Low drift tank mix additive for low, medium and high volume spray applications

Abstract

The present invention is directed to tank-mix additives for low, medium and high volume spray applications, which include combinations of different drift reducing agents.

Description

[Technical field]

[0001] The present invention is directed to tank-mix additives for low, medium and high volume spray applications that contain combinations of different drift reducing agents. [Background technology]

[0002] Low and medium volume spray applications are becoming increasingly popular because they require less water, lighter vehicles, and in some cases, less adjuvants are carried into the environment.

[0003] However, currently available formulations are often only available for high or medium application rates or for low or medium application rates, but do not cover the entire range. Nevertheless, it would be desirable and economically feasible for farmers to use one formulation for all types of application, depending on the application method, requirements, environmental conditions, etc.

[0004] On the other hand, it is economically advantageous for a supplier to offer only one formulation for the entire range.

[0005] Tank-mix additives are important additives for improving the performance of crop protection products, especially when they contain ingredients that improve wetting, spreading and uptake by target crops and plants. However, these wetting, spreading and uptake enhancing ingredients, especially when these ingredients are surfactants, can increase drift by reducing droplet size in the spray solution after spraying.

[0006] To address this risk of drift, drift reducing agents can be included in the tank-mix adjuvant formulation.

[0007] It is known in the art that different drift reducing additives work more effectively at different application rates due to different concentrations in the diluted spray solution.

[0008] Polymer-based drift-reducing additives are most effective at high concentrations where their viscosity-raising effect is strong. Drift-reducing polymers increase the viscosity of the tank-mix composition, and there is an upper viscosity limit above which the tank-mix formulation becomes too thick to be used. As a result, it is difficult for 0.5-0.25 L / ha formulations to contain enough polymer to reduce drift when applied at high spray volumes, because high amounts of polymer make the tank-mix formulation too viscous to be used. However, this is not the case when low spray volumes are used, and much less polymer is needed in the formulation to provide an effective concentration in the spray solution. Conversely, a tank-mix formulation that contains enough polymer to reduce drift at high spray volumes will be unapplicable at low spray volumes, where the high polymer concentration inhibits the atomization process, thereby rendering the spray solution unapplicable.

[0009] Oil-based drift reducing additives work well over a wide range of concentrations. However, their effectiveness may be reduced in the diluted spray solution by surfactants as dispersants, emulsifiers, wetting agents, spreading agents or uptake promoters from the components in the product or tank-mix adjuvants used in the spray dilution. As a result, oil-based drift reducing additives may lose their effectiveness at low spray volumes where the concentration of these surfactants in the spray solution is higher.

[0010] Thus, there is a need for a drift reducing tank-mix additive that can work at both low and high spray rates, which is achieved by the present invention in which both polymeric and oil-based drift reducing additives are combined at effective levels in the tank-mix formulation.

[0011] Surprisingly, it has been found that a tank-mix additive including a combination of a particular polymer and an oil-based drift reducing additive can reduce drift in the tank-mix at fairly low concentrations and over a wide range of application volumes.

[0012] The combination of hydroxypropylated guar gum or other guar gums with oils in drift reducing compositions has already been disclosed in US2002 / 108415A1, WO2022 / 023255A1, WO2021 / 127865A1 and US2018 / 184647A1. However, the oil component is always used in very large amounts and serves different purposes besides drift reduction, such as serving as a carrier and uptake enhancer. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] US2002 / 108415A1 [Patent Document 2] WO2022 / 023255A1 [Patent Document 3] WO2021 / 127865A1 [Patent Document 4] US2018 / 184647A1 [Brief description of the drawings]

[0014] [Figure 1] FIG. 1 shows the % spray droplet size <100 microns for different spray volumes for the formulation in Example 1. [Diagram 2] FIG. 2 shows the % spray droplet size <100 microns for different spray volumes for the formulation in Example 2. [Diagram 3] FIG. 3 shows the % spray droplet size <100 microns for different spray volumes for the formulation in Example 3. [Figure 4]FIG. 4 shows the percent dispensed droplet size <100 microns for example polymer 1 versus different PEO polymer molar masses and concentrations. [Diagram 5] FIG. 5 shows the % dispensed droplet size <100 microns for different PEO polymer molar masses and PCF values ​​for Example Polymer 2. Summary of the Invention [Means for solving the problem]

[0015] Each tank-mix additive according to the invention, or more precisely the specific combination of adjuvants contained therein, is described below.

[0016] In one aspect, the present invention relates to a tank-mix additive for an agrochemical formulation comprising: (a) one or more polymeric drift reducing additives selected from the group consisting of poly(ethylene oxide) (hereinafter PEO) and hydroxypropylated guar (hereinafter HP guar); (b) one or more oil-based drift reducing additives; (c) one or more spreading agents and / or uptake enhancing additives; (d) other formulation aids; (e) one or more carriers up to a predetermined volume, at least one of the carriers being water; wherein (a) is present at 0.2 to 50 g / L, preferably 0.5 to 40 g / L, and more preferably 1 to 15 g / L; wherein (b) is present at 0.5 to 45 g / L, preferably 1 to 30 g / L, and more preferably 5 to 25 g / L; wherein (c) is present at 10 to 200 g / L, preferably 20 to 160 g / L, and more preferably 25 to 140 g / L; and Here, (d) is present in an amount of 20 to 300 g / L, preferably 30 to 180 g / L, and more preferably 30 to 135 g / L.

[0017] In a preferred embodiment, (a) is present at 0.2-50 g / L; (b) is present at 0.5-45 g / L; (c) is present at 10-200 g / L; (d) is present at 20-300 g / L; (e) Carriers up to a specified volume.

[0018] In a further preferred embodiment, (a) is present at 0.5-40 g / L; (b) is present at 1-30 g / L; (c) is present at 20-160 g / L; (d) is present at 30-180 g / L; (e) Carriers up to a specified volume.

[0019] In an even more preferred embodiment, (a) is present at 1-15 g / L; (b) is present at 5-25 g / L; (c) is present at 25-140 g / L; (d) is present at 30-135 g / L; (e) Carriers up to a specified volume.

[0020] It is understood that when combining various ingredients, the percentages of all ingredients in the tank-mix additive will always total 100.

[0021] Unless otherwise indicated, "%" in this application means percent by weight (% w / w).

[0022] Additionally, unless otherwise indicated, references to "to volume" with respect to a carrier indicate that the carrier (particularly water) is added to bring the total volume of the tank-mix additive to 1000 mL (1 L). For clarity, if unknown, the density of the tank-mix additive is assumed to be 1 g / cm 3 It is understood that it is understood to be.

[0023] Unless otherwise defined in this application, molecular weight refers to the weight average molecular weight Mw measured by GPC at 25° C. in methylene chloride using polystyrene as the standard.

[0024] In the context of the present invention, the tank-mix additive can be applied using a wide range of spray volumes, from 1 L / ha to 2000 L / h, preferably from 5 L / ha to 1500 L / ha, more preferably from 8 L / ha to 1200 L / ha.

[0025] Thus, a further aspect of the present invention is a method of applying the pesticide tank-mix additive according to the present invention to a crop, wherein the tank-mix additive is applied at a spray volume of 1 L / ha to 2000 L / ha, preferably 5 L / ha to 1500 L / ha, more preferably 8 L / ha to 1200 L / ha.

[0026] Therefore, another aspect of the present invention is the use of a tank-mix additive according to the present invention for application to a crop, wherein the tank-mix additive is applied in a spray volume of from 1 L / ha to 2000 L / ha, preferably from 5 L / ha to 1500 L / ha, more preferably from 8 L / ha to 1200 L / ha.

[0027] Furthermore, in the case of low spray rates, the tank-mix additive according to the invention is applied at a spray rate of 1-25 L / ha, preferably 2-20 L / ha, more preferably 5-15 L / ha.

[0028] Thus, a further aspect of the present invention is a method of applying the pesticide tank-mix additive according to the present invention to a crop, wherein the tank-mix additive is applied in a spray volume of 1 to 25 L / ha, preferably 2 to 20 L / ha, more preferably 5 to 15 L / ha.

[0029] Therefore, another aspect of the present invention is the use of a tank-mix additive according to the invention for application to a crop, wherein the tank-mix additive is applied in a spray volume of 1 to 25 L / ha, preferably 2 to 20 L / ha, more preferably 5 to 15 L / ha.

[0030] Preferably, the tank-mix additive is applied as a spray solution containing the tank-mix additive in the spray solution rates described above.

[0031] The ratio of (a) to (b) in the tank-mix additive according to the present invention is from 1:40 to 10:1, more preferably from 1:10 to 5:1, and most preferably from 1:6 to 2:1.

[0032] The ratio of (a), (b) and (c) in the tank-mix additive according to the present invention is from 1:40:150 to 10:1:10, more preferably from 1:12:120 to 2:1:5, and most preferably from 1:8:50 to 1:2:5.

[0033] Preferably, the above ratios are the same for spray solutions containing the tank-mix additive.

[0034] A further aspect of the present invention is the use of a tank-mix additive according to the present invention for delivery to an agricultural target plot.

[0035] The amount of (a) is preferably 0.5 to 15 g / ha, more preferably 1 to 12 g / ha, and most preferably 1 to 10 g / ha.

[0036] The amount of (b) is preferably 0.5 to 40 g / ha, more preferably 1 to 20 g / ha, and most preferably 2 to 10 g / ha.

[0037] The amount of (c) is preferably 10 to 200 g / ha, more preferably 15 to 160 g / ha, and most preferably 20 to 100 g / ha.

[0038] In a further preferred embodiment of the invention, the tank-mix additive consists solely of components (a)-(d) listed above in the amounts and ranges specified.

[0039] It is further understood that the given preferred ranges of application volumes or application rates, and the given preferred ranges of each component described in this application, can be freely combined, and while all combinations are disclosed herein, in more preferred embodiments the components are preferably present within the same preferred ranges, and even more preferably the components are present within their most preferred ranges.

[0040] In the context of the present invention, suitable agrochemical formulations to which the tank-mix additive according to the invention is added are, inter alia, suspension concentrates, aqueous suspensions, suspo-emulsions or capsule suspensions, emulsion concentrates, dispersion concentrates, soluble liquids, water dispersible granules, oil dispersions, emulsifiable concentrates, dispersible concentrates, wettable granules, preferably suspension concentrates, aqueous suspensions, suspo-emulsions and oil dispersions, where in the case of non-aqueous or solid formulations a sprayable formulation is obtained by adding water.

[0041] Suitable pesticide formulations to which the tank-mix additive according to the invention is added are insecticides, herbicides, fungicides, antimicrobials, host defense inducers, nutrient formulations, or safeners or biological agent formulations, and mixtures thereof, and any other suitable products delivered to plants by spray application.

[0042] Polymer-based drift reducing additives (a) Suitable drift reducing polymers are poly(ethylene oxide), preferably having an average molecular weight of 0.5 to 14 million g / mol, more preferably 0.75 to 10 million g / mol, and most preferably 1 to 8 million g / mol, and hydroxypropyl guar (HP guar).

[0043] In one embodiment, the polymeric drift reducing additive is poly(ethylene oxide) (PEO), wherein more preferably the tank-mix additive is PEO and exhibits a Polymer Concentration Factor (PCF) value of 0.5-12, more preferably 1-10, even more preferably 2-9.

[0044] The polymer concentration factor (PCF) for the PEO polymer content in the tank-mix additive is defined as follows, where C is the concentration of the drift-reducing polymer (a) in the tank-mix additive (g / L) and M is the molar mass of the drift-reducing polymer (a) (g / mol / 1×10 6 ), a is the value of 1.4, and D is the dose of tank-mix additive per hectare (L / ha). The PCF value is calculated from the following formula:

number

[0045] Oil-based drift reducing additive (b) Suitable drift reducing oils are vegetable oils and vegetable oil esters and diesters, including esters with glycerin and propylene glycol.

[0046] Particularly preferred are the methyl, ethyl, isopropyl, isobutyl, butyl, hexyl and ethylhexyl esters.

[0047] More preferably, the vegetable oils and esters are selected from the group consisting of methyl oleate, methyl palmitate, rapeseed oil methyl ester, isopropyl myristate, isopropyl palmitate, ethylhexyl palmitate, ethylhexyl oleate, ethylhexyl myristate / ethylhexyl laurate mixture, ethylhexyl laurate, ethylhexyl caprylate / ethylhexyl caprate mixture, diisopropyl adipate, coconut propylene glycol diester, sunflower oil, rapeseed oil, corn oil, soybean oil, rice bran oil, olive oil, peanut oil, mixed caprylic and capric triglycerides, and mixed decanoyl and octanoyl glycerides.

[0048] Particularly preferred are rapeseed oil, rapeseed oil methyl ester or sunflower oil.

[0049] Additionally, mineral oils are suitable as drift reducing agents.

[0050] Spreading agents and uptake enhancing additives (c): Some compounds suitable as spreading agents, due to their chemical properties, also act as uptake enhancing additives and vice versa, and therefore are grouped under compound (c).

[0051] A spreading agent is a compound that promotes the spreading of a tank-mix additive, or of a pesticide formulation containing the tank-mix additive, to plant parts, especially the leaves.

[0052] Suitable spreading agents are selected from the group comprising: mono- and diesters of metal sulfosuccinates with branched or linear alcohols containing 1 to 10 carbon atoms, especially the alkali metal salts, more especially the sodium salts, most especially sodium dioctyl sulfosuccinate; As well as organosilicon alkoxylates, for example organomodified polysiloxane / trisiloxane alkoxylates, preferably polyalkylene oxide modified heptamethyltrisiloxane, where the alkylene oxide is preferably selected from ethylene oxide (EO) or propylene oxide (PO), in particular the following: CAS No. 27306-78-1 (Poly(oxy-1,2-ethanediyl), alpha-methyl-omega-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-omega-hydroxy), CAS No. No. 134180-76-0 (oxirane, methyl-, oxirane-containing polymer, mono 3-1,3,3,3-tetramethyl-1-(trimethylsilyl)oxydisiloxanylpropyl ether), such as Silwet® L77, Silwet® 408, Silwet® 806, BreakThru® S240, BreakThru® S278.

[0053] Another suitable spreading agent is: Ethoxylated diacetylene-diols having 1 to 6 ethylene oxide (EO) units, such as Surfynol® 420 and 440; as well as alcohol alkoxylates, preferably selected from the group comprising ethoxylated or propoxy-ethoxylated alcohols, more preferably those containing from 6 to 22 carbon atoms and an average of 5 to 40 ethylene oxide (EO) and / or propylene oxide (PO) units, in particular Genapol® EP0244, Genapol® EP2584 or Synergen® W06 or 1-Hexanol, 3,5,5-trimethyl-, ethoxylated, propoxylated (CAS-No 204336-40-3), e.g. Break-Thru® Vibrant; and further alkyl polysaccharides such as Agnique® PG8107, PG8105 from BASF; Atplus® 438, AL-2559, AL-2575 from Croda.

[0054] The term "alcohol" in this context denotes an alcohol, which may be branched or straight-chain, saturated or unsaturated, having 6 to 22 carbon atoms, optionally bearing additional substituents such as OH groups.

[0055] Preferably, the spreading agent is selected from the group comprising metal sulfosuccinates and mono- and diesters of branched or linear alcohols containing 1-10 carbon atoms, organically modified polysiloxane / trisiloxane alkoxylates, ethoxylated diacetylenic diols having 1-6 ethylene oxide (EO) units, alcohol alkoxylates containing 6-22 carbon atoms, or alkyl polysaccharides; More preferably, they are selected from sodium dioctyl sulfosuccinate, polyalkylene oxide modified heptamethyltrisiloxane, ethoxylated diacetylenic diols having 1 to 6 EO units, or ethoxylated or propoxy-ethoxylated alcohols having 6 to 22 carbon atoms and an average of 5 to 40 ethylene oxide (EO) and / or propylene oxide (PO) units; and, in particular, selected from the group comprising sodium dioctyl sulfosuccinate, polyalkylene oxide modified heptamethyltrisiloxane and ethoxylated diacetylenic diols having 1 to 6 ethylene oxide units.

[0056] In a further preferred embodiment of the present invention, the spreading agent (c) is selected from the group comprising polyalkylene oxide-modified heptamethyltrisiloxane, dioctyl sulfosuccinate, alcohol ethoxylates and ethoxylated diacetylenic diols having an EO of 1 to 6, more preferably selected from the group comprising polyalkylene oxide-modified heptamethyltrisiloxane, dioctyl sulfosuccinate and ethoxylated diacetylenic diols having an EO of 1 to 6.

[0057] An uptake-enhancing additive is a compound that enhances the uptake of the tank-mix additive or an agrochemical formulation containing the tank-mix additive into plants or plant parts, particularly the leaves.

[0058] Suitable uptake enhancing additives are alcohol alkoxylates, preferably alcohol alkoxylates selected from the group including: ethoxylated alcohols or propoxy-ethoxylated alcohols, more preferably those containing from 6 to 22 carbon atoms and an average of 5 to 40 ethylene oxide (EO) and / or propylene oxide (PO) units; ethoxylated carboxylic acids or propoxyl-ethoxylated carboxylic acids, preferably containing from 6 to 22 carbon atoms and an average of 5 to 40 ethylene oxide (EO) and / or propylene oxide (PO) units; Or ethoxylated mono-, di-, or triesters of glycerin containing fatty acids having 8 to 18 carbon atoms and an average of 5 to 60 (preferably 5 to 40) EO units.

[0059] The ethoxylated or propoxy-ethoxylated alcohols or carboxylic acids may optionally be further modified by adding a methyl radical to the remaining alcohol functionality (cf. "Me end-capping").

[0060] Further suitable uptake enhancing additives are selected from the following: alkoxylated sorbitan fatty acid esters containing fatty acids having 8 to 18 carbon atoms and an average of 10 to 50 ethylene oxide and propylene oxide units; or ethoxylated coconut alcohol containing 2-20 EO units; or castor oil ethoxylates containing an average of 5 to 40 EO units.

[0061] The term "alcohol" in this context denotes an alcohol, which may be branched or straight-chained, saturated or unsaturated, having 6 to 22 carbon atoms, optionally bearing additional substituents such as OH groups. The term "carboxylic acid" in this context denotes a carboxylic acid, which may be branched or straight-chained, saturated or unsaturated, having 6 to 22 carbon atoms, optionally bearing additional substituents such as OH groups.

[0062] Preferably, the uptake enhancing additive (c) is selected from the group comprising alcohol alkoxylates containing 6 to 22 carbon atoms, ethoxylated or propoxy-ethoxylated carboxylic acids containing 6 to 22 carbon atoms, ethoxylated mono-, di- or triesters of glycerin containing fatty acids having 8 to 18 carbon atoms and an average of 5 to 60 EO units, alkoxylated sorbitan fatty acid esters containing fatty acids having 8 to 18 carbon atoms and an average of 10 to 50 ethylene oxide and propylene oxide units, ethoxylated coconut alcohol containing 2 to 20 EO units or castor oil ethoxylates containing an average of 5 to 40 EO units; More preferably, they are selected from ethoxylated or propoxy-ethoxylated alcohols containing from 6 to 22 carbon atoms and an average of 5 to 40 ethylene oxide (EO) and / or propylene oxide (PO) units, ethoxylated or propoxy-ethoxylated carboxylic acids containing from 6 to 22 carbon atoms and an average of 5 to 40 ethylene oxide (EO) and / or propylene oxide (PO) units, ethoxylated mono-, di- or triesters of glycerin containing fatty acids having from 8 to 18 carbon atoms and an average of 5 to 60 EO units, or alkoxylated sorbitan fatty acid esters containing fatty acids having from 8 to 18 carbon atoms and an average of 10 to 50 ethylene oxide and propylene oxide units, ethoxylated coconut alcohol containing from 2 to 20 EO units, or castor oil ethoxylates containing an average of 5 to 40 EO units; and in particular from the group of ethoxylated or propoxy-ethoxylated alcohols containing from 6 to 22 carbon atoms and an average of 5 to 40 ethylene oxide (EO) and / or propylene oxide (PO) units, ethoxylated or propoxy-ethoxylated carboxylic acids containing from 6 to 22 carbon atoms and an average of 5 to 40 ethylene oxide (EO) and / or propylene oxide (PO) units, ethoxylated mono-, di- or triesters of glycerol containing fatty acids having from 8 to 18 carbon atoms and an average of 5 to 60 ethylene oxide units, alkoxylated sorbitan fatty acid esters containing fatty acids having from 8 to 18 carbon atoms and an average of 10 to 50 ethylene oxide and propylene oxide units.

[0063] In a further preferred embodiment of the invention, the uptake enhancer (c) is selected from the group comprising ethoxylated alcohols, propoxylated ethoxylated alcohols, ethoxylated carboxylic acids, propoxy-ethoxylated carboxylic acids, or ethoxylated mono-, di- or triesters of glycerin containing fatty acids having 8 to 18 carbon atoms and an average of 5 to 40 EO units, alkoxylated sorbitan fatty acid esters containing fatty acids having 8 to 18 carbon atoms and an average of 10 to 50 EO and PO units.

[0064] Suitable components (c) are, by way of example, the following: * ethoxylated linear and / or branched fatty alcohols containing 2 to 20 EO units (for example, Genapol® X type from Clariant); * Methyl end-capped ethoxylated linear and / or branched fatty alcohols containing 2-20 EO units (e.g., Genapol® XM type from Clariant); * Ethoxylated coconut alcohol containing 2 to 20 EO units (e.g. Genapol® C type from Clariant); * Ethoxylated C12 / 15 alcohols containing 2 to 20 EO units (e.g. Synperonic® A type from Croda); * Propoxy-ethoxylated alcohols, branched or linear, such as Antarox® B / 848 from Solvay, Atlas® G5000 from Croda, Lucramul® HOT5902 from Levaco; * Propoxy-ethoxylated fatty acids, Me end capped, e.g., Leofat® OC0503M from Lion; * alkyl ether citrate surfactants (e.g. Adsee CE range, Akzo Nobel); * Alkyl polysaccharides (e.g. Agnique® PG8107, PG8105 from BASF; Atplus® 438, AL-2559, AL-2575 from Croda); * ethoxylated mono- or diesters of glycerin containing fatty acids having 8 to 18 carbon atoms and an average of 10 to 60 (preferably 10 to 40) EO units (e.g. Crovol® product range from Croda); * Castor oil ethoxylates containing an average of 5 to 40 EO units (e.g. Berol® range from Nouryon, Emulsogen® EL range from Clariant); * Ethoxylated oleic acids containing 2 to 20 EO units (e.g. Alkamuls® A and AP); * Alkoxylated sorbitan fatty acid esters containing fatty acids with 8 to 18 carbon atoms and an average of 10 to 50 EO and / or PO units (eg Arlatone® T, Tween range).

[0065] Other formulation aids (d): In the context of the present invention, other formulation auxiliaries (d) are further additives which are usually used in agrochemical formulations and which are not included in components (a) to (c).

[0066] Preferably, the other formulation auxiliaries are one or more substances selected from rain resistance additives, surfactants, rheology modifiers, antifoaming substances, antifreeze agents, preservatives, biocides, colorants, pH adjusters, buffers, stabilizers, antioxidants, inert fillers, wetting agents, crystal growth inhibitors or micronutrients.

[0067] (d1) Weather resistance additive: Suitable weatherproofing additives are acrylic emulsion polymers or polymer dispersions and styrene emulsion polymers or polymer dispersions (d), which are aqueous polymer dispersions having a Tg in the range of -100°C to 30°C, preferably -60°C to 20°C, more preferably -50°C to 10°C, most preferably -45°C to 5°C, such as Acronal V215, Acronal 3612, Licomer ADH205 and Atplus FA. Particularly preferred are Licomer ADH205 and Atplus FA.

[0068] Preferably, the polymer is selected from the group consisting of acrylic polymers, styrene polymers, vinyl polymers and their derivatives, polyolefins, polyurethanes and natural polymers and their derivatives.

[0069] More preferably, the polymer is selected from the group consisting of acrylic polymers, styrene butadiene copolymers, styrene-maleic anhydride copolymers, polyvinyl alcohol, polyvinyl acetate, partially hydrolyzed polyvinyl acetate, methyl vinyl ether-maleic anhydride copolymers, carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, and silicone-modified polyvinyl alcohol, isopropylene-maleic anhydride copolymers, polyurethanes, cellulose, gelatin, casein, oxidized starch, starch-vinyl acetate graft copolymers, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, and acetyl cellulose.

[0070] Most preferably, the polymer is selected from copolymers of acrylates and styrene, the acrylates being selected from the list comprising 2-ethyl-hexyl acrylate, butyl acrylate, sec-butyl acrylate, ethyl acrylate, methyl acrylate, acrylic acid, acrylamide, iso-butyl acrylate, methyl methacrylate or combinations thereof, and the styrenes being selected from the list comprising styrene, tert-butyl styrene, para-methyl styrene or combinations thereof.

[0071] In a preferred embodiment, the above described polymers have a molecular weight of less than or equal to 40000 g / mol, preferably less than or equal to 10000 g / mol.

[0072] In a preferred embodiment, the polymer d is an emulsion polymer as described in WO2017 / 202684.

[0073] Glass transition temperatures (Tg) are known for many polymers and, unless otherwise defined herein, are measured according to ASTM E1356-08(2014) "Standard Test Method for Assignment of the Glass Transition Temperatures by Differential Scanning Calorimetry" where samples are dried at 110°C for 1 hour prior to DSC to remove water and / or solvent effects, DSC sample size is 10-15 mg, and run from -100°C to 100°C at 20°C / min under N2. Tg is defined as the midpoint of the transition region.

[0074] (d2) Surfactant: Suitable nonionic surfactants or dispersants are all substances of this type that can be conventionally used in agrochemicals. Preferably, polyethylene oxide-polypropylene oxide block copolymers (preferably with a molecular weight of more than 5000 g / mol or a polyethylene oxide content of more than 35%, more preferably with a molecular weight of more than 6000 g / mol and a polyethylene oxide content of more than 45%), polyoxyalkyleneamine derivatives, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinylpyrrolidone, and copolymers of (meth)acrylic acid and (meth)acrylic acid esters. Of the above examples, selected classes may optionally be phosphorylated, sulfonated or sulfated and neutralized with bases.

[0075] Possible anionic surfactants are all substances of this type that can be conventionally used in agrochemicals.Preference is given to the alkali metal, alkaline earth metal and ammonium salts of alkylsulfonic or alkylphosphoric acids, as well as alkylarylsulfonic or alkylarylphosphoric acids.Further preferred groups of anionic surfactants or dispersants are the alkali metal, alkaline earth metal and ammonium salts of polystyrenesulfonic acid, the salts of polyvinylsulfonic acid, the salts of alkylnaphthalenesulfonic acids, the salts of naphthalene-sulfonic acid-formaldehyde condensation products, the salts of naphthalenesulfonic acid, phenolsulfonic acid and formaldehyde condensation products, and the salts of lignosulfonic acid.

[0076] (d3) Rheology modifier: Rheology modifiers are additives that provide a substantial increase in viscosity at low shear rates when added to a formulation at a concentration that reduces gravitational separation of dispersed active ingredients during storage. For purposes of this invention, low shear rates are defined as rates below 0.1 s -1 A substantial increase is defined as greater than a factor of 2. The viscosity can be measured with a rotational shear rheometer.

[0077] Suitable rheology modifiers (d3) are, by way of example, * Polysaccharides including xanthan gum and hydroxyethylcellulose, examples of which are Kelzan®, Rhodopol® G and 23, Satiaxane® CX911, and Natrosol® 250 range; * Clays including montmorillonite, bentonite, sepiolite, attapulgite, laponite, hectorite, examples of which are Veegum® R, VanGel® B, Bentone® 34, 38, CT, HC, EW, Pangel® M100, M200, M300, S, M, W, Attagel® 50, Laponite® RD; * Fumed and precipitated silicas, examples of which are Aerosil® 200, Sipernat® 22; *Microcrystalline cellulose.

[0078] Preferred are xanthan gum, montmorillonite clay, bentonite clay and fumed silica.

[0079] (d4) Antifoaming substances: Suitable antifoaming substances (d4) are all substances that are conventionally usable in agrochemicals for this purpose. Silicone oils and silicone oil preparations are preferred. Examples are Silcolapse® 426 and 432 from Bluestar Silicones, Silfoam® SRE and SC132 from Wacker, SAF-184® from Silchem, Foam-Clear ArraPro-S® from Basildon Chemical Company Ltd, SAG® 1572 and SAG® 30 from Momentive (dimethylsiloxanes and silicones, CAS No. 63148-62-9). Preferred is SAG® 1572.

[0080] (d5) Antifreeze: Suitable antifreeze agents are all substances which are customarily usable for this purpose in agrochemicals. Suitable examples are propylene glycol, ethylene glycol, urea and glycerin.

[0081] (d6) Further formulation auxiliaries: Suitable further formulation auxiliaries (d6) are selected from preservatives, biocides, colorants, pH regulators, buffers, stabilizers, antioxidants, inert filler substances, humectants, crystal growth inhibitors, micronutrients.

[0082] Examples of these are:

[0083] Possible preservatives are all substances that are customarily usable in pesticides for this purpose.Suitable examples of preservatives are preparations that contain 5-chloro-2-methyl-4-isothiazolin-3-one [CAS-No. 26172-55-4], 2-methyl-4-isothiazolin-3-one [CAS-No. 2682-20-4] or 1,2-benzisothiazol-3(2H)-one [CAS-No. 2634-33-5].Examples that may be mentioned are Preventol® D7 (Lanxess), Kathon® CG / ICP (Dow), Acticide® SPX (Thor GmbH) and Proxel® GXL (Arch Chemicals).

[0084] Possible colorants are all substances which can be customarily used in agrochemicals for this purpose: titanium dioxide, carbon black, zinc oxide, blue pigments, Brilliant Blue FCF, red pigments and Permanent Red FGR may be mentioned by way of example.

[0085] Possible pH regulators and buffers are all substances customarily usable in pesticides for this purpose: citric acid, sulfuric acid, hydrochloric acid, sodium hydroxide, sodium hydrogen phosphate (Na2HPO4), sodium dihydrogen phosphate (NaH2PO4), potassium dihydrogen phosphate (KH2PO4), potassium dihydrogen phosphate (K2HPO4) may be mentioned as examples.

[0086] Suitable stabilizers and antioxidants are all substances which can be customarily used in agrochemicals for this purpose. Butylhydroxytoluene [3,5-di-tert-butyl-4-hydroxytoluene, CAS No. 128-37-0] is preferred.

[0087] Carrier (e) are carriers that can be customarily used for this purpose in pesticide formulations.

[0088] Carrieris a solid or liquid natural or synthetic organic or inorganic substance that is generally inert and can be used as a solvent. The carrier generally improves the application of the compound, for example, to plants, plant parts or seeds. Examples of suitable solid carriers include, but are not limited to, ammonium salts, especially ammonium sulfate, ammonium phosphate and ammonium nitrate, natural rock powders such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth, silica gel, and synthetic rock powders such as micronized silica, alumina and silicates. Examples of typically useful solid carriers for preparing granules include, but are not limited to, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, synthetic granules made of inorganic and organic powders, and granules made of organic materials such as paper, sawdust, coconut shells, corn cobs and tobacco stems.

[0089] Preferred solid supports are selected from clays, talcs and silicas.

[0090] Examples of suitable liquid carriers include, but are not limited to, water, organic solvents, and combinations thereof. Examples of suitable solvents include polar and non-polar organochemical liquids, such as those selected from the following classes: * alcohols and polyols (which may optionally be substituted, etherified and / or esterified; for example ethanol, propanol, butanol, benzyl alcohol, cyclohexanol or glycol, 2-ethylhexanol); * Ethers, such as dioctyl ether, tetrahydrofuran, dimethyl isosorbide, solketal, cyclopentyl methyl ether, solvents offered by Dow in the "Dowanol Product Range", such as Dowanol DPM, anisole, phenetole, various molecular weight grades of dimethyl polyethylene glycol (less than 1000 g / mol), various molecular weight grades of dimethyl polypropylene glycol (less than 1000 g / mol), dibenzyl ether; * Ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, acetophenone, propiophenone); * Lactic acid esters, for example, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-ethylhexyl lactate; * Unsubstituted and substituted amines; * amides (for example dimethylformamide or N,N-dimethyl lactamide or N-formylmorpholine or fatty acid amides such as N,N-dimethyl decanamide or N,N-dimethyl dec-9-enamide) and their esters; * lactams (for example 2-pyrrolidone or N-alkylpyrrolidones, for example N-methylpyrrolidone or N-butylpyrrolidone or N-octylpyrrolidone or N-dodecylpyrrolidone or N-methylcaprolactam, N-alkylcaprolactam); * Lactones (e.g., gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, or alpha-methyl gamma-butyrolactone); * Sulfones and sulfoxides (e.g., dimethyl sulfoxide); * nitriles (for example linear or cyclic alkyl nitriles, in particular acetonitrile, cyclohexanecarbonitrile, octanonitrile, dodecanonitrile); * Linear and cyclic carbonates, such as diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dioctyl carbonate, or ethylene carbonate, propylene carbonate, butylene carbonate, carbonate.

[0091] The most preferred carrier is water.

[0092] By means of the tank-mix additives according to the invention it is possible to deliver pesticidal active substances to plants and / or their habitat in a particularly advantageous manner.

[0093] The present invention is further directed to the use of a pesticide formulation comprising a tank-mix additive according to the invention for applying the pesticidal active compounds contained therein to plants and / or their habitat.

[0094] The tank mix additive of the present invention can be used to treat all plants and plant parts. By plants, we mean all plants and plant populations, such as desirable and undesirable wild plants or crop plants, including naturally occurring crop plants. Crop plants can be plants that can be obtained by conventional breeding and optimization methods, or by biotechnological and genetic engineering methods, or by a combination of these methods. Such crop plants also include transgenic plants, and also include plant varieties that can and cannot be protected by proprietary rights. Plant parts mean all above-ground and below-ground parts and all organs of a plant, such as shoots, leaves, flowers and roots, an exemplary list of which includes leaves, needles, stems, trunks, flowers, fruiting bodies, fruits and seeds, and also roots, tubers and rhizomes. Plant parts also include harvested material, and also vegetative and generative propagation material.

[0095] The application rates of the tank-mix additives according to the invention can vary within relatively wide limits, guided by the particular active pesticides and their amounts in the pesticide formulation.

[0096] A further aspect of the present invention is the use of a tank-mix additive according to the present invention in the application of a pesticidal compound to control pests, wherein a formulation or spray containing the tank-mix additive is applied by an unmanned aerial vehicle UAV or an unmanned guided vehicle UGV, or by a spray nozzle device using pulse width modulation PWM.

[0097] The formulation or spray containing the tank-mix additive is applied by conventional methods, i.e., for example, by spraying, pouring or injection, in particular by spraying, most particularly by spraying with an unmanned aerial vehicle (UAV) or an unmanned guided vehicle (UGV), or by a spray nozzle device using pulse width modulation (PWM).

[0098] drawing FIG. 1 shows the % spray droplet size <100 microns for different spray volumes for the formulation in Example 1.

[0099] FIG. 2 shows the % spray droplet size <100 microns for different spray volumes for the formulation in Example 2.

[0100] FIG. 3 shows the % spray droplet size <100 microns for different spray volumes for the formulation in Example 3.

[0101] FIG. 4 shows the percent dispensed droplet size <100 microns for example polymer 1 versus different PEO polymer molar masses and concentrations.

[0102] FIG. 5 shows the % dispensed droplet size <100 microns for different PEO polymer molar masses and PCF values ​​for Example Polymer 2.

[0103] Table of Materials material [Table 1] [Table 2] TIFF2025515158000004.tif33160 [Table 3] TIFF2025515158000006.tif79163 [Table 4] [Table 5] [Table 6] TIFF2025515158000010.tif205168 Experimental Method Method 1: How to prepare a tank-mix additive Methods for preparing liquid tank-mix compositions are known in the art and may be prepared by known methods familiar to those skilled in the art.

[0104] A 1-4% solution of the drift-reducing polymer (a) was prepared by mixing the polymer in glycerin (25%) and pouring the mixture into water (up to 100%) with stirring until homogeneous. A 50% oil-in-water emulsion of drift-reducing oil (b) was prepared by adding the oil (50%) to a solution of water (49%) and Synperonic PE / F127 (1%) under high shear mixing (Ultra-Turrax®) to achieve a droplet size (Dv50) of 1-4 microns. Other formulation aids (d), spreading agents and / or uptake enhancing additives (c) were mixed with the remaining water with stirring, followed by mixing the above prepared polymer (a) solution and the above prepared 50% oil (b) emulsion with low shear stirring until homogeneous. Additional water (e) was added as necessary to reach the final volume. Finally, the pH was adjusted with acid or base (d) as required.

[0105] Polymer (a) solutions are prepared according to the viscosity concentration limits and contents required in the formulation. Typical values ​​are as follows: Polyox WSR301 (1-2%), Polyox WSR N60K (1-3%), Polyox WSR N12K (2-4%), AgRho DR2000 (1-2%).

[0106] Method 2: Measuring the spray droplet size P15 The composition was diluted with water (deionized water) to the required concentration and sprayed through a TeeJet® TP8002EVS nozzle at a pressure of 3 bar, and the droplet size spectrum was measured using an Oxford Lasers VisiSize P15, which captures images of the sprayed droplets to measure their size. The spray nozzle was positioned 20 cm above the image capture point and moved slowly with a motorized slider across the image capture window of the VisiSize P15, thereby ensuring that the full width of the spray fan was measured. A minimum of 5000-10000 droplet images were acquired. The droplet size spectrum was calculated by the instrument software as the volume % below 100 microns and the volume % below 150 microns, which are generally considered to be the drift-prone portion of the sprayed droplets.

[0107] -------------------------------------- EXAMPLES

[0108] Working Example Example 1 [Table 7] Physical Aspects The physical aspects relating to viscosity were assessed visually. [Table 8] The above results indicate that the polymer Polyox® WSR N12K can be incorporated into adjuvant tank-mix formulations at concentrations between 2 and 12 g / L without unduly increasing the viscosity of the resulting samples.

[0109] Droplet size The spray droplet size was measured according to Method 2. [Table 9] The results show that the combination of the polymer Polyox® WSR N12K (PEO 1 million) with rapeseed oil is able to reduce the driftable fraction of spray droplets less than 100 microns or less than 150 microns over the range of spray volumes from 5 to 1000 L / ha (see FIG. 1). The polymer alone is only able to reduce the driftable fraction of spray droplets at low spray volumes, whereas the oil alone is only able to reduce the driftable fraction of spray droplets at high spray volumes, and only the combination of both is effective at both low and high spray volumes. Furthermore, the amount of polymer Polyox® WSR N12K is important, with 2 g / L, corresponding to 1 g / ha, being less effective compared to 8 g / L and 12 g / L, corresponding to 4 g / ha and 6 g / ha. It is also surprising how small the amounts of polymer Polyox® WSR N12K and rapeseed oil required to reduce the driftable fraction of the spray droplets are, far below the typical use rates (g / ha) of these materials. [Table 10] Example 2 [Table 11] Physical Aspects The physical aspects relating to viscosity were assessed visually. [Table 12] The above results indicate that the polymer Polyox® WSR301 can be incorporated into adjuvant tank-mix formulations at concentrations of 1-4 g / L without unduly increasing the viscosity of the resulting samples.

[0110] Droplet size The spray droplet size was measured according to Method 2. [Table 13] The results show that the combination of polymer Polyox® WSR301 (PEO 4 million) and rapeseed oil methyl ester is able to reduce the driftable fraction of spray droplets less than 100 or 150 microns over a range of spray volumes from 5 to 1000 L / ha (see FIG. 2). Moreover, the amount of polymer Polyox® WSR301 in the formulation is important, with 1 g / L, corresponding to 0.5 g / ha, being less effective compared to 2.2 g / L and 4 g / L, corresponding to 1.1 g / ha and 2 g / ha. Moreover, it is surprising how little the amount of polymer Polyox® WSR301 and rapeseed oil methyl ester needed to reduce the driftable fraction of spray droplets is, far below the typical use rates (g / ha) of these materials. [Table 14] Example 3 [Table 15] Physical Aspects The physical aspects relating to viscosity were assessed visually. [Table 16] The above results show that the polymer Polyox® WSR N60K can be incorporated into a tank-mix adjuvant formulation at a concentration of 4.4 g / L without unduly increasing the viscosity of the resulting sample.

[0111] Droplet size The spray droplet size was measured according to Method 2. [Table 17] The above results show that the combination of the polymer Polyox® WSR N60K and sunflower oil is able to reduce the driftable fraction of spray droplets less than 100 microns or less than 150 microns over a range of spray volumes from 5 to 200 L / ha (see FIG. 3). Moreover, it is surprising how little the amount of polymer Polyox® WSR N60K (2.2 g / ha) and sunflower oil (10 g / ha) required to reduce the driftable fraction of spray droplets is, which is far below the typical use rates (g / ha) of these materials. [Table 18] Example Polymer 1: [Table 19] These results show that many high molecular weight (molar mass) polymers have little or no effect in reducing the driftable fraction of the sprayed droplets. However, the effect of poly(ethylene oxide) (PEO) is clear and shows the strongest effect here. Furthermore, AgRho® DR2000 (HP Guar) also stands out in its effect in reducing the driftable fraction of the sprayed droplets.

[0112] For k-carrageenan and xanthan polymers, a limited reduction in the driftable fraction of the spray droplet is observed, but so much polymer is needed in the formulation to achieve a significant reduction in the driftable fraction of the spray droplet that the tank-mix formulation at such a level is too viscous to be poured from a bottle and easily dispersed in the spray liquid.

[0113] Example Polymer 2: [Table 20] The results in Table P2.1 show that the molar mass (molecular weight) of the PEO Polyox polymer has a large effect on the fraction of the droplet that can drift, with a 4 million molar mass PEO having a much stronger effect than a 2 million molar mass PEO, which in turn has a stronger effect than a 1 million molar mass PEO. This is plotted in Figure 4.

[0114] To account for this effect, the polymer concentration factor (PCF) for the PEO polymer content in the tank-mix additive is defined as follows, where C is the concentration of the drift-reducing polymer (a) in the tank-mix additive (g / L) and M is the molar mass of the drift-reducing polymer (a) (g / mol / 1×10 6 ), a is the value of 1.4, and D is the dose of tank-mix additive per hectare (L / ha). The PCF value is calculated from the following formula:

number

Claims

1. A tank mix additive for pesticide formulations, (a) One or more polymer-based drift-reducing additives selected from the group consisting of poly(ethylene oxide) and hydroxypropylated guar; (b) One or more oil-based drift-reducing additives; (c) One or more spreading agents and / or uptake-promoting additives; (d) Other pharmaceutical adjuvants; (e) one or more carriers up to a predetermined volume, at least one of which is water; (a) is present in concentrations of 0.2 to 50 g / L; (b) is present in concentrations of 0.5 to 45 g / L; (c) is present in concentrations of 10 to 200 g / L; (d) is present in concentrations of 20–300 g / L; A tank mix additive characterized by the following features.

2. (a) is present in concentrations of 1 to 15 g / L; (b) is present in concentrations of 5 to 25 g / L; (c) is present in concentrations of 25–140 g / L; (d) is present at concentrations of 30–135 g / L; (e) A carrier up to a predetermined volume; The tank mix additive for the pesticide formulation according to claim 1.

3. (a) is preferably selected from the group comprising poly(ethylene oxide) having an average molecular weight of 0.5 to 14 million g / mol, more preferably 0.75 to 10 million g / mol, and most preferably 1 to 8 million g / mol, the tank mix additive for the pesticide formulation according to claim 1 or 2.

4. The tank mix additive for an agrochemical formulation according to claim 3, wherein the formulation has a polymer concentration coefficient (PCF) of 1 to 10.

5. The polymer concentration coefficient (PCF) for the PEO polymer content in the aforementioned tank mix additive is given by the following formula: [Math 1] The tank mix additive according to claim 4, wherein C is the concentration (g / L) of the drift-reducing polymer (a) in the tank mix additive, M is the molar mass (g / mol / 1 × 10⁶) of the drift-reducing polymer (a), a is a value of 1.4, and D is the amount of the tank mix additive per hectare (L / ha).

6. (b) is selected from the group comprising vegetable oils and vegetable oil esters and diesters, which include esters with glycerin and propylene glycol, according to claim 1 or 2, as a tank mix additive for a pesticide formulation.

7. The tank mix additive for an agrochemical formulation according to claim 1 or 2, wherein the spreading agent (c) is selected from sodium dioctyl sulfosuccinate, polyalkylene oxide-modified heptamethyltrisiloxane, ethoxylated diacetylenediol having 1 to 6 ethylene oxide units, or ethoxylated alcohol or propoxy-ethoxylated alcohol having 6 to 22 carbon atoms and an average of 5 to 40 ethylene oxide units and / or propylene oxide units, and preferably selected from sodium dioctyl sulfosuccinate, polyalkylene oxide-modified heptamethyltrisiloxane, and ethoxylated diacetylenediol having 1 to 6 ethylene oxide units.

8. The uptake-promoting additive (c) is selected from the group comprising: alcohol alkoxylates containing 6 to 22 carbon atoms; ethoxylated carboxylic acids or propoxyethoxylated carboxylic acids containing 6 to 22 carbon atoms; ethoxylated mono-, di-, or triesters of glycerin containing 8 to 18 carbon atoms and an average of 5 to 60 ethylene oxide units; alkoxylated sorbitan fatty acid esters containing 8 to 18 carbon atoms and an average of 10 to 50 ethylene oxide and propylene oxide units; ethoxylated coconut alcohol containing 2 to 20 ethylene oxide units; or castor oil ethoxylates containing an average of 5 to 40 ethylene oxide units, preferably containing 6 to 22 carbon atoms. A tank mix additive for a pesticide formulation according to claim 1 or 2, selected from ethoxylated alcohols or propoxyethoxylated alcohols containing carbon atoms and an average of 5 to 40 ethylene oxide and / or propylene oxide units; ethoxylated carboxylic acids or propoxyethoxylated carboxylic acids containing 6 to 22 carbon atoms and an average of 5 to 40 ethylene oxide and / or propylene oxide units; ethoxylated mono-, di-, or triesters of glycerin containing a fatty acid having 8 to 18 carbon atoms and an average of 5 to 60 ethylene oxide units; and alkoxylated sorbitan fatty acid esters containing a fatty acid having 8 to 18 carbon atoms and an average of 10 to 50 ethylene oxide and propylene oxide units.

9. The tank mix additive for a pesticide formulation according to claim 1 or 2, wherein the other formulation aid (d) is one or more substances selected from rainproofing additives, surfactants, rheology modifiers, defoaming substances, antifreezes, preservatives, biocides, colorants, pH adjusters, buffers, stabilizers, antioxidants, inert fillers, wetting agents, crystal growth inhibitors, or micronutrients.

10. The tank mix additive for a pesticide formulation according to claim 1 or 2, wherein the ratio of (a) to (b) in the tank mix additive is 1:40 to 10:1, more preferably 1:10 to 5:1, and most preferably 1:6 to 2:

1.

11. The tank mix additive for a pesticide formulation according to claim 1 or 2, wherein the ratio of (a), (b), and (c) in the tank mix additive is 1:40:150 to 10:1:10, more preferably 1:12:120 to 2:1:5, and most preferably 1:8:50 to 1:2:

5.

12. A method for applying the pesticide tank mix additive described in claim 1 or 2 to a crop, wherein the tank mix additive is applied at a spray volume of 1 L / ha to 2000 L / ha, preferably 5 L / ha to 1500 L / ha, and more preferably 8 L / ha to 1200 L / ha.

13. A method for applying the pesticide tank mix additive composition described in claim 1 or 2 to a crop, wherein the tank mix additive is applied at a spray volume of 1 L / ha to 25 L / ha, preferably 2 L / ha to 20 L / ha, and more preferably 5 L / ha to 15 L / ha.

14. In the agricultural plots, (a) in an amount of 0.5 to 15 g / ha, more preferably 1 to 12 g / ha, most preferably 1 to 10 g / ha, and (b) in amounts of 0.5 to 40 g / ha, more preferably 1 to 20 g / ha, most preferably 2 to 10 g / ha, and (c) in an amount of 10 to 200 g / ha, more preferably 15 to 160 g / ha, and most preferably 20 to 100 g / ha. Use of the tank mix additive according to claim 1 or 2 for delivering [the specified substance].

15. In the use of the tank mix additive according to claim 1 or 2 in the application of a pesticide compound for controlling harmful organisms, wherein the formulation or spray solution containing the tank mix additive is applied by an unmanned aerial vehicle (UAV) or unmanned guided vehicle (UGV), or by a spray nozzle device using pulse width modulation (PWM).

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