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WO2025046127A1 - Composition agricole - Google Patents

Composition agricole Download PDF

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Publication number
WO2025046127A1
WO2025046127A1 PCT/EP2024/074375 EP2024074375W WO2025046127A1 WO 2025046127 A1 WO2025046127 A1 WO 2025046127A1 EP 2024074375 W EP2024074375 W EP 2024074375W WO 2025046127 A1 WO2025046127 A1 WO 2025046127A1
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WO
WIPO (PCT)
Prior art keywords
surfactant
agricultural composition
typically
colloidal silica
amount
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2024/074375
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English (en)
Inventor
Ruifei Wang
Peter Harry Johan Greenwood
Ulf Peter WESTBYE
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Nouryon Chemicals International BV
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Nouryon Chemicals International BV
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Filing date
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Publication of WO2025046127A1 publication Critical patent/WO2025046127A1/fr
Pending legal-status Critical Current
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides

Definitions

  • the present disclosure generally relates to an agricultural composition and more particularly relates to an agricultural composition that includes an adjuvant component that includes colloidal silica and/or a particular surfactant.
  • Rainfastness typically describes the ability of a pesticide composition to withstand rainfall or irrigation after application without being washed off the target plant or diluted. In other words, a rainfast pesticide composition will adhere to the surface of the target plant and continue to provide effective pest control even in the presence of water.
  • a pesticide composition If a pesticide composition is not rainfast, it can be easily washed away by rain or irrigation, reducing its effectiveness in controlling pests. This can lead to incomplete pest control and the need for re-application, which adds to the cost and environmental impact of pesticide use.
  • Rainfast pesticide compositions also save both time and money for farmers, as such compositions do not need to be reapplied after every rainfall event. This is especially important for large-scale farming operations.
  • the retention of a pesticide composition typically describes the ability of a pesticide composition to adhere to the plant surface during and after application. Pesticide compositions ideally remain on the plant surface to be effective. Typical factors affecting retention include the formulation of the pesticide composition, the plant's surface characteristics, and environmental conditions. Adding a adjuvant that helps spray droplets to stick and spread over the leaf surface can be helpful.
  • Pesticides need sufficient contact time with pests to be effective. High retention of pesticide compositions ensures that the pesticide compositions remain on the plant long enough to come into contact with the target pests, improving control.
  • Pesticide compositions that exhibit good rainfastness and retention properties have increased efficacy, reduced need to reapplication, lower costs, and can mitigate potential environmental risks associated with pesticide use.
  • This disclosure provides an agricultural composition including (A) an adjuvant component (B) water, and (C) an agrochemical.
  • the (A) adjuvant component includes a sol and/or a surfactant component comprising a first surfactant and/or a second surfactant.
  • the sol includes colloidal silica present in an amount of from about 1 to about 50 weight percent SiOi based on a total weight of the component.
  • the first surfactant includes an alcohol alkoxylate having from 6 to 20 carbon atoms and an average degree of alkoxylation of from about 0.5 to about 12 moles of alkylene oxide.
  • the first surfactant if present, is present in an amount of from about 1 to about 50 weight percent actives based on a total weight of the adjuvant component.
  • the second surfactant if present, includes a linear or branched alkyl glucoside having 6 to 12 carbon atoms and is present in an amount of from about 1 to about 50 weight percent actives based on a total weight of the adjuvant component.
  • FIG. 1 is an illustration of the results of the evaluation of comparative results of Example 1 including four different comparative compositions
  • FIG. 2 is an illustration of the evaluation of results of Example 2 including inventive and comparative compositions.
  • FIG. 3 is an illustration of the evaluation of results of Example 3 including six different compositions including inventive and comparative compositions.
  • FIG. 4A is a first illustration of the evaluation of results of Example 4 relative to Mixtures 1-5 and a reference;
  • FIG. 4B is a second illustration of the evaluation results of Example 4 relative to Mixtures 6-15;
  • FIG. 5 A is a bar graph setting forth a first set of results associated with Example 5; and [0022] FIG. 5B is a bar graph setting forth a second set of results associated with Example 5.
  • Embodiments of the present disclosure are generally directed to agricultural compositions, silica, surfactants, and methods for forming the same.
  • conventional techniques related to making agricultural compositions, silica sols, surfactants, etc. may not be described in detail herein.
  • the various tasks and process steps described herein may be incorporated into a more comprehensive procedure or process having additional steps or functionality not described in detail herein.
  • steps in the manufacture of agricultural compositions, silica sols, surfactants, etc are well-known and so, in the interest of brevity, many conventional steps will only be described briefly herein or will be omitted entirely without providing the well-known process details.
  • percent actives is well recognized in the art and means the percent amount of active or actual compound or molecule present as compared to, for example, a total weight of a diluted solution of a solvent and such a compound. Some compounds, such as a solvent, are not described relative to a percent actives because it is well known to be approximately 100% actives. Any one or more of the values describe herein may be alternatively described as percent actives as would be understood by the skilled person.
  • the terminology “free of’ describes embodiments that include less than about 5, 4, 3, 2, 1, 0.5, or 0.1, weight percent (or weight percent actives) of the compound or element at issue using an appropriate weight basis as would be understood by one of skill in the art. In other embodiments, the terminology “free of’ describes embodiments that have zero weight percent of the compound or element at issue.
  • polymers and compositions disclosed herein may typically comprise, consist of, or consist essentially of the components, elements, and process delineations described herein.
  • the embodiments illustratively disclosed herein suitably may be practiced in the absence of any element which is not specifically disclosed herein.
  • This disclosure provides an agricultural composition including (A) an adjuvant component (B) water, and (C) an agrochemical.
  • the (A) adjuvant component includes a sol and/or a first surfactant and/or a second surfactant.
  • the sol includes colloidal silica present in an amount of from about 1 to about 50 weight percent SiOi based on a total weight of the component.
  • the (A) adjuvant component also includes the first surfactant and/or the second surfactant.
  • the first surfactant includes an alcohol alkoxylate having from 6 to 20 carbon atoms and an average degree of alkoxylation of from about 0.5 to about 12 moles of alkylene oxide.
  • the first surfactant if present, is present in an amount of from about 1 to about 50 weight percent actives based on a total weight of the adjuvant component.
  • the second, if present, surfactant includes a linear or branched alkyl glucoside having 6 to 12 carbon atoms and is present in an amount of from about 1 to about 50 weight percent actives based on a total weight of the adjuvant component. Each is described in greater detail below.
  • the agricultural composition includes or is (A)-(C).
  • the agricultural composition may consist essentially of (A)-(C).
  • the agricultural composition may consist of (A)-(C).
  • the agricultural composition includes (A)-(C) and one or more additives described below.
  • the agricultural composition consists essentially of (A)-(C) and one or more additives described below.
  • the agricultural composition consists of (A)-(C) and one or more additives described below.
  • the agricultural composition may or may not include water as independently added.
  • the water may be introduced as part of one or more of (A)-(C).
  • the water may be independently added.
  • the water may be part of one of more of (A)-(C) and also independently added.
  • the terminology “consists essentially of’ describes that the agricultural composition may be free of, or include less than 5, 4, 3, 2, 1, or 0.5, weight percent actives of one or more polymers, solvents, actives, or additives that are not (A)-(C). Alternatively, in such embodiments, the composition may be entirely free of such polymers, solvents, actives, or additives that are not (A)-(C). In addition, such embodiments may or may not include water.
  • the agricultural composition may be a liquid and may be a solution, emulsion, or suspension. Moreover, the agricultural composition may be diluted or concentrated. In still other embodiments, the agricultural composition is an agricultural suspension concentrate formulation.
  • the agrochemical composition can be used as a ready to use (RTU) composition and/or can be used as a tank-mix additive or formulated in an in-can formulation.
  • the composition includes the (A) adjuvant component.
  • the adjuvant component is not particularly limited relative to an amount that is used in the composition.
  • the adjuvant component is typically present in an amount of from about 0.05 to about 10, about 0.1 to about 10, about 1 to about 10, about 0.05 to about 1, about 0.05 to about 0.1, about 0.1 to about 1, about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 or about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1, weight percent actives based on a total weight of the composition.
  • weight percent actives based on a total weight of the composition.
  • the adjuvant component is typically present in an amount of from about 1 to about 50, about 5 to about 50, about 10 to about 45, about 15 to about 40, about 20 to about 35, or about 25 to about 30, weight percent actives based on a total weight of the composition.
  • weight percent actives based on a total weight of the composition.
  • the use concentration of the adjuvant component in an in-can pesticide formulation is not particularly limited.
  • the amount may be from about 0.005 % to about 30 %, typically about 0.05 % to about 20 %, and more typically about 0.5 % to about 15 % in weight %.
  • the pesticide concentration is typically from about 5 % to 65 %, typically from 10 % to 60 %, and more typically from 30 % to 55 %, and still more typically from 40 % to 55 %, based on weight % active ingredient.
  • the use concentration of the adjuvant component in a tank mix pesticide spray solution is not particularly limited.
  • the amount may be from about 0.001 % to about 5 %, typically about 0.01 % to about 2 %, and more typically about 0.075% to about 1 % (in weight % mixture basis) in the total spray solution.
  • the use rate of the adjuvant component for a tank mix is about 0.05 to about 10 wt% actives, e.g. about 0.05 to about 2 wt% actives.
  • PCT PATENT APPLICATION Attorney Docket No.: 364.1659PC the use rate for in-can applications is about 1 to about 50 wt% actives, e.g. about 5 to about 25 wt% actives.
  • the adjuvant component optionally includes a sol including colloidal silica, e.g. also known as a silica sol.
  • a sol including colloidal silica e.g. also known as a silica sol.
  • the sol may or may not be used.
  • the terminology “sol” typically describes a stable dispersion of colloidal silica (SiO2) particles in a liquid, such as water.
  • the silica sol may also be described as a colloidal silica dispersion.
  • the sol includes colloidal silica, e.g. silica particles.
  • the terms “silica sol” and “colloidal silica” have the same meaning.
  • the term “colloidal silica” refers to a dispersion comprising about 1 to about 50 wt% silica particles dispersed in an aqueous medium.
  • the aqueous medium may comprise organic solvent, but where it does so it typically comprises less than 10 wt% organic solvent. If an organic solvent is present, the aqueous medium more typically includes no more than about 5 wt% organic solvent.
  • Typical organic solvents when present, are water- miscible, for example being chosen from one or more of C 1-4 alkyl alcohols, C 1-4 aldehydes, C 1-4 ketones, C 1-4 carboxylic acids their C 1-4 alkyl esters, and combinations thereof.
  • the sol may include one or more individual types of colloidal silica. In such embodiments, at least one is of the type described herein and one or more additional types may be of the type described herein or of the type not described herein or may be a mixture of both.
  • the composition as a whole may include one or more independent sols.
  • at least one is of the type described herein and one or more additional types may be of the type described herein or of the type not described herein or may be a mixture of both.
  • Silane-modified colloidal silica particles can be utilized as a pre-formulated silica sol with a solid content of, e.g.10-80%, which can be provided as a silane-modified dispersion or can be reacted with the silane.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • Colloidal silica particles may be derived from e.g. precipitated silica, micro silica (silica fume), pyrogenic silica (fumed silica) or silica gels, and mixtures thereof.
  • the colloidal silica particles are negatively charged.
  • Such particles can be prepared from a soluble silicate source, for example an alkali metal silicate solution such as water glass, or an ammonium silicate solution.
  • the soluble silicate can be ion exchanged to produce polysilicic acid, and the pH can be raised to enable growth of anionic colloidal silica particles.
  • Sols made in this way tend to have very low amounts of aggregated silica particles, compared for example to dispersing solid forms of silica in a liquid medium.
  • the adjuvant component may include the sol including the colloidal silica present in an amount of from about 1 to about 50 weight percent SiCT based on a total weight of the adjuvant component. In various embodiments, this amount is from about 1 to about 25, about 25 to about 45, about 30 to about 40, about 35 to about 40, about 5 to about 50, about 10 to about 45, about 15 to about 40, about 20 to about 35 or about 25 to about 30, weight percent SiCT based on a total weight of the adjuvant component.
  • this amount is from about 2 to about 24, about 3 to about 23, about 4 to about 22, about 5 to about 21, about 6 to about 20, about 7 to about 19, about 8 to about 18, about 9 to about 17, about 10 to about 16, about 11 to about 15, about 12 to about 14, or about 13 to about 14, weight percent SiCT based on a total weight of the adjuvant component.
  • the silica content in the sol is, e.g., from 1 to 80 wt.%, typically from 5 to 80 wt.%, more typically from 10 to 80 wt.%, e.g. still more typically 20 to 80 wt.%, yet more typically from 25 to 70 wt.%, and even more typically 30 to 60 wt.%.
  • the pH of the silica sol suitably is, e.g., from 1 to 13, typically from 6 to 12, more typically from 7.5 to 11.
  • the pH suitably is, e.g., from 1 to 12, typically from 3.5 to 11.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the colloidal silica particles can be suitably present in an aqueous solvent, suitably in the presence of stabilising cations such as K + , Na + , Li + , NH4 + , organic cations, primary, secondary or tertiary amines, quaternary ammonium compounds, or mixtures thereof so as to form an aqueous silica sol.
  • stabilising cations such as K + , Na + , Li + , NH4 + , organic cations, primary, secondary or tertiary amines, quaternary ammonium compounds, or mixtures thereof so as to form an aqueous silica sol.
  • colloidal silica dispersed in partially organic dispersions including e.g.
  • water-miscible solvents such as lower alcohols with 1 to 4 carbon atoms, acetone or mixtures thereof may be used, wherein the volume of the organic portion can be in an amount of, for example, from 1 to 20 %, typically from 1 to 10 %, and more typically 1 to 5 % by volume of the total aqueous and organic volume.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the sol itself is not particularly limited and can have a S i O2 content of from about 5 to about 60 wt% depending on particle size. In various embodiments, this content is from about 10 to about 55, about 15 to about 50, about 20 to about 45, about 25 to about 40, or about 30 to about 35, weight % based on a total weight of the sol.
  • the sol may be diluted for use herein such that the colloidal silica is present in an amount of from about 1 to about 50 weight percent SiOi based on a total weight of the adjuvant component.
  • the sol is not further diluted such that the weight percent SiOi of the colloidal silica in the sol matches the weight percent SiOi of the colloidal silica present relative to the total weight of the adjuvant component.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • Aqueous silica sols can be basic, having a pH of from about 8.0 to about 11.0, for example from about 8.5 to about 11.0.
  • Other optional components of such sols include the presence of alkali metals, typically one or more of lithium, sodium and potassium. Typically sodium is the sole or predominant alkali metal.
  • the alkali metals can be derived from soluble silicate solutions (e.g. water glass) that can be used to make the colloidal silica using conventional processes.
  • suitable aqueous alkali metal silicates or water glass that can be used to make aqueous silica sols include lithium, sodium and potassium silicates, typically sodium silicate.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the silica particles are typically amorphous nanoparticles, and most typically have a particle diameter of from about 2 to about 170 nm.
  • the colloidal silica particles typically have an average particle diameter of from about 2 to about 100 nm or from about 3 to about 75 nm.
  • the particle diameter is from about 4 to about 50 nm, from about 5 to about 30 nm or from about 7 to about 25 nm. In other embodiments, the particle diameter is from about 5 to about 25, about 10 to about 20, about 10 to about 15, etc.
  • colloidal silica particles employed suitably have an average particle diameter usually ranging from 2 to 150, typically from 2 to 100, more typically 3 to 50, still more typically 4 to 40, yet more typically 4 to 15, and even more typically 5 to 12 nm.
  • the colloidal silica particles can have a specific surface area, e.g., from 20 to 1500, typically from 50 to 900, more typically 70 to 700 and still more typically from 100 to 600 m 2 /g, yet more typically 150 to 500, and even more typically 200 to 400 nm, measured by Sears titration (G.W.Sears; Anal. Chem., 1956, 28(12) pp1981-1983).
  • a specific surface area e.g., from 20 to 1500, typically from 50 to 900, more typically 70 to 700 and still more typically from 100 to 600 m 2 /g, yet more typically 150 to 500, and even more typically 200 to 400 nm, measured by Sears titration (G.W.Sears; Anal. Chem., 1956, 28(12) pp1981-1983).
  • G.W.Sears Sears titration
  • ES-DMA electro-spray differential mobility analysis
  • CLS centrifugal liquid analysis
  • SEM scanning electron microscopy
  • TEM transmission electron micro
  • Particle size may be determined using one or more methods such as ASTM D5861, ISO 13320:2009, ISO 13320:2020, or the like. Moreover, the particle size may be further defined as Dv10, Dv50, Dv90, Dn10, Dn50, Dn90, Dv95, Dv99, Dn95, Dn99, etc. It is also contemplated that one or more of the particle size measurements may fall outside of the aforementioned ranges. Moreover, the particle size may be determined using any apparatus known in the art, e.g. a Malvern Mastersizer such as the Mastersizer 3000.
  • the colloidal silica particles may have a narrow particle size distribution, i.e. a low relative standard deviation of the particle size.
  • the relative standard deviation of the particle size distribution is the ratio of the standard deviation of the particle size distribution to the mean particle size by numbers.
  • the relative standard deviation of the particle size distribution may be lower than, e.g., 60% by numbers, typically lower than 30% by numbers, more typically lower than 15% by numbers. In various additional non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the colloidal silica has an S value of from about 20 to about 95 %, for example from about 30% to about 90% or from about 50 to about 85%
  • the S-value is measured and calculated as described by Iler & Dalton (Iler & Dalton; J. Phys. Chem. 60(1956), 955-957).
  • the S-value indicates a degree of aggregate or microgel formation and a lower S-value is indicative of a higher degree of aggregation.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the silica sol may have an S-value, e.g., from 20 to 100, typically from 30 to 90, more typically from 60 to 90.
  • the S-value typically depends on the silica content, the viscosity, and the density of the colloidal silica particles.
  • a high S-value indicates a low microgel content.
  • the S-value represents the amount of SiOi in percent by weight present in the dispersed phase of e.g. a silica sol.
  • the degree of microgel can be controlled during the production process as further described in e.g. US 5,368,833.
  • Commercially available examples for suitable sols include the LevasilTM series of Nouryon.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the colloidal silica is made from particle growth from a soluble silicate or a polysilicic acid solution, and is not prepared by creating a dispersion from a solid form of silica nanoparticle.
  • the colloidal silica is not derived from solid forms of silica such as amorphous forms of fumed silica, silica fume and precipitated silica.
  • the colloidal silica is not derived from crystalline forms of silica, such as micro-quartz or nano-quartz, which suffer the additional disadvantage of potential health risks.
  • Soluble silicate- derived colloidal silicas tend to have less aggregation of the silica particles compared to dispersions made from solid forms of silica. This is because, in general, solid forms of silica nanoparticles tend to be in the form of agglomerates of the primary nanoparticles, and it is not usually possible to disperse such silicas to create a colloidal silica comprising predominantly the discrete primary particles because larger agglomerates tend to remain. The silica particles in such colloidal silicas therefore tend to settle (precipitate) relatively rapidly. In contrast, colloidal silicas made from particle growth from a soluble silicate or a polysilicic acid solution do not include such large silica agglomerates. They tend to be stable and do not typically noticeably gel or precipitate for many months, typically for greater than 12 months.
  • the colloidal silica is made by converting soluble alkali metal silicate to polysilicic acid (with a pH typically of from about 1 to about 3) by ion exchange or treatment with acid, and raising the pH to about 7 or more, typically about 8 to about 11, for example about 9 to about 11, using a basic alkali metal salt such as alkali metal hydroxide or alkali metal silicate.
  • the content of alkali metals in the starting silica sol can be of from about 0.1 to about 5.0 wt%, expressed as alkali metal oxide. In some embodiments, this content is from about 0.2 to about 3.0 wt%.
  • the silica concentration in the colloidal silica is of from about 1 to about 40 wt%, for example from about 2 to about 35 wt% or from about 3 to about 30 wt%.
  • silica concentrations are typically expressed as SiOi.
  • a typical minimum concentration is about 5 wt%, and most typical ranges are therefore about 5 to about 50 wt%, and more typically about 5 to about 40 wt%, for example about 5 to about 35 wt% or about 5 to about 30 wt%.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the colloidal silica particles typically have a surface area of from about 30 to about 1000 m 2 g -1 , for example of from about 40 to about 700 m 2 g -1 , such as of from about 60 to about 550 m 2 g _
  • the specific surface area of colloidal silica particles in a silica sol can be calculated from NaOH titration following the method of Sears (Sears; Anal. Chem., 1956, 28(12), 1981-1983). In various additional non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the density of the silica sol is at least in part dependent on the silica content, and is typically of from about 1.01 to about 1.45 g cm' 3 , and typically of from about 1.01 to about 1.30 g cm' 3 .
  • a silica sol of density 1.2 g cm' 3 has typically a silica content of 30 wt-% S1O2 while a silica sol of density 1.4 g cm' 3 has typically a silica content of 50-wt% SiOi.
  • Density can be determined using ASTM D4052-18a. In various additional non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the viscosity of the silica sol is typically less than about 40, 35, 30, 25, or 20, 15, 10, or 5 cP, measured at about 20°C. Viscosities of silica sols, including those described herein, can be measured using a conventional rotational viscometer. A method that can be used is ASTM D4016- 14. In various additional non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the colloidal silica particles can be dispersed in the presence of stabilizing cations, which can be chosen from alkali metals (e.g. K + , Na + , Li + ), ammonium (NH 4+ ), organic cations, quaternary amino, tertiary amino, secondary amino, and primary amino, or mixtures thereof. Typically, they are selected from alkali metals and ammonium.
  • stabilizing cations can be chosen from alkali metals (e.g. K + , Na + , Li + ), ammonium (NH 4+ ), organic cations, quaternary amino, tertiary amino, secondary amino, and primary amino, or mixtures thereof. Typically, they are selected from alkali metals and ammonium.
  • sols that can be used as starting aqueous silica sols include silica sols marketed under the name LevasilTM or BindzilTM from Nouryon.
  • Aluminum-modified silica sols can be prepared by adding an appropriate amount of aluminate ions, A1(OH)4‘ to a conventional non-modified silica sol under agitation.
  • the aluminate ion solution is typically a diluted sodium or potassium aluminate solution.
  • the silica particles typically have from about 0.05 to about 2, typically from about 0.1 to about 2, Al atoms per nm 2 surface area of the silica particles.
  • the aluminum-modified silica particles can include inserted or exchanged aluminate ions, creating aluminosilicate sites having a fixed negative surface charge.
  • the aluminum-modified silica particles can remain their high negative surface charge down to about pH 3 in contrast to conventional non-modified silica sols, for which the negative surface charge decreases when the pH decreases, normally down to a pH of about 2, which is the point of zero charge for a non- modified silica sol.
  • the surface charge is thus typically lower for non-modified silica particles than aluminum-modified silica sol at a pH below about 8.
  • the pH of the aluminum-modified silica sol can be adjusted, typically by using an ion exchange resin, typically to a pH ranging from about 3 to about 11, typically from about 4 to about 10.
  • the aluminum modified silica sol can thereafter be concentrated to yield a silica content from about 1 to about 60 wt%, typically from about 5 to about 50 wt%.
  • the aluminum modified silica particles can have an AI2O3 content of from about 0.05 to about 3, typically of from about 0.1 to about 2, and most typically from about 0.1 to about 1 wt%.
  • the diameter of the aluminum-modified silica particles typically is of from about 2 to about 200 nm, typically from about 3 nm to about 100 nm.
  • the procedure of preparing aluminum-modified silica sol is further described e.g. in “The Chemistry of Silica”, by Iler, K. Ralph, pages 407-409, John Wiley & Sons (1979) and in US 5,368,833, each incorporated herein by reference in various non-limiting embodiments.
  • the colloidal silica can include one or more of the following characteristics:
  • the colloidal silica can have about 0.15 wt% added aluminate as AI2O3 on the total product.
  • AI2O3 aluminate
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the colloidal silica may be modified or unmodified. If modified, the modified colloidal silica can be modified with at least one organosilane moiety comprising a silicon atom bound to the carbon atom of an organic group. In other words, in the modified colloidal silica at least a portion of the surface silanol groups can be replaced with one or more chemically bound organosilane groups.
  • the modified colloidal silica can be any known in the art. In various embodiments, the modified colloidal silica may be as described in US App. Ser Nos. 16/982,130 or 14/397,424, each of which is incorporated by reference in its entirety herein in various non- limiting embodiments.
  • the chemically bound organosilane groups can include a silicon atom attached to a group — R. From one to three — R groups can be present on the silicon atom of the organosilane moiety. Typically, there are at most two — R groups, and in some embodiments only one. Where there is more than one — R group, they can be the same as each other or different from each other.
  • the -R group may be alkyl, alkenyl, aryl, etc., and have from about 1 to about 20, about 2 to about 19, about 3 to about 18, about 4 to about 17, about 5 to about 16, about 6 to about 15, about 7 to about 14, about 8 to about 13, about 9 to about 12, or about 10 to about 11, carbon atoms.
  • the group may be linear, branched, or cyclic. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • Silane compounds can be admixed with colloidal silica particles may, e.g., be selected from organosilanes, such as mono-organosilanes and oligomeric organosilanes comprising 2 to 10 silicon atoms.
  • the silane compounds include at least one hydrolysable group such as halogen or alkoxy, so that they can undergo a condensation relation with the silanol groups on the surface of the silica particles.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • Typical organosilanes include those of general formula R x SiX4- x wherein x is an integer of 0 to 3, R is an organic residue, which is bonded to the silicon atom by a C-Si bond, and X is halogen or alkoxy.
  • the silane is a mono-organosilane, where x is 1. Where x is more than one, each R can be the same or different.
  • each R has 1 to 20 carbon atoms and includes a reactive group such as an epoxy group or a carbon-carbon double bond. As typical instances of the reactive group of R, epoxy, glycidoxy, glycidoxypropyl, vinyl and gamma- methacryloxypropyl may be mentioned.
  • X typically is chlorine or Ci-4 alkoxy and x is typically 2 or 3, more typically 3.
  • a mixture of two or more kinds of organosilanes may also be used. It is also possible to use oligo-silanes formed by condensation of two or more molecules of the organosilane(s). In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • silane compounds include tris-(trimethoxy)silane , octyl triethoxysilane, methyl triethoxysilane, methyl trimethoxysilane; isocyanate silane such as tris-[3- (trimethoxysilyl)propyl]isocyanurate; gamma-mercaptopropyl trimethoxysilane, bis-(3- [triethoxysilyl]propyl)polysulfide, beta-(3,4-epoxycyclohexyl)-ethyl trimethoxysilane; silanes containing an epoxy group (epoxy silane), glycidoxy and/or a glycidoxypropyl group such as gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl methyldiethoxysilane, (3- glycidoxypropyl)tri
  • silane modification may be performed by mixing the silane compound with the colloidal silica particles.
  • the silane and colloidal silica particles are admixed in a weight ratio of silane to silica ranging, e.g., from 0.05 to 1.5, typically from 0.1 to 0.8, more typically from 0.15 to 0.5.
  • a weight ratio of silane to silica ranging, e.g., from 0.05 to 1.5, typically from 0.1 to 0.8, more typically from 0.15 to 0.5.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the ratio of silane and colloidal silica also can be specified in terms of molecule number per surface area.
  • the amount of added silane to the colloidal silica particles suitably may be, e.g., from 0.1 to 6, typically from 0.3 to 3, more typically from 1 to 2 silane molecules per nm 2 surface area of the colloidal silica particles.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • At least 1 % by number of the silanol surface groups on the colloidal silica particles are capable of binding or linking to silane groups of the silane compounds, for example at least 5 %, typically least 10 %, more typically at least 30 %, even more typically at least 50 % bind or link to a silane group.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the silane compound can be diluted before mixing it with the colloidal silica particles, for example with water to form a premix of silane and water, suitably in a weight ratio of silane to water from, e.g., 1:8 to 8:1, typically from 3:1 to 1:3, more typically from 1.5:1 to 1:1.5.
  • the resulting silane-water solution is substantially clear and stable and easy to mix with the colloidal silica particles.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • silane and silica may be carried out at a pH from 1 to 13, typically from 6 to 12, more typically from 7.5 to 11, still more typically from 9 to 10.5.
  • a pH from 1 to 13, typically from 6 to 12, more typically from 7.5 to 11, still more typically from 9 to 10.5.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the mixing of silane and colloidal silica particles may be carried out continuously, for example at a temperature from 20 to 95°C, typically from 50 to 75°C, more typically from 60 to 70°C.
  • the silane may be slowly added to the silica particles under vigorous agitation at a controlled rate, which suitably is, e.g., from 0.01 to 100, typically from 0.1 to 10, more typically from 0.5 to 5, still more typically from 1 to 2 silane molecules per nm 2 colloidal silica surface area (on the colloidal silica particles) and hour.
  • the addition of silane can be continued for any suitable time depending on the addition rate, amount of silane to be added, and degree of desired silanisation.
  • silane may be continued up to 5 hours, for example up to 2 hours until a suitable amount of silane has been added.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the mixing may be continued from 1 second to 30 minutes, typically from 1 to 10 minutes after the addition of silane is stopped.
  • the dispersion may include besides silanized colloidal silica particles also, at least to some extent, non-silanized colloidal silica particles depending, e.g., on the size of the silica particles, weight ratio of silane to silica, type of silane compound mixed and the reaction conditions.
  • At least 40 wt.% of the colloidal silica particles are silanized, typically at least 65 wt.%, more typically at least 90 wt.%, still more typically at least 95 wt.%, and yet more typically at least 99 wt.%.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the dispersion may comprise besides silane in the form of silane groups or silane derivatives bound or linked to the surface of the silica particles also at least to some extent freely dispersed unbound silane compounds.
  • at least 40 wt.%, typically at least 60 wt.%, more typically at least 75 wt.%, still more typically at least 90 wt.%, even more typically at least 95 wt.% of the silane compounds are bound or linked to the surface of the silica particles.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • Pre-formulated silane modified silica sols such as the LevasilTM CC series of Nouryon can also be used.
  • a typical example is LevasilTM CC 401, which is a glycidyloxypropyl silane- modified silica sol with a solid content of 40 wt.% and an average particle size of 12 nm.
  • LevasilTM CC 401 is a glycidyloxypropyl silane- modified silica sol with a solid content of 40 wt.% and an average particle size of 12 nm.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the reaction conditions used in modifying the colloidal silica can cause a change in the reactive group.
  • the reactive group is or comprises an epoxy group
  • hydrolysis can occur to form corresponding vicinal diol groups.
  • an epoxy group becomes a diol group
  • a glycidyloxy alkyl group becomes a 3-(l,2-propandiol)-alkoxy group (e.g. a 3-(l,2-propandiol)- propoxy group).
  • the epoxy silane group can be hydrolyzed to form corresponding a vicinal diol silane group, e.g. in the presence of water, in the presence of an acid or a base catalyst, etc.
  • the colloidal silica may also include the vicinal diol silane group equivalents of the epoxy silane group.
  • the adjuvant component can include the first surfactant or be free of the first surfactant.
  • One first surfactant or more than one first surfactant may be utilized. If utilized, this surfactant is or includes an alcohol alkoxylate having from 6 to 20 carbon atoms. In various embodiments, the number of carbon atoms is from 6 to 20, 7 to 19, 6 to 18, 8 to 18, 9 to 17, 10 to 16, 11 to 15, 12 to 14, or 13 to 14. In other embodiments, the number of carbon atoms is 6 to 14, 6 to 12, 6 to 10, 6 to 8, 8 to 12, 8 to 10, 10 to 12, etc. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the first surfactant typically has an average degree of alkoxylation of from about 0.5 to about 12 moles of alkylene oxide.
  • the degree of alkoxylation may refer to ethoxylation, propoxylation, butoxylation, and/or combinations thereof.
  • the average degree of ethoxylation, propoxylation, and/or butoxylation may each independently be from about 0.5 to about 12. In various embodiments, this is from about 1 to about 12, about 2 to about 11, about 3 to about 10, about 4 to about 9, about 5 to about 8, or about 6 to about 7.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the first surfactant is a C9-11 alcohol ethoxylate that is linear or branched and is ethoxylated with from about 5 to about 6, from about 4 to about 7, or from about 3 to about 8, moles of ethylene oxide.
  • the first surfactant is a linear or branched CIO alcohol that is ethoxylated with from about 7 to about 8, about 6 to about 7, or about 6 to about 8, moles of ethylene oxide.
  • the first surfactant is a C16- C18 alcohol that is linear or branched and that is alkoxylated with from about 4 to about 5, about 4 to about 6, or about 4.5 to about 5.5, moles of ethylene oxide, and from about 7 to about 9, about 6 to about 8, or about 7 to about 8, moles of propylene oxide.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the first surfactant is present in an amount of from about 1 to about 50 weight percent actives based on a total weight of the adjuvant component. In various embodiments, this amount is from about 5 to about 45, about 10 to about 40, about 15 to about 35, about 20 to about 30, or about 25 to about 30, weight percent actives based on a total weight of the adjuvant component. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the adjuvant component can also include the second surfactant or be free of the second surfactant.
  • the adjuvant component includes the first and/or second surfactant. Therefore, the first surfactant may be used to the exclusion of the second surfactant or may be used in conjunction with the second surfactant. Alternatively, the second surfactant may be used to the exclusion of the first surfactant. One second surfactant or more than one second surfactant may be utilized.
  • this second surfactant is or includes a linear or branched alkyl glucoside having 6 to 12 carbon atoms. It is also contemplated that this second surfactant may be an alkyl polyglucoside. In one embodiment, the second surfactant is linear. In another embodiment, the second surfactant is branched. In various embodiments, the second surfactant has 6, 7, 8, 9, 10, 11, or 12 carbon atoms. The second surfactant is present in an amount of from about 1 to about 50 weight percent actives based on a total weight of the adjuvant component.
  • this amount is from about 5 to about 45, about 10 to about 40, about 15 to about 35, about 20 to about 30, or about 25 to about 30, weight percent actives based on a total weight of the adjuvant component.
  • the alkyl glucoside has 8 carbon atoms.
  • the alkyl glucoside is 2-ethylhexyl glucoside.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the first surfactant and the second surfactant are present in a molar ratio of about 0.95:1.05 to about 1.05:0.95, respectively. In other embodiments, this ratio is from about 0.5:1 to about 2:1, or about 0.75:1 to about 1.75:1, or about 1:1, or about 1.25:1 to about 2:1, or about 1.5:1 to about 2:1, etc. In still other embodiments, the first surfactant is not utilized. In other embodiments, the second surfactant is not utilized. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the adjuvant component is, includes, consists essentially of, or consists of, the sol. In various embodiments, the adjuvant component is, includes, consists essentially of, or consists of, the first surfactant. In various embodiments, the adjuvant component is, includes, consists essentially of, or consists of, the second surfactant. In various embodiments, the adjuvant component is, includes, consists essentially of, or consists of, the sol and the first surfactant. In various embodiments, the adjuvant component is, includes, consists essentially of, or consists of, the sol and the second surfactant.
  • the adjuvant component is, includes, consists essentially of, or consists of, the first surfactant and the second surfactant.
  • the terminology “consists essentially of’ can describe embodiments that are free of other surfactants that are not the first or second surfactants, other optional surfactants whether described herein or known in the art, additives, polymers, solvents, water, other silicon compounds that are not the sol, silicone compounds, etc.
  • the agrochemical composition also includes water.
  • the agricultural composition may or may not include water as independently added.
  • the water may be introduced as part of one or more of (A)-(C).
  • the water may be independently added apart from any one of (A)-(C).
  • the water may be both part of one of more of (A)-(C) and also independently added.
  • the water is not limited to any particular amount.
  • the water is present in an amount of from about 1 to about 99.99, depending on the application, e.g. RTU, in-can, or tank-mix.
  • the water is present in an amount that balances the weight of (A) and (C), e.g.
  • A+B+C is equal to about 100 weight percent of the total weight of the agrochemical composition.
  • the water is present in an amount of from about 1 to about 99.9, about 1 to about 99, about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 45 to about 50, weight percent based on a total weight of the agrochemical composition.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the agrochemical itself is not particularly limited and may be any known in the art.
  • an agrochemical is a chemical used in agricultural formulations.
  • Non-limiting examples of agrochemicals include fertilizers, micronutrients, activator adjuvants or potentiators, drift control agents, emulsifiers, deposition aids, water conditioners, wetting agents, dispersants, compatibility agents, suspension aids, pesticides such as herbicides, fungicides, and insecticides, and growth inhibitors.
  • agrochemical is described herein without specifying the counterions, it means both its acid form and salt form throughout the specification.
  • the agrochemical is a pesticide.
  • the agrochemical is a fertilizer.
  • the agrochemical is chosen from a pesticide, a fertilizer, and combinations thereof.
  • the agrochemical is chosen from herbicides, fungicides, insecticides, and combinations thereof.
  • the agrochemical is chosen from herbicides, fungicides, insecticides, fertilizers, and combinations thereof.
  • Suitable herbicides include, but are not limited to, acifluorfen, aclonifen, alachlor, ametryn, amidosulfuron, aminopyralid, amitrole, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin, benfluralin, bensulfuron-methyl, bentazone, bifenox, binalafos, bispyribac-sodium, bromacil, bromoxynil, butachlor, butroxidim, cafenstrole, carbetamide, carfentrazone-ethyl, chloridazon, chlorimuron-ethyl, chlorobromuron, chlorotoluron, chlorsulfuron, cinidon-ethyl, cinosulfuron, clethodim, clomazone, clopyralid, cloransulam- methyl, clorsul
  • the herbicide is chosen from atrazine, dicamba, glufosinate, paraquat, 2,4-D and mixtures and combinations thereof. In various embodiments, the herbicide is chosen from 2,4-D, atrazine, dicamba, and glufosinate and mixtures and combinations thereof. In various embodiments, the herbicide is glufosinate.
  • the herbicide is an acid, it can be used in the acid form though it is typical that the herbicide be in the salt form selected from at least one of the group of an amine, lithium, sodium, ammonium or potassium.
  • the agrochemical is chosen from Diuron, Azoxystrobin, Captan, Atrazine, Tebuconazol. In other embodiments, the agrochemical is a solid water insoluble or sparingly soluble pesticide, as would be recognized by one of skill in the art.
  • fungicides include, but are not limited to, acibenzolar-S-methyl, aldimorph, amisulbrom, anilazine, azaconazole, azoxystrobin, benalaxyl, benodanil, benomyl, benthiavalicarb, binapacryl, biphenyl, bitertanol, blasticidin- S, boscalid, bromuconazole, bupirimate, captafol, captan, carbendazim, carboxin, carpropamid, chloroneb, chlorothalonil, chlozolinate, copper, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, diflumetori
  • suitable insecticides include, but are not limited to, kerosene or borax, botanicals or natural organic compounds (nicotine, pyrethrin, strychnine and rotenone), chlorinated hydrocarbon (DDT, lindane, chlordane), organophosphates (malathion and diazinon), carbamates (carbaryl and propoxur), fumigants (naphthalene) and benzene (mothballs), synthetic pyrethroids, and mixtures and combinations thereof.
  • kerosene or borax botanicals or natural organic compounds (nicotine, pyrethrin, strychnine and rotenone), chlorinated hydrocarbon (DDT, lindane, chlordane), organophosphates (malathion and diazinon), carbamates (carbaryl and propoxur), fumigants (naphthalene) and benzene (mothballs), synthetic pyrethroids, and mixtures and combinations thereof
  • agrochemicals can be used including, for example, 2,4- dichlorophenoxyacetic acid (2,4-D), dicamba, and glufosinate. Each can be used individually or in combination with one or more others.
  • the agrochemical is chosen from diuron, captan, atrazine, and combinations thereof. Each can be used individually or in combination with one or more others.
  • the agrochemical is chosen from herbicides, fungicides, insecticides, miticides, biologicals, fertilizers, and combinations thereof.
  • the agrochemical is chosen from fungicides, insecticides, miticides, biologicals, fertilizers, and combinations thereof.
  • agrochemical composition can optionally comprise other additives such as ammonium sulfate, potassium sulfate, potassium chloride, sodium sulfate, urea, glycerol, glycols, polyglycols, or mixtures thereof.
  • the agrochemical may be or include a biopesticide, biostimulant, biofertilizer, inoculant, plant growth regulator, safener, or combinations thereof.
  • the agrochemical is present in an amount of from about 1 to about 99.99, depending on the application, e.g. RTU, in-can, or tank-mix. In various embodiments, the agrochemical is present in an amount that balances the weight of (A) and (B), e.g. A+B+C is equal to about 100 weight percent of the total weight of the agrochemical composition.
  • the agrochemical is present in an amount of from about 1 to about 99.9, about 1 to about 99, about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 45 to about 50, weight percent actives based on a total weight of the agrochemical composition.
  • a typical agrichemical concentration in RTU or spray tank applications is about 0.05 to about 50 g/L, e.g. about 0.1 to about 50 g/L.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • a second agrochemical e.g. a second active agent
  • it is typically utilized in an amount of from about 5 to about 90, about 10 to about 85, about 15 to about 80, about 20 to about 75, about 25 to about 70, about 30 to about 65, about 35 to about 60, about 40 to about 55, or about 45 to about 50, weight percent actives based on a total weight percent of the agricultural composition.
  • the weight ratio of the agrochemical to the second active agent generally is from about 1:1 to about 10:1, from about 1:1 to about 6:1, or from about 2:1 to about 6:1.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the concentration of the agrochemical is typically at least about 180, 200, 220, 240, 260, 280 or 300 grams acid equivalent per liter ("g a.e./L"), such as at least about 360 g a.e./L, or such as at least about 390 g a.e./L.
  • the concentration of the agrochemical is not lower than 400 g a.e./L or about 420 g a.e./L, in particularly typical compositions not lower than about 480 g a.e./L, about 500 g a.e./L, about 540 g a.e./L, about 580 g a.e./L, about 600 g a.e./L, or even about 620 g a.e./L, for example about 480 to about 540 g a.e./L, or about 480 to about 600 g a.e./L, or more.
  • the concentration of the agrochemical is from about 300 g a.e./L and about 600 g a.e./L, between about 420 g a.e./L and about 600 g a.e./L, or between about 480 g a.e./L and about 540 g a.e./L.
  • the concentration of the agrochemical may be from about 480 g a.e./L to about 620 g a.e./L, for example from about 480 g a.e./L to about 600 g a.e./L, or from about 540 to about 620 g a.e./L.
  • the concentration of the agrochemical is further described as an RTU formulation prepared by diluting the agrochemical with appropriate amounts of water.
  • the concentration of the agrochemical can be from about 1 g a.e./L to about 50 g a.e./L. In other embodiments, the concentration of the agrochemical is more typically from about 5 g a.e./L to about 20 g a.e./L. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • a weight ratio of agrochemical (a.e.) to the adjuvant component including the silica sol and first and/or second surfactants is from about 1 : 1 to about 100: 1 ,from about 1 to 1.1 :50, or from about 1 : 1 to about 50: 1.
  • the weight ratio is from about 1:1 to about 30:1 or from about 1:1 to about 20:1.
  • the weight ratio is between about 1:1 and about 30:1 or between about 2:1 and about 25:1 (e.g., typically between about 2.5:1 and about 20:1, between about 1:1 and about 15:1, between about 2:1 and about 10:1, between about 3:1 and about 15: 1, or between about 3.5:1 and about 8:1).
  • the weight ratio is from about 1:1 to about 15:1, more typically from about 1:1 to about 10:1 and, still more typically, from about 1:1 to about 8:1 (e.g., from about 1:1 to about 6:1, or from about 1:1 to about 4:1). In still other embodiments, the weight ratio is from about 3:1 to about 5:1, or from about 3:1 to about 4:1.
  • the concentration of agrochemical is in the range of from about 360 to about 600 g a.e./L, and the weight ratio of agrochemical (wt.% a.e.) to the adjuvant component is between about 2:1 and about 25:1 (e.g., between about 2.5:1 and about 20:1, or between about 3.5:1 and about 8:1. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the agricultural composition may include, or be free of, one or more additives that may include, but are not limited to, additional surfactants, defoamers, diluents, compatibility agents, biocides, thickeners, drift control agents, dyes, fragrances, and chelating agents.
  • additives may include, but are not limited to, additional surfactants, defoamers, diluents, compatibility agents, biocides, thickeners, drift control agents, dyes, fragrances, and chelating agents.
  • Co-surfactants in addition to the first and/or second surfactants described above, can also be present in, or excluded from, the agrochemical composition and may be anionic, nonionic, and/or amphoteric, or combinations thereof.
  • the additional surfactants may be of any type.
  • typical cationic surfactants are alkoxylated alkylamine and its quaternary derivative, alkoxylated etheramine and its quaternary derivative, alkoxylated alkyl amines and oxides, alkoxylated alkyl etheramines and oxides, alkyl amidopropyl amines and oxide, alkyl trimethyl ammonium chloride, and alkyl (typically C ⁇ > to Cio) dimethylamidopropylamine .
  • Non-limiting examples of typical anionic surfactants are alkylsulfate, alkylethersulfate, alkylsulfonate, alkylsulfosuccinate, alkoxylated phosphate ester, alkyl alpha olefin sulfonate, alkyl n-methyl taurate, fatty acid isethionate, and alkyl ether carboxylate.
  • Non-limiting examples of typical nonionic surfactants are alkoxylated mono and/or diglycerides, sorbitan ester and its alkoxylated derivative, sorbitol ester and its alkoxylated derivative, fatty acid ester, castor oil alkoxylate, alcohol alkoxylate, alkanolamide, alkanolamide alkoxylate, and alkyl polyglycoside.
  • Non-limiting examples of typical amphoteric surfactants are alkyl betaine, alkyl amidopropyl betaine, alkylamphoacetate, alkylamphodiacetate, alkylamphocarboxylate, alkylamphopropionate, alkylamphodipropionate, alkyl amidoamine carboxylate, alkylamphohydroxypropyl sulfonate, alkyl sultaine, alkyl amidopropyl hydroxyl sultaine, alkyl dihydroxyethyl glycinate, and alkyl aminopropionate.
  • the application for which the agricultural composition is used is not particularly limited.
  • the application is of a pesticide, or an herbicide, or a fungicide, or combinations thereof.
  • this disclosure provides methods for controlling unwanted vegetation comprising applying an effective amount of the agricultural composition to the unwanted vegetation.
  • this may be described as a method of controlling unwanted insects or unwanted fungi.
  • the method includes the step of applying an effective amount of the agricultural composition to a target.
  • the agrochemical composition should be applied to the target, e.g. plant foliage, at an application rate sufficient to give the desired effect.
  • Application rates are usually expressed as amount of agrochemical ae per unit area of land treated, e.g. grams ae per hectare (g a.e./ha).
  • Suitable efficacious application or spray rates will vary depending on the particular composition and concentration of active ingredients, the desired effects, plant species treated, weather and other factors. What constitutes a "desired effect" varies according to the standards and practice of those who investigate, develop, market, and use agrochemical products. For example, the amount of agrochemical a.e.
  • compositions of the disclosure provide equivalent herbicidal efficacy by comparison with commercial standard formulations of agrochemical.
  • Herbicidal efficacy refers to any observable measure of control of plant growth, which can include one or more of the actions of (1) killing, (2) inhibiting growth, reproduction or proliferation, and (3) removing, destroying, or otherwise diminishing the occurrence and activity of pests such as plants.
  • agrochemical application rate is an herbicidally effective amount of about 0.1 to about 10 kg a.e./ha and typically from about 0.25 to about 2.5 kg a.e./ha, although greater or lesser amounts may be applied.
  • the agricultural composition may be formed using any method known in the art.
  • the composition may be formed by combining (A), (B), and (C), and any additives or water, in batch form or continuously, e.g. using a mechanical stirrer or any other suitable container or device producing the necessary amount of agitation or circulation to thoroughly mix the ingredients.
  • the order of addition may be any combination of ingredients either in whole or in part.
  • water is added to a mixing vessel followed by the addition of the agrochemical and the first and/or second surfactants.
  • the first and second surfactants may be added as a preblended mixture.
  • Co- surfactants may be added singly, either before or after addition of the first and/or second surfactants.
  • This disclosure also provides methods for killing or controlling weeds or other unwanted plants, a method for killing pests, and a method for controlling disease.
  • These methods include spraying or otherwise applying an (e.g. herbicidally) effective amount of the agricultural composition to a target, e.g. the foliage of the plants to be treated, via any known method.
  • the composition is packaged in a portable container suitable for hand carry by a user and fitted with an apparatus for manually releasing the composition from the container onto the target in the form of a spray, e.g. from a tractor, drone, airplane, robot, farmer, etc.
  • the composition can be used to kill or control the growth of a wide variety of pests including insects, fungi, plants, etc.
  • the plants may include, without limitation, velvetleaf (Abutilon theophrasti), pigweed (Amaranthus spp.), buttonweed (Borreria spp.), oilseed rape, canola, indian mustard, etc. (Brassica spp.), commelina (Commelina spp.), filaree (Erodium spp.), sunflower (Helianthus spp.), momingglory (Ipomoea spp.), kochia (Kochia scoparia), mallow (Malva spp.), wild buckwheat, smartweed, etc.
  • plant species that may be killed or controlled include, without limitation, wild oat (Avenafatua), carpetgrass (Axonopus spp.), downy brome (Bromus tectorum), crabgrass (Digitaria spp), barnyardgrass (Echinochloa crus-galli), goosegrass (Eleusine indicd), annual ryegrass (Lolium multiflorum), rice (Oryza sativa), ottochloa (Ottochloa nodosa), bahiagrass (Paspalum notatum), canary grass (Phalaris spp.), foxtail (Setaria spp.), wheat (Triticum aestivum) and com (Zea mays).
  • wild oat Avenafatua
  • carpetgrass Axonopus spp.
  • downy brome Bromus tectorum
  • crabgrass Digitaria spp
  • barnyardgrass Echinochloa cru
  • mugwort Articleemisia spp.
  • milkweed Asclepias spp.
  • Thistle Cirsium arvense
  • field bindweed Convolvulus arvensis
  • kudzu Pueraria spp.
  • brachiaria (Brachiaria spp.), bermudagrass (Cynodon dactylon), quackgrass (Elymus repens), lalang (Imperata cylindrica), perennial ryegrass (Eolium perenne), guineagrass (Panicum maximum), dallisgrass (Paspalum dilatatum), reed (Phragmites spp.), johnsongrass (Sorghum halepense) and cattail (Typha spp.).
  • brachiaria (Brachiaria spp.), bermudagrass (Cynodon dactylon), quackgrass (Elymus repens), lalang (Imperata cylindrica), perennial ryegrass (Eolium perenne), guineagrass (Panicum maximum), dallisgrass (Paspalum dilatatum), reed (Phragmites spp.), johnsongrass (Sorghum halepens
  • Example 1 Comparative [00123] A first series of four different compositions was formed and evaluated to determine rainfastness. None of these compositions include silica. [00124] The first composition (Ref) includes water and 5 wt% blue pigment. [00125] The second composition (Surf A) includes a linear C9-11 alcohol ethoxylate, 5.5EO. [00126] The third composition (Surf B) includes a branched C10 alcohol ethoxylate, 7EO.
  • the fourth composition includes a C16-C18 alcohol alkoxylate, 4.8EO, 8PO.
  • each of the four compositions is diluted to about 0.4 weight percent actives in water and added with 5% blue pigment suspension.
  • the mixture is deposited in drops (50 ⁇ l in volume) in a 4x4 matrix on parafilm and dried overnight at room temperature. Subsequently, the compositions on the parafilm were washed using 400 g of artificial rain (water) for 10 seconds by pouring down of the water from a height of 5.5 cm. Illustrations of the dried deposits before and after washing are set forth in Figure 1.
  • Example 2 Adjuvant Component [00130] A second series of six different compositions was also formed. [00131] The fifth composition (Ref) includes water. This is a comparative composition. [00132] The sixth composition (first SiO2 + Surf A) includes colloidal silica (4% solid by weight), a linear C9-11 Alcohol ethoxylate, 5.5 EO (4% actives by weight).
  • the colloidal silica is a negatively charged silica having Na + as a counterion, a pH of 8-11, and a surface area of from about 80-200 m 2 /g. Therefore, this composition includes the sol and the first surfactant but does not include the second surfactant.
  • the seventh composition (second SiO2 + Surf A) includes colloidal silica (4% solid by weight), a linear C9-11 Alcohol ethoxylate, 5.5 EO (4% actives by weight)
  • the colloidal silica is a negatively charged silica having NH 3 + as a counterion, a pH of 8-11, and a surface area of from about 80-200 m 2 /g.
  • this composition includes the sol and the first surfactant but does not include the second surfactant.
  • each of these compositions is diluted to 0.04 weight percent surfactant actives in water and combined with a 5% blue pigment suspension to form a mixture.
  • the mixture is deposited in eighteen drops (50 ⁇ l in volume ) on parafilm and dried overnight at room temperature. Subsequently, the compositions on the parafilm were washed using 800 g of artificial rain for 30 seconds by pouring down from a height of 5.5 cm. Illustrations of the dried deposits before and after washing are set forth in Figure 2.
  • Example 3 Adjuvant Component [00135] A third series of six different compositions was also formed. [00136]
  • the eighth composition (Ref) includes water.
  • the ninth composition includes colloidal silica (4% solid by weight), a linear C9-11 Alcohol ethoxylate, 5.5 EO (4% actives by weight).
  • the colloidal silica is aluminum modified silica with a specific surface area of between 145-185 m 2 /g. Therefore, this composition includes the sol and the first surfactant but does not include the second surfactant.
  • the tenth composition includes the same colloidal silica as immediately above (4% solid by weight), a branched C10 Alcohol ethoxylate, 7 EO (4% actives by weight).
  • composition includes the sol and the first surfactant but does not include the second surfactant.
  • the eleventh composition includes the same colloidal silica as immediately above (4% solid by weight), a branched C16-C18 Alcohol alkoxylate, 4.8EO, 8PO (4% actives by weight). Therefore, this composition includes the sol and the first surfactant but does not include the second surfactant.
  • the twelfth composition includes the same colloidal silica as immediately above (4% solid by weight), 2-Ethylhexyl glucoside (4% actives by weight). Therefore, this composition includes the sol and the second surfactant but does not include the first surfactant.
  • the thirteenth composition includes only the immediately aforementioned silica and does not include any surfactant. This is a comparative composition.
  • each of these compositions is diluted to 0.04 weight percent surfactant actives/ solid in water and combined with 5% blue pigment suspension to form a mixture.
  • the mixture is deposited in eighteen drops (50 pl in volume ) on parafilm and dried overnight at room temperature. Subsequently, the compositions on the parafilm were washed using 800 g of artificial rain for 30 seconds by pouring down from a height of 5.5 cm. Illustrations of the dried deposits before and after washing are set forth in Figure 3.
  • Surfactant 1 is a linear C9-11 alcohol ethoxylate, 5.5 EO.
  • Surfactant 2 is 2-Ethylhexyl glucoside.
  • the SiOi is aluminum modified colloidal silica as describe above. The balance of each mixture is water.
  • each of the fifteen mixtures is diluted to 2 weight percent mixture in water and combined with a 5% blue pigment suspension to form a mixture.
  • the mixture is deposited in drops (50 pl in volume) on parafilm and dried overnight at room temperature. Subsequently, the compositions on the parafilm were washed using 800 g-quantity of artificial rain for 30 seconds as described above. Illustrations of the dried deposits before and after washing are set forth in Figures 4A and 4B. These results show that the water resistance clearly differs among the compositions. Water resistance depends on the presence of silica particles in the composition. The performance can be further tuned by the ratio of surfactants.
  • fungicides i.e., examples of the agrochemical of this disclosure
  • agrochemical of this disclosure Two commercial adjuvants were used for comparison.
  • Ref 1 is based on orange peel oil and proprietary surfactants.
  • Ref 2 is organosilicone spreader.
  • Comp 1 includes a linear C9-11 alcohol ethoxylate, 5.5 EO (15% actives wt%), 2- Ethylhexyl glucoside (14.95% actives by wt%), and the third SiCE (15% solids by wt%) with the balance of water.
  • Unizeb Gold The spray rate of Unizeb Gold was 2 kg per ha. Unizeb Gold includes 750 g mancozeb per kg.
  • the spray rate of Status was 1 liter per ha. Status includes 588 g copper oxychloride per liter.
  • Comp-1 showed clearly enhanced efficacy of example commercial fungicide formulations (Mancozeb WP and copper oxychloride SC). In comparison with typical adjuvant commercial products, Comp-1 also illustrated enhanced performance in higher efficacy of the fungicide formulations.

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Chemical & Material Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Toxicology (AREA)
  • Dentistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mycology (AREA)
  • Microbiology (AREA)
  • Dispersion Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

Une composition agricole comprend (A) un composant adjuvant, (B) de l'eau, et (C) un produit agrochimique. Le composant adjuvant (A) comprend un sol et/ou un composant tensioactif comprenant un premier tensioactif et/ou un second tensioactif. Le sol comprend de la silice colloïdale présente en une quantité d'environ 1 à environ 50 pour cent en poids de SiO2 sur la base d'un poids total du composant. Le premier tensioactif comprend un alcoxylate d'alcool présentant de 6 à 20 atomes de carbone et un degré moyen d'alcoxylation d'environ 0,5 à environ 12 moles d'oxyde d'alkylène. Le premier tensioactif, s'il est présent, est présent en une quantité d'environ 1 à environ 50 pour cent en poids d'agents actifs. Le second tensioactif, s'il est présent, comprend un glucoside d'alkyle linéaire ou ramifié présentant de 6 à 12 atomes de carbone et est présent en une quantité d'environ 1 à environ 50 pour cent en poids d'agents actifs.
PCT/EP2024/074375 2023-08-30 2024-08-30 Composition agricole Pending WO2025046127A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927749A (en) 1986-04-09 1990-05-22 Jeanette Simpson Reagent for cell separation
US5368833A (en) 1989-11-09 1994-11-29 Eka Nobel Ab Silica sols having high surface area
WO2007081553A2 (fr) * 2006-01-05 2007-07-19 E. I. Du Pont De Nemours And Company Formulations liquides d'arthropodicides de type carboxamides
WO2008030749A2 (fr) * 2006-09-06 2008-03-13 Syngenta Participations Ag Formulations d'émulsions de pickering
WO2012080197A1 (fr) * 2010-12-16 2012-06-21 Akzo Nobel Chemicals International B.V. Composition de dégraissage provoquant peu de stries
WO2016008696A1 (fr) * 2014-07-14 2016-01-21 Basf Se Émulsion huile-dans-eau agrochimique comprenant des particules de silice et un émulsifiant non-ionique soluble dans l'eau
WO2017202684A1 (fr) * 2016-05-25 2017-11-30 Bayer Cropscience Aktiengesellschaft Formulation agrochimique à base de polymères en émulsion
WO2017216285A1 (fr) * 2016-06-15 2017-12-21 Prebona Ab Sols composites

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927749A (en) 1986-04-09 1990-05-22 Jeanette Simpson Reagent for cell separation
US5368833A (en) 1989-11-09 1994-11-29 Eka Nobel Ab Silica sols having high surface area
WO2007081553A2 (fr) * 2006-01-05 2007-07-19 E. I. Du Pont De Nemours And Company Formulations liquides d'arthropodicides de type carboxamides
WO2008030749A2 (fr) * 2006-09-06 2008-03-13 Syngenta Participations Ag Formulations d'émulsions de pickering
WO2012080197A1 (fr) * 2010-12-16 2012-06-21 Akzo Nobel Chemicals International B.V. Composition de dégraissage provoquant peu de stries
WO2016008696A1 (fr) * 2014-07-14 2016-01-21 Basf Se Émulsion huile-dans-eau agrochimique comprenant des particules de silice et un émulsifiant non-ionique soluble dans l'eau
WO2017202684A1 (fr) * 2016-05-25 2017-11-30 Bayer Cropscience Aktiengesellschaft Formulation agrochimique à base de polymères en émulsion
WO2017216285A1 (fr) * 2016-06-15 2017-12-21 Prebona Ab Sols composites

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
G.W.SEARS, ANAL. CHEM., vol. 28, no. 12, 1956, pages 1981 - 1983
HERDALTON, J. PHYS. CHEM., vol. 60, 1956, pages 955 - 957
ILER, K. RALPH: "The Chemistry of Silica", 1979, JOHN WILEY & SONS, pages: 407 - 409

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