty alcohol ether sulfates; k) Glyceryl ether sulfate; l) Fatty acid ether sulfates; m) Hydroxy mixed ether sulfate; n) Glyceryl monoester (ether) sulfate, o) Fatty acid amide (ether) sulfate; p) mono- and dialkyl sulfosuccinates; q) Dialkyl (EO) sulfonyl succinate; r) mono- and dialkyl sulfosuccinates; s) sulfoglycerides; t) Alkyl oligoglucosinolate sulfate; u) Alkyl ether sulfates; v) Alkyl naphthalene sulfonic acid (salt); w) Naphthalenesulfonic acid formaldehyde condensation product (salt); x) A salt of the condensation product of naphthalenesulfonic acid, phenolsulfonic acid, and formaldehyde. y) Alkali metal salts of alkyl naphthalene sulfonic acids; z) Sodium dodecylbenzenesulfonate (SDBS); aa) Sodium lauryl sulfate Sodium lauryl ether sulfate (bb) cc) Salt of naphthalenesulfonic acid-formaldehyde condensation product; dd) Monoesters and diesters of sulfosuccinate metal salts with branched or straight-chain alcohols; Sodium dioctyl sulfosuccinate (ee) Sodium cocoyl hydroxyethyl sulfonate (ff) (gg) Allyl / alkyl or alcohol, polyoxyethylene sulfate; hh) alkyl succinate sulfate; and ii) Any and all of its combinations.
48. The pourable, storage-stable, concentrated insecticidal oil-based dispersion composition as described in claim 47, wherein, The sulfate- or sulfonate-based surfactants are selected from, a) Branched or straight-chain alkylbenzene sulfonates; b) Calcium alkylbenzene sulfonate; c) Alkyl (C 10-16 )benzenesulfonic acid (calcium salt); d) Dodecylbenzene sulfonate; e) Branched alkylbenzenes (C 11-13 ) sulfonates (calcium salts); f) Sodium lauryl sulfate g) Sodium lauryl ether sulfate; and h) Any and all of its combinations.
49. The pourable, storage-stable, concentrated insecticidal oil-based dispersion composition as described in claim 42, wherein, The alkyl glycoside is selected from, a) Alkyl glucoside; b) Alkyl monoglucoside; c) Alkyl polyglucosides; d) Alkyl monosaccharide glycoside; e) Alkyl polysaccharide glycosides; f) Alkyl polysaccharides and g) Any combination thereof.
50. The pourable, storage-stable, concentrated insecticidal oil-based dispersion composition as described in claim 42, wherein, The thickener and / or rheology additive are selected from, a) Organic derivatives of lithium montmorillonite clay; b) Vegetable oil derivatives, such as blends of vegetable oil bases; c) Natural oils; d) Fumed silica; e) Colloidal silica; f) Diamide wax; g) Polyamide wax; h) Amide-modified hydrogenated vegetable oil; i) Modified hydrogenated castor oil; j) Hydrogenated castor oil; k) Urea-modified nonpolar polyamide; l) Polyhydroxycarboxylic acid amides; m) Modified urea; n) Peralkalized calcium sulfate complex; o) Montmorillonite clay; as well as p) Any combination of them.
51. The pourable, storage-stable, concentrated insecticidal oil-based dispersion composition as described in claim 42, wherein, The end-use dispersible stabilizer / compensator is selected from the following amines: a) Tertiary alkylamines b) Triethylamine; c) N,N-diisopropylethylamine; d) Butylamine e) Triethanolamine; and f) Any and all combinations of two or more of them.
52. The pourable, storage-stable, concentrated insecticidal oil-based dispersion composition as described in claim 42, wherein, The vegetable oil-based liquid carrier is selected from, a) Vegetable oil; b) Alkylated vegetable oils c) Methyl soybean oleate; d) Palm methyl ester oil; e) Methyl oleate; f) Methyl linoleate; g) Methyl linoleate; h) Methyl stearate; i) Methyl palmitate; and j) Its combination.
53. The pourable, storage-stable, concentrated insecticide oil-based dispersion composition of claim 42, comprising, a) Pymetrozine in solid particles between 0% and 32% w / w. b) Alkoxylation auxiliaries at approximately 1% to 10% w / w c) Anionic surfactants based on phosphate esters or phosphonates, at approximately 1% to 7%. d) Anionic surfactants based on sulfates or sulfonates, at a concentration between approximately 0.5% and approximately 4% w / w. e) Alkyl glycosides (alkyl sugars) at approximately 1% to approximately 10% w / w, f) Thickeners and / or rheology modifiers between 0.1% and about 3% w / w, g) Dispersible stabilizers / compensators for end-use applications in the range of 0.01% to approximately 1% w / w, and h) Liquid carriers based on vegetable oils.
54. The pourable, storage-stable, concentrated biocidal oil-based dispersion composition as described in claim 42, suitable for end-use dispersion in excess aqueous media after storage, characterized in that... Low viscosity and stable water dispersibility, comprising: a) Solid particulate non-prehydrated pymetrozine b) PEG polyisobutylene anhydride-talc fatty acid copolymer (Atlox 4914), c) Isotridecyl polyoxyethyl phosphate mono / diester, acid form ( 1306), d) Organic derivatives of lithium montmorillonite clay (Bentone SD-3) e) Triethylamine; f) D-glucanopyranose, oligosaccharides 10-16 A mixture of alkyl glycosides, and D-glucanopyranose, oligodecyl octyl glycoside ( 650EC), g) Methyl soybean oleate The water content in the concentrated pymetrozine oil-based dispersion is between 0% and 5% based on the total weight of the concentrated pest-killing oil-based dispersion.
55. The pourable, storage-stable, concentrated biocidal oil-based dispersion composition as described in claim 42, suitable for end-use dispersion in excess aqueous media after storage, characterized in that... Low viscosity and stable water dispersibility, comprising: a) Solid microparticles of pymetrozine, b) Flupyradifon c) PEG polyisobutylene anhydride-talc fatty acid copolymer (Atlox 4914), d) Isotridecyl polyoxyethyl phosphate mono / diester, acid form ( 1306), e) Organic derivatives of lithium montmorillonite clay (Bentone SD-3) f) Triethylamine; g) D-glucanopyranose, oligosaccharides 10-16 A mixture of alkyl glycosides, and D-glucanopyranose, oligodecyl octyl glycoside ( 650EC), h) Methyl soybean oleate The water content in the concentrated oil-based dispersion is less than 5% by weight of the total dispersion.
56. The pourable, storage-stable, concentrated biocidal oil-based dispersion composition as described in claim 42, suitable for end-use dispersion in excess aqueous media after storage, characterized in that... Low viscosity and stable water dispersibility, comprising: a) Pymetrozine, b) A copolymer of polyethylene glycol and 12-hydroxystearic acid (Atlox) TM 4912), c) Isotridecyl polyoxyethyl phosphate mono / diester, acid form ( 1306), d) Organic derivatives of lithium montmorillonite clay (Bentone SD-3) e) Triethylamine; f) D-glucanopyranose, oligosaccharides 10-16 A mixture of alkyl glycosides, and D-glucanopyranose, oligodecyl octyl glycoside ( 650EC), g) Oil-based carrier.
57. The pourable, storage-stable, concentrated biocidal oil-based dispersion composition as described in claim 42, suitable for end-use dispersion in excess aqueous media after storage, characterized in that... Low viscosity and stable water dispersibility, comprising: a) Pymetrozine, b) Flupyradifurone, c) A copolymer of polyethylene glycol and 12-hydroxystearic acid (Atlox) TM 4912), d) Isotridecyl polyoxyethyl phosphate mono / diester, acid form ( 1306), e) Organic derivatives of lithium montmorillonite clay (Bentone SD-3) f) Triethylamine; g) D-glucanopyranose, oligosaccharides 10-16 A mixture of alkyl glycosides, and D-glucanopyranose, oligodecyl octyl glycoside ( 650EC), h) Oil-based carrier.
58. The pourable, storage-stable, concentrated biocidal oil-based dispersion composition as described in claim 42, suitable for end-use dispersion in excess aqueous media after storage, characterized in that... Low viscosity and stable water dispersibility, comprising: a) Pymetrozine, b) A copolymer of polyethylene glycol and 12-hydroxystearic acid as an alkoxylation auxiliary agent. c) Isotridecyl polyoxyethyl phosphate monoester / dieser, in acid form, as an anionic surfactant based on phosphate esters / phosphonates. d) Branched or straight-chain alkylbenzene sulfonates as anionic surfactants based on sulfates or sulfonates, e) Organic derivatives of lithium montmorillonite clay as rheology modifiers. f) Triethylamine as a dispersible stabilizer / compensator for end-use applications g) D-glucose pyranose as an alkyl glycoside, oligo-C 10-16 A mixture of alkyl glycosides, and D-glucopyranose, oligodecyl octyl glycoside h) Oil-based carrier.
59. The pourable, storage-stable, concentrated biocidal oil-based dispersion composition as described in claim 42, suitable for end-use dispersion in excess aqueous media after storage, characterized in that... Low viscosity and stable water dispersibility, comprising: a) Pymetrozine, b) Flupyradifurone, c) A copolymer of polyethylene glycol and 12-hydroxystearic acid as an alkoxylation auxiliary agent. d) Isotridecyl polyoxyethyl phosphate monoester / diester, in acid form, as an anionic surfactant based on phosphate esters / phosphonates. e) Branched or straight-chain alkylbenzene sulfonates as sulfate- or sulfonate-based anionic surfactants, f) Organic derivatives of lithium montmorillonite clay as rheology modifiers. g) Triethylamine as a dispersible stabilizer / compensator for end-use applications. h) D-glucose pyranose as an alkyl glycoside, oligo-C 10-16 A mixture of alkyl glycosides, and D-glucopyranose, oligodecyl octyl glycoside i) Oil-based carrier.
60. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a concentrated biocidal oil-based dispersion composition comprising, a) Pymetrozine, b) A copolymer of polyethylene glycol and 12-hydroxystearic acid as an alkoxylation auxiliary agent. c) Tridecyl polyethylene glycol ether phosphate as an anionic surfactant based on phosphate esters / phosphonates d) Alkyl (C) compounds as sulfate- or sulfonate-based anionic surfactants 10-16 )benzenesulfonate, e) Alkoxylated branched C as an alkoxylation auxiliary 8-18 alcohol, f) Rheology modifiers, g) Oil-based carrier.
61. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a concentrated biocidal oil-based dispersion composition comprising, a) Pymetrozine, b) Flupyradifurone, c) A copolymer of polyethylene glycol and 12-hydroxystearic acid as an alkoxylation auxiliary agent. d) Tridecyl polyethylene glycol ether phosphate as an anionic surfactant based on phosphate esters / phosphonates, e) Branched or straight-chain alkylbenzene sulfonates as sulfate- or sulfonate-based anionic surfactants, f) Alkoxylated branched C as an alkoxylation auxiliary 8-18 alcohol, g) Rheology modifiers, h) Oil-based carrier.
62. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a concentrated biocidal oil-based dispersion composition comprising, A. Pymetrozine, B. Flupyradifonide, C. A copolymer of polyethylene glycol and 12-hydroxystearic acid as an alkoxylation auxiliary agent. D. Tridecyl polyethylene glycol ether phosphate as an anionic surfactant based on phosphate esters / phosphonates E. Alkyl (C) compounds as sulfate- or sulfonate-based anionic surfactants 10-16 )benzenesulfonate, F. Alkoxylated branched C as an alkoxylation aid 8-18 alcohol, G. Rheology modifiers H. Oil-based carrier.
63. The concentrated biocidal oil-based dispersion composition of claim 60, comprising, a) Pymetrozine, b) A copolymer of polyethylene glycol and 12-hydroxystearic acid as an alkoxylation auxiliary agent. c) Tridecyl polyethylene glycol ether phosphate as an anionic surfactant based on phosphate esters / phosphonates d) Alkyl (C 10-16 Benzenesulfonates (anionic surfactants based on sulfates or sulfonates) e) Alkoxylated branched C as an alkoxylation auxiliary 8-18 alcohol, f) Rheology modifiers, g) Triethylamine as a dispersible stabilizer / compensator for end-use applications. h) Alkyl polysaccharides as alkyl glycosides i) Oil-based carrier.
64. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a concentrated biocidal oil-based dispersion composition comprising, a) Pymetrozine, b) Flupyradifurone, c) A copolymer of polyethylene glycol and 12-hydroxystearic acid as an alkoxylation auxiliary agent. d) Tridecyl polyethylene glycol ether phosphate as an anionic surfactant based on phosphate esters / phosphonates, e) Alkyl (C) as anionic surfactants based on sulfates or sulfonates 10-16 )benzenesulfonate, f) Alkoxylated branched C as an alkoxylation auxiliary 8-18 alcohol, g) Rheology modifiers h) Triethylamine as a dispersible stabilizer / compensator for end-use applications i) Alkyl polysaccharides as alkyl glycosides j) Oil-based carrier.
65. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage, characterized by low viscosity and stable water dispersibility, comprising: a) Pymetrozine, b) PEG polyisobutylene anhydride-talc fatty acid copolymer (Atlox 4914), c) Polyethylene glycol tridecyl ether phosphate ( RS 610), d) Organic derivatives of lithium montmorillonite clay (Bentone SD-3), e) Triethylamine, f) D-glucanopyranose, oligosaccharides 10-16 A mixture of alkyl glycosides, and D-glucanopyranose, oligodecyl octyl glycoside ( 650EC), g) Methyl soybean oleate The water content in the concentrated oil-based dispersion is less than 5% by weight of the total dispersion.
66. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage, characterized by low viscosity and stable water dispersibility, comprising: a) Pymetrozine, b) Flupyradifon c) PEG polyisobutylene anhydride-talc fatty acid copolymer (Atlox 4914), d) Polyethylene glycol tridecyl ether phosphate ( RS 610) e) Organic derivatives of lithium montmorillonite clay (Bentone SD-3) f) Triethylamine; g) D-glucanopyranose, oligosaccharides 10-16 A mixture of alkyl glycosides, and D-glucanopyranose, oligodecyl octyl glycoside ( 650EC), h) Methyl soybean oleate The water content in the concentrated oil-based dispersion composition is less than 5% by weight of the total dispersion.
67. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage, characterized by low viscosity and stable water dispersibility, comprising: a) Pymetrozine, b) PEG polyisobutylene anhydride-talc fatty acid copolymer (Atlox 4914), c) Tridecyl polyethylene glycol ether phosphate (SERVOXYL VPDZ), d) Organic derivatives of lithium montmorillonite clay (Bentone SD-3) e) Triethylamine; f)C8 / C 10 Alkyl polysaccharide ( PG 8107), g) Methyl soybean oleate The water content in the concentrated oil-based dispersion composition is less than 5% by weight of the total dispersion.
68. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage, characterized by low viscosity and stable water dispersibility, comprising: a) Pymetrozine, b) Flupyradifon c) PEG polyisobutylene anhydride-talc fatty acid copolymer (Atlox 4914), d) Tridecyl polyethylene glycol ether phosphate (SERVOXYL VPDZ) e) Organic derivatives of lithium montmorillonite clay (Bentone SD-3) f) Triethylamine; g)C8 / C 10 Alkyl polysaccharide (Agnique PG 8107), h) Methyl soybean oleate The water content in the concentrated oil-based dispersion is less than 5% by weight of the total dispersion.
69. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a concentrated biocidal oil-based dispersion composition comprising, a) Pymetrozine, b) Sorbitol laurate, Sorbitol monolaurate (SPAN 20) c) α-Isotridecyl-ω-hydroxy-poly(oxy-1,2-ethylenedimethyl)phosphate, d) Alkoxylated branched C 8-18 Imbentin e) Silicon dioxide f) Oil-based carrier.
70. The composition of any one of claims 61-69, comprising: at least one branched or linear alkylbenzene sulfonate anionic surfactant.
71. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a concentrated biocidal oil-based dispersion composition comprising, a) Solid microparticles of pymetrozine, b) Sorbitol laurate, Sorbitol monolaurate (SPAN 20) c) Tristyrylphenol ether sulfate salt d) Alkoxylated branched C 8-18 Imbentin e) Silicon dioxide f) Oil-based carrier.
72. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a concentrated biocidal oil-based dispersion composition comprising, a) Pymetrozine, b) Flupyradifurone, c) Sorbitol laurate, Sorbitol monolaurate (SPAN 20) d) Tristyrylphenol ether sulfate salt, e) Alkoxylated branched C 8-18 Imbentin f) Silicon dioxide g) Oil-based carrier.
73. The composition of any one of claims 71-72, comprising: at least one anionic surfactant based on phosphate esters and / or phosphonates.
74. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a concentrated biocidal oil-based dispersion composition comprising, a) Pymetrozine, b) Sorbitol laurate, Sorbitol monolaurate (SPAN 20) c) α-Isotridecyl-ω-hydroxy-poly(oxy-1,2-ethylenedimethyl)phosphate, d) Alkoxylated branched C 8-18 Imbentin e) Triethylamine; f) Alkyl polysaccharide, g) Silicon dioxide h) Oil-based carrier.
75. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a concentrated biocidal oil-based dispersion composition comprising, a) Solid microparticles of pymetrozine, b) Sorbitol laurate, Sorbitol monolaurate (SPAN 20) c) α-Isotridecyl-ω-hydroxy-poly(oxy-1,2-ethylenedimethyl)phosphate, d) Alkoxylated branched C 8-18 Imbentin e) Triethylamine; f) Alkyl polysaccharide, g) Silicon dioxide, h) Oil-based carrier.
76. The composition of any one of claims 74-75, comprising: at least one branched or linear alkylbenzene sulfonate anionic surfactant.
77. The non-aqueous biocidal suspension composition of claim 1, wherein, The composition is a concentrated biocidal oil-based dispersion composition comprising, a) Solid microparticles of pymetrozine, b) Sorbitol laurate, Sorbitol monolaurate (SPAN 20) c) Tristyrylphenol ether sulfate salt d) Alkoxylated branched C 8-18 Imbentin, triethylamine; e) Alkyl polysaccharide, f) Triethylamine; g) Silicon dioxide h) Oil-based carrier.
78. The composition of claim 77, comprising at least one anionic surfactant based on phosphate esters and / or phosphonates.
79. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion suitable for end-use dispersion in excess aqueous media after the storage period, characterized by low viscosity and stable water dispersibility, comprising: a) Approximately 20% w / w pymetrozine, b) Approximately 5% w / w of PEG polyisobutylene anhydride-talc fatty acid copolymer as an alkoxylation auxiliary agent. c) Approximately 4% w / w of isotridecyl polyoxyethyl phosphate monoester / diester, in acid form, as an anionic surfactant based on phosphate esters / phosphonates. d) 0.5% of an organic derivative of lithium montmorillonite clay as a rheology modifier. e) Approximately 0.05% w / w of triethylamine as a dispersible stabilizer / compensator for end-use applications. f) 4.5% w / w C as an alkyl glycoside 8-10 Alkyl polysaccharides, g) Methyl soybean oleate as a liquid carrier based on vegetable oil, The water content in the concentrated oil-based dispersion is between 0.5% and 5% based on the total weight of the dispersion.
80. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage, characterized by low viscosity and stable water dispersibility, comprising: a) Approximately 20% w / w pymetrozine, b) Flupyradifurone as an adjunct to the pesticide compound at approximately 10% w / w. c) Approximately 5% w / w of PEG polyisobutylene anhydride-tal oil fatty acid copolymer as an alkoxylation aid. d) Approximately 4% w / w isotrimethylene polyoxyethyl phosphate monoester / diester, in acid form, as an anionic surfactant based on phosphate esters / phosphonates. e) Organic derivatives of lithium montmorillonite clay, approximately 0.5% w / w, used as rheology modifiers. f) Approximately 0.05% w / w of triethylamine as a dispersible stabilizer / compensator for end-use applications. g) 4.5% C 8-10 Alkyl polysaccharides (alkyl glycosides), h) Methyl soybean oleate (a vegetable oil-based liquid carrier), The water content in the concentrated pymetrozine oil-based dispersion is between 0.5% and 5% based on the total weight of the dispersion.
81. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage, characterized by low viscosity and stable water dispersibility, comprising: a) Approximately 20% w / w pymetrozine, b) Approximately 5% w / w of PEG polyisobutylene anhydride-talc fatty acid copolymer as an alkoxylation auxiliary agent. c) Approximately 4% w / w of isotridecyl polyoxyethyl phosphate monoester / diester, in acid form, as an anionic surfactant based on phosphate esters / phosphonates. d) Approximately 0.5% of an organic derivative of lithium montmorillonite clay as a rheology modifier. e) Approximately 0.05% w / w of triethylamine as a dispersible stabilizer / compensator for end-use applications. f) Approximately 4.5% D-glucopyranose and oligo-C as alkyl glycosides 10-16 A mixture of alkyl glycosides, and D-glucopyranose, oligodecyl octyl glycoside g) Methyl soybean oleate as a liquid carrier based on vegetable oil, The water content in the concentrated oil-based dispersion is between 0.5% and 5% based on the total weight of the dispersion.
82. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage, characterized by low viscosity and stable water dispersibility, comprising: a) 20% pymetrozine, b) 10% w / w flonicamid (a biocidal compound other than pymetrozine), c) 5% w / w PEG polyisobutylene anhydride-tal oil fatty acid copolymer (alkoxylation aid), d) 4% w / w isotridecyl polyoxyethyl phosphate monoester / diester, acid form (anionic surfactant based on phosphate ester / phosphonate). e) 0.5% organic derivatives of lithium montmorillonite clay (rheology modifier), f) 0.05% w / w triethylamine (end-use dispersible stabilizer / compensator), 4.5% D-glucopyranose, oligosaccharides 10-16 A mixture of alkyl glycosides, and D-glucopyranose, oligodecyl octyl glycoside h) Methyl soybean oleate (a vegetable oil-based liquid carrier), The water content in the concentrated pymetrozine oil-based dispersion is between 0.5% and 5% based on the total weight of the dispersion.
83. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage, characterized by low viscosity and stable water dispersibility, comprising: a) Approximately 20% w / w pymetrozine, b) Approximately 5% w / w of PEG polyisobutylene anhydride-talc fatty acid copolymer as an alkoxylation auxiliary agent. c) Approximately 4% w / w of isotridecyl polyoxyethyl phosphate monoester / diester, in acid form, as an anionic surfactant based on phosphate esters / phosphonates. d) Approximately 0.5% of an organic derivative of lithium montmorillonite clay as a rheology modifier. e) Approximately 0.05% w / w of triethylamine as a dispersible stabilizer / compensator for end-use applications. f) Approximately 4.5% w / w C as an alkyl glycoside 8-10 Alkyl polysaccharides, g) Methyl soybean oleate as a liquid carrier based on vegetable oil, h) Branched or linear alkylbenzene sulfonate anionic surfactants, such as branched alkylbenzenes (C... 11-13 ) sulfonate salts, The water content in the concentrated pymetrozine oil-based dispersion is between 0.5% and 5% based on the total weight of the dispersion.
84. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage, characterized by low viscosity and stable water dispersibility, comprising: a) Approximately 20% w / w pymetrozine, b) Approximately 10% w / w flonicamid, c) Approximately 5% w / w of PEG polyisobutylene anhydride-tal oil fatty acid copolymer as an alkoxylation aid. d) Approximately 4% w / w isotrimethylene polyoxyethyl phosphate monoester / diester, in acid form, as an anionic surfactant based on phosphate esters / phosphonates. e) 0.5% organic derivatives of lithium montmorillonite clay (rheology modifier), f) Approximately 0.05% w / w of triethylamine as a dispersible stabilizer / compensator for end-use applications. g) as approximately 4.5% C as an alkyl glycoside 8-10 Alkyl polysaccharides, h) Methyl soybean oleate as a liquid carrier based on vegetable oil, i) Branched or straight-chain alkylbenzene sulfonate anionic surfactants, such as branched alkylbenzenes (C... 11-13 ) sulfonate salts, The water content in the concentrated oil-based dispersion is between 0.5% and 5% based on the total weight of the dispersion.
85. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage, characterized by low viscosity and stable water dispersibility, comprising: a) Approximately 20% w / w pymetrozine, b) Approximately 5% w / w of PEG polyisobutylene anhydride-talc fatty acid copolymer as an alkoxylation auxiliary agent. c) Approximately 4% w / w of isotridecyl polyoxyethyl phosphate monoester / diester, in acid form, as an anionic surfactant based on phosphate esters / phosphonates. d) Approximately 0.5% of an organic derivative of lithium montmorillonite clay as a rheology modifier. e) 0.05% w / w triethylamine (end-use dispersible stabilizer / compensator), f) Approximately 4.5% D-glucopyranose and oligo-C as alkyl glycosides 10-16 A mixture of alkyl glycosides, and D-glucopyranose, oligodecyl octyl glycoside g) Methyl soybean oleate as a liquid carrier based on vegetable oil, h) Branched or linear alkylbenzene sulfonate anionic surfactants, such as branched alkylbenzenes (C... 11-13 ) sulfonate salts, i) The water content in the concentrated oil-based dispersion is between 0.5% and 5% based on the total weight of the dispersion.
86. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage, characterized by low viscosity and stable water dispersibility, comprising: a) Approximately 20% w / w pymetrozine, b) Approximately 10% w / w flonicamid, c) Approximately 5% w / w of PEG polyisobutylene anhydride-tal oil fatty acid copolymer as an alkoxylation aid. d) Approximately 4% w / w isotrimethylene polyoxyethyl phosphate monoester / diester, in acid form, as an anionic surfactant based on phosphate esters / phosphonates. e) Approximately 0.5% of an organic derivative of lithium montmorillonite clay as a rheology modifier. f) Approximately 0.05% w / w of triethylamine as a dispersible stabilizer / compensator for end-use applications. g) Approximately 4.5% D-glucopyranose and oligo-C as alkyl glycosides 10-16 A mixture of alkyl glycosides, and D-glucopyranose, oligodecyl octyl glycoside h) Methyl soybean oleate as a liquid carrier based on vegetable oil, i) Branched or straight-chain alkylbenzene sulfonate anionic surfactants, such as branched alkylbenzenes (C... 11-13 ) sulfonate salts, The water content in the concentrated oil-based dispersion is between 0.5% and 5% based on the total weight of the dispersion.
87. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage, characterized by low viscosity and stable water dispersibility, comprising: a) Pymetrozine, b) Flupyradifurone (a biocidal compound other than pymetrozine), c) PEG polyisobutylene anhydride-tal oil fatty acid copolymer as an alkoxylation aid d) Isotridecyl polyoxyethyl phosphate monoester / diester, in acid form, as an anionic surfactant based on phosphate esters / phosphonates. e) Branched or linear alkylbenzene sulfonate anionic surfactants, sulfate- or sulfonate-based anionic surfactants. f) Organic derivatives of lithium montmorillonite clay as rheology modifiers. g) Triethylamine as a dispersible stabilizer / compensator for end-use applications. h) D-glucanopyranose, oligosaccharides 10-16 A mixture of alkyl glycosides, and D-glucanopyranose, oligodecyl octyl glycoside ( 650EC), i) Methyl soybean oleate as a liquid carrier based on vegetable oil, The water content in the concentrated oil-based dispersion is less than 5% by weight of the total dispersion.
88. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage, characterized by low viscosity and stable water dispersibility, comprising: a) Pymetrozine, b) PEG polyisobutylene anhydride-tal oil fatty acid copolymer as an alkoxylation aid c) Isotridecyl polyoxyethyl phosphate monoester / dieser, in acid form, as an anionic surfactant based on phosphate esters / phosphonates. d) Branched or straight-chain alkylbenzene sulfonate anionic surfactants as sulfate- or sulfonate-based anionic surfactants. e) Organic derivatives of lithium montmorillonite clay as rheology modifiers. f) Triethylamine as a dispersible stabilizer / compensator for end-use applications g) D-glucose pyranose as an alkyl glycoside, oligo-C 10-16 A mixture of alkyl glycosides, and D-glucopyranose, oligodecyl octyl glycoside h) Methyl soybean oleate as a liquid carrier based on vegetable oil, The water content in the concentrated oil-based dispersion is less than 5% by weight of the total dispersion.
89. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage, characterized by low viscosity and stable water dispersibility, comprising: a) Pymetrozine, b) Flupyradifurone, c) PEG polyisobutylene anhydride-tal oil fatty acid copolymer as an alkoxylation aid d) Isotridecyl polyoxyethyl phosphate monoester / diester, in acid form, as an anionic surfactant based on phosphate esters / phosphonates. e) Branched or straight-chain alkylbenzene sulfonate anionic surfactants as sulfate- or sulfonate-based anionic surfactants. f) Organic derivatives of lithium montmorillonite clay as rheology modifiers. g) Triethylamine as a dispersible stabilizer / compensator for end-use applications. h) D-glucose pyranose as an alkyl glycoside, oligo-C 10-16 A mixture of alkyl glycosides, and D-glucopyranose, oligodecyl octyl glycoside i) Methyl soybean oleate as a liquid carrier based on vegetable oil, The water content in the concentrated oil-based dispersion is less than 5% by weight of the total dispersion.
90. The non-aqueous biocidal suspension composition as described in claim 1, wherein, The composition is a pourable, storage-stable, concentrated biocidal oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage, characterized by low viscosity and stable water dispersibility, comprising: a) Pymetrozine, b) PEG polyisobutylene anhydride-talc fatty acid copolymer (alkoxylation aid), c) Isotridecyl polyoxyethyl phosphate mono / diester, acid form (anionic surfactant based on phosphate ester / phosphonate ester), d) Branched or straight-chain alkylbenzene sulfonate anionic surfactants (sulfate- or sulfonate-based anionic surfactants), e) Organic derivatives of lithium montmorillonite clay (rheology modifiers) f) Triethylamine as a dispersible stabilizer / compensator for end-use applications g) D-glucanopyranose, oligosaccharides 10-16 A mixture of alkyl glycosides, and D-glucanopyranose, oligodecyl octyl glycoside (alkyl glycoside), h) Methyl soybean oleate (a vegetable oil-based liquid carrier), The water content in the concentrated pymetrozine oil-based dispersion is less than 5% by weight of the entire dispersion.
91. The pourable, storage-stable, concentrated biocidal oil-based dispersion composition according to any one of claims 42-90, suitable for end-use dispersion in an excess aqueous medium after storage, wherein, The adaptation method includes packaging the concentrated composition in a container to provide an amount of the final-use dispersion diluted between 50 and 500 liters in an aqueous medium, the container being accompanied by instructions for dispersing and diluting the concentrated biocidal oil-based dispersion composition in excess aqueous medium, wherein the container is impermeable to both moisture and light such that the water content of the contained concentrated biocidal oil-based dispersion composition does not increase by more than 5% w / w after a one-month storage period in the container at 40°C / 75% RH, and the pymetrozine content degrades by no more than 5% w / w when the packaged concentrated biocidal oil-based dispersion composition is stored exposed to sunlight and / or artificial light with wavelengths between 250 nm and 400 nm.
92. The non-aqueous biocidal suspension composition of claim 12, wherein, The composition is a packaged, storage-stable, concentrated biocidal oil-based dispersion composition suitable for end-use dispersion in excess aqueous media after storage, comprising: a) Pymetrozine, b) Alkoxylation auxiliaries, c) Anionic surfactants selected from the following groups: i) Anionic surfactants based on sulfates or sulfonates; ii) Anionic surfactants based on phosphate esters / phosphonates; and iii) Its combination, d) Rheology modifiers e) Dispersible stabilizers / compensators for end-use applications f) Alkyl polyglucosides g) Methyl soybean oleate The adaptation method includes packaging the concentrated composition in a container to provide a dilute end-use dispersion in an aqueous medium in amounts between 50 and 500 liters, the container being accompanied by instructions for dispersing and diluting the concentrated biocidal oil-based dispersion composition in excess aqueous medium, wherein the container is impermeable to both moisture and light such that the percentage increase in water content of the OBPD contained in the container after a period of storage at 40°C / 75% RH does not exceed 5% w / w, and the pymetrozine content degrades by no more than 5% w / w when stored exposed to sunlight and / or artificial light with wavelengths between 250 nm and 400 nm.
93. A method for preparing a composition as described in any one of 1-92, comprising the following steps: a) Introduce the oil-based liquid carrier into the container. b) Add non-insecticide formulation aids, other than thickeners and / or rheology modifiers—if present. c) Mix until homogeneous d) Add the pymetrozine and optionally additional pest-killing compounds—if present—while stirring under high shear force. e) Add thickeners and / or rheology modifiers—if present—and apply high shear stress to obtain a dispersion. f) Grind the dispersion. g) Package the obtained milled dispersion into a container. The container is selected from one or more of the following: i) For a water-impermeable container, such that after a period of storage in the container at 40°C / 75%RH, the water content % of the contained OBPD increases by no more than 5% w / w. ii) The container is light-impermeable, such that when stored in sunlight and / or artificial light with wavelengths between 250 and 400 nm, the photodegradation of the pymetrozine content does not exceed 5% w / w. iii) A container that is impermeable to both moisture and light, such that after a period of storage in the container at 40°C / 75%RH, the water content of the contained OBPD increases by no more than 5% w / w, and the pymetrozine content degrades by no more than 5% w / w when stored in sunlight and / or artificial light with wavelengths between 250 nm and 400 nm. During storage at elevated temperatures and / or elevated relative humidity, such as at 54°C for at least two weeks and / or at 40°C / 75% RH for at least one month, the water content, excluding any water associated with the prehydrated pymetrozine—if present—is maintained by the container at less than 5% by weight of the total dispersion.
94. The method of claim 93, further comprising the following steps: a) Introducing a vegetable oil-based liquid carrier into a container. b) Add non-insecticide formulation aids, other than thickeners and / or rheology modifiers—if present. c) Mix until homogeneous d) Add pymetrozine and other biocidal compounds besides pymetrozine—if present—while stirring under high shear force. e) Add thickeners and / or rheology modifiers—if present—and apply high shear stress to obtain a dispersion. f) Grind the dispersion. g) Package the obtained milled dispersion into a container. The container is selected from one or more of the following: i) For a water-impermeable container, such that after a period of storage in the container at 40°C / 75%RH, the water content % of the contained OBPD increases by no more than 5% w / w. ii) The container is light-impermeable, such that when stored in sunlight and / or artificial light with wavelengths between 250 and 400 nm, the photodegradation of the pymetrozine content does not exceed 5% w / w. iii) A container that is impermeable to both moisture and light, such that after a period of storage in the container at 40°C / 75%RH, the water content of the contained OBPD increases by no more than 5% w / w, and the pymetrozine content degrades by no more than 5% w / w when stored in sunlight and / or artificial light with wavelengths between 250 nm and 400 nm. During storage at elevated temperatures and / or elevated relative humidity, such as at 54°C for at least two weeks and / or at 40°C / 75% RH for at least one month, the total water content is maintained by the container at less than 5% by weight of the total dispersion.
95. The method of claim 93, further comprising the following steps: a) Introducing a vegetable oil-based liquid carrier into a container. b) Add non-insecticide formulation aids other than the aforementioned thickeners and / or rheology additives and sulfate- or sulfonate-based anionic surfactants. c) Mix until homogeneous. d) Add the pymetrozine and any additional pest-killing compounds—if present—while stirring under high shear force. e) Add thickeners and / or rheology modifiers—if present—and apply high shear stress to obtain a dispersion. f) Grind the dispersion. g) Add an anionic surfactant based on sulfate or sulfonate and mix to obtain a final homogeneous dispersion. h) Package the obtained final homogeneous dispersion into a container. The container is selected from one or more of the following: i) For a water-impermeable container, such that after a period of storage in the container at 40°C / 75%RH, the water content % of the contained OBPD increases by no more than 5% w / w. ii) The container is light-impermeable, such that when stored in sunlight and / or artificial light with wavelengths between 250 and 400 nm, the photodegradation of the pymetrozine content does not exceed 5% w / w. iii) A container that is impermeable to both moisture and light, such that after a period of storage in the container at 40°C / 75%RH, the water content of the contained OBPD increases by no more than 5% w / w, and the pymetrozine content degrades by no more than 5% w / w when stored in sunlight and / or artificial light with wavelengths between 250 nm and 400 nm. During storage at elevated temperatures and / or elevated relative humidity, such as at 54°C for at least two weeks and / or at 40°C / 75% RH for at least one month, the total water content is maintained by the container at less than 5% by weight of the total dispersion.
96. The method of claim 93, further comprising the following steps: a) Introduce the oil-based liquid carrier into the container. b) Add, i) Alkoxylation auxiliaries, ii) Anionic surfactants based on phosphate esters / phosphonates, iii) Dispersible stabilizers / compensators for end-use applications, if present. iv) Alkyl glycosides c) Mix until homogeneous. d) Add the pymetrozine and any additional pest-killing compounds—if present—while stirring under high shear force. e) Add a rheology modifier and apply high shear force to obtain a dispersion. f) Grind the dispersion. g) Add an anionic surfactant based on sulfate or sulfonate and mix to obtain a final homogeneous dispersion. h) Package the obtained final homogeneous dispersion into a container. The container is selected from one or more of the following: i) For a water-impermeable container, such that after a period of storage in the container at 40°C / 75%RH, the water content % of the contained OBPD increases by no more than 5% w / w. ii) The container is light-impermeable, such that when stored in sunlight and / or artificial light with wavelengths between 250 and 400 nm, the photodegradation of the pymetrozine content does not exceed 5% w / w. iii) A container that is impermeable to both moisture and light, such that after a period of storage in the container at 40°C / 75%RH, the water content of the contained OBPD increases by no more than 5% w / w, and the pymetrozine content degrades by no more than 5% w / w when stored in sunlight and / or artificial light with wavelengths between 250 nm and 400 nm. During storage at elevated temperatures and / or elevated relative humidity, such as at 54°C for at least two weeks and / or at 40°C / 75% RH for at least one month, the total water content is maintained by the container at less than 5% by weight of the total dispersion.
97. The method of claim 93, further comprising the following steps: a) Introduce the oil-based liquid carrier into the container. b) Add, i) Alkoxylation auxiliaries, ii) Anionic surfactants based on phosphate esters / phosphonates, iii) Dispersible stabilizers / compensators for end-use applications, if present. iv) Alkyl glycosides c) Mix until homogeneous. d) Add the pymetrozine and any additional pest-killing compounds—if present—while stirring under high shear force. e) Add a rheology modifier and apply high shear force to obtain a dispersion. f) Grind the dispersion. g) Add an anionic surfactant based on sulfate or sulfonate—if present—and mix to obtain a final homogeneous dispersion. h) Package the obtained final homogeneous dispersion into a container. The container is selected from one or more of the following: i) For a water-impermeable container, such that after a period of storage in the container at 40°C / 75%RH, the water content % of the contained OBPD increases by no more than 5% w / w. ii) The container is light-impermeable, such that when stored in sunlight and / or artificial light with wavelengths between 250 and 400 nm, the photodegradation of the pymetrozine content does not exceed 5% w / w. iii) A container that is impermeable to both moisture and light, such that after a period of storage in the container at 40°C / 75%RH, the water content of the contained OBPD increases by no more than 5% w / w, and the pymetrozine content degrades by no more than 5% w / w when stored in sunlight and / or artificial light with wavelengths between 250 nm and 400 nm. During storage at elevated temperatures and / or elevated relative humidity, such as at 54°C for at least two weeks and / or at 40°C / 75% RH for at least one month, the total water content is maintained by the container at less than 5% by weight of the total dispersion.
98. The method of claim 93, further comprising the following steps: a) Introduce the oil-based liquid carrier into the container. b) Add, i) Alkoxylation auxiliaries, ii) Anionic surfactants based on phosphate esters / phosphonates, iii) Anionic surfactants based on sulfates or sulfonates, if present. iv) Dispersible stabilizers / compensators for end-use applications, if present v) Alkyl glycosides c) Mix until homogeneous. d) Add the pymetrozine and any additional pest-killing compounds—if present—while stirring under high shear force. e) Add a rheology modifier and apply high shear force to obtain a dispersion. f) Grind the dispersion. g) Package the obtained milled dispersion into a container. The container is selected from one or more of the following: i) For a water-impermeable container, such that after a period of storage in the container at 40°C / 75%RH, the water content % of the contained OBPD increases by no more than 5% w / w. ii) The container is light-impermeable, such that when stored in sunlight and / or artificial light with wavelengths between 250 and 400 nm, the photodegradation of the pymetrozine content does not exceed 5% w / w. iii) A container that is impermeable to both moisture and light, such that after a period of storage in the container at 40°C / 75%RH, the water content of the contained OBPD increases by no more than 5% w / w, and the pymetrozine content degrades by no more than 5% w / w when stored in sunlight and / or artificial light with wavelengths between 250 nm and 400 nm. During storage at elevated temperatures and / or elevated relative humidity, such as at 54°C for at least two weeks and / or at 40°C / 75% RH for at least one month, the total water content is maintained by the container at less than 5% by weight of the total dispersion.