HIGH SPREADING ULV FORMULATIONS FOR AGROCHEMICAL COMPOUNDS II

Abstract

The present invention relates to agrochemical compositions: their use for foliar application; their use at low spray volumes; their use by unmanned aerial systems (UAS), unmanned guided vehicles (UGV), and tractor mounted boom sprayers fitted with conventional nozzles but also pulse width modulation spray nozzles or rotating disc droplet applicators; and their application for controlling agricultural pests, weeds or diseases, in particular on waxy leaves.

Claims

1: An agrochemical formulation comprising a) one or more active ingredients, b) one or more spreading agents, c) other formulants, d) one or more carriers to volume, wherein b) is present in an amount from 5 to 200 g/l.

2: An agrochemical formulation according to claim 1, wherein b) is selected from the group consisting of mono- and diesters of sulfosuccinate metal salts with branched or linear alcohols comprising 1-10 carbon atoms, in particular alkali metal salts, more particularly sodium salts, ethoxylated diacetylene-diols with 1 to 6 EO, and alcohol ethoxylates.

3: An agrochemical formulation according to claim 1, wherein b) is selected from the group consisting of dioctylsulfosuccinate sodium and ethoxylated diacetylene-diols with 1 to 6 EO.

4: An agrochemical according to claim 1, wherein a) is present in an amount from 5 to 300 g/l, preferably from 10 to 280 g/l, and most preferably from 10 to 250 g/l.

5: An agrochemical formulation according to claim 1 wherein b) is present in 5 to 200 g/l, preferably from 10 to 150 g/l, and most preferred from 10 to 130 g/l.

6: An agrochemical formulation according to claim 1, wherein c) is present in an amount from 4 to 250 g/l, preferably from 8 to 120 g/l, and most preferably from 10 to 80 g/1.

7: An agrochemical formulation according to claim 1, wherein the active ingredient is selected from the group consisting of fluopicolide, fluopyram, fluoxapiprolin, inpyrfluxam, isoflucypram, clothianidin, beta-cyfluthrin, deltamethrin, ethiprole, fipronil, flubendiamide, imidacloprid, spidoxamate, spiromesifen, spirotetramat, tetraniliprole, thiacloprid, tembotrione, triafamone, and isoxadifen-ethyl.

8: An agrochemical formulation according to claim 1, wherein component c) comprises at least one non-ionic surfactant and/or ionic surfactant (c1), one rheological modifier (c2), one antifoam substance (c3) and at least one antifreeze agent (c4).

9: An agrochemical formulation according to claim 1, comprising the components a) to e) in the following amounts a) from 5 to 300 g/l, preferably from 10 to 280 g/l, and most preferred from 10 to 250 g/l, b) from 5 to 200 g/l, preferably from 10 to 150 g/l, and most preferably from 10 to 130 g/l, c1) from 4 to 250 g/l, preferably from 8 to 120 g/l, and most preferably from 10 to 80 g/l, c2) from 0 to 60 g/l, preferably from 1 to 20 g/l, and most preferably from 2 to 10 g/l, c3) from 0 to 30 g/l, preferably from 0.5 to 20 g/l, and most preferably from 1 to 12 g/l, c4) from 0 to 200 g/l, preferably from 5 to 150 g/l, and most preferably from 10 to 120 g/l, c5) from 0 to 200 g/l, preferably from 0.1 to 120 g/l, and most preferably from 0.5 to 80 g/l, d) carrier to volume.

10: An agrochemical formulation according to claim 1, wherein the formulation is applied at a spray volume of between 1 and 20 l/ha, preferably 2 and 15 l/ha, more preferably 5 and 15 l/ha.

11: A method of applying the agrochemical composition according to claim 1, onto crops, wherein the formulation is applied at a spray volume of between 1 and 20 l/ha, preferably 2 and 15 l/ha, and more preferably 5 and 15 l/ha.

12: The method according to claim 11, wherein the applied amount of a) to the crop is between 2 and 150 g/ha, preferably between 5 and 120 g/ha, and more preferred between 20 and 200 g/ha.

13: The method according to claim 11, wherein the spreading agent b) is preferably applied from 5 g/ha to 150 g/ha, more preferably from 7.5 g/ha to 100 g/ha, and most preferably from 10 g/ha to 60 g/ha.

14: The method according to claim 11, wherein the formulation is applied on plants or crops with textured leaf surfaces.

15: A method of controlling harmful organisms, comprising applying the agrochemical formulation according to claim 1, wherein the formulation is applied by an unmanned aerial vehicle (UAV), an unmanned guided vehicle (UGV), or a pulse-width-module (PWM).

16: A method of controlling harmful organisms, comprising contacting the harmful organisms, their habitat, their hosts, such as plants and seed, and the soil, the area and the environment in which they grow or could grow, but also comprising contacting materials, plants, seeds, soil, surfaces or spaces which are to be protected from attack or infestation by organisms that are harmful to plants, with an effective amount of the agrochemical formulation according to claim 1, wherein the formulation is applied by an unmanned aerial vehicle (UAV), an unmanned guided vehicle (UGV), or a pulse-width-module (PWM).

Description

FIGURES

[0243] FIG. 1 shows scanning electron micrographs of leaf surface textures, wherein the upper picture shows a grapevine leaf surface (untextured) and the lower picture shows a soybean leaf surface (textured)

[0244] Since soy and corn change leaf properties over their lifetime, according to the present invention the treatment in regard to leaf properties can be adapted, i.e. the formulations according to the invention can be applied in a growth stadium where the leafs are hard to wet.

[0245] The invention is illustrated by the following examples.

EXAMPLES

[0246] Method 1: SC Preparation

[0247] The method of the preparation of suspension concentrate formulations are known in the art and can be produced by known methods familiar to those skilled in the art. A 2% gel of the xanthan (c) in water and the biocides (c) was prepared with low shear stirring. The active ingredient (a), non-ionic and anionic dispersants (c), antifoam (c) and other formulants (c) were mixed with water to form a slurry, first mixed with a high shear rotor-stator mixer (Ultra-Turrax®) to reduce the particle size D(v,0.9) to approximately 50 microns, then passed through one or more bead mills (Eiger® 250 Mini Motormill) to achieve a particles size D(v,0.9) typically 1 to 15 microns. Then the additives (b), (c) and (d) and xanthan gel prepared above were added and mixed in with low shear stirring until homogeneous. Finally, the pH is adjusted if needed with acid or base (e).

[0248] Method 2: WG Preparation

[0249] The methods of the preparation water dispersible granule formulations are known in the art and can be produced by known methods familiar to those skilled in the art.

[0250] For example, to produce a fluid bed granule first a water-based technical concentrate has to be prepared. With low shear stirring all ingredients (a, b and c) like e.g. the active ingredient, surfactants, dispersants, binder, antifoam, spreader, and filler are mixed in water and finally pre-milled in a high shear rotor-stator mixer (Ultra-Turrax®) to reduce the particle size D(v,0.9) to approximately 50 microns, afterwards passed through one or more bead mills (KDL, Bachofen, Dynomill, Buhler, Drais, Lehmann) to achieve a particles size D(v,0.9) typically 1 to 15 microns. This water-based technical concentrate is then spray-dried in a fluid-bed granulation process to form the wettable granules (WG).

[0251] The particle size is determined according to CIPAC (CIPAC=Collaborative International Pesticides Analytical Council; www.cipac.org) method MT 187. The particle size distribution is determined by means of laser diffraction. A representative amount of sample is dispersed in degassed water at ambient temperature (self-saturation of the sample), treated with ultrasound (usually 60 s) and then measured in a device from the Malvern Mastersizer series (Malvern Panalytical). The scattered light is measured at various angles using a multi-element detector and the associated numerical values are recorded. With the help of the Fraunhofer model, the proportion of certain size classes is calculated from the scatter data and from this a volume-weighted particle size distribution is calculated. Usually the d50 or d90 value=active ingredient particle size (50 or 90% of all volume particles) is given. The average particle size denotes the d50 value.

[0252] Likewise, any other spraying process, like e.g. classical spray drying can be used as granulation method.

[0253] A further technique to produce water dispersible granules is for example low pressure extrusion. The ingredients of the formulation are mixed in dry from and are subsequently milled, e.g. using air-jet milling to reduce the particle size. Subsequently this dry powder is stirred while water is added to the mixture (approximately 10-30 wt %, dependent on the composition of the formulation). In a further step the mixture is pushed through an extruder (like a dome extruder, double dome extruder, basket extruder, sieve mill, or similar device) with a die size of usually between 0.8 and 1.2 mm to form the extrudates. In a last step the extrudates are post-dried, e.g. in a fluidized bed dryer to reduce the water content of the powder, commonly to a level of 1-3 wt % of residual water.

[0254] Method 3: EC Preparation

[0255] The method of the preparation of EC formulations are known in the art and can be produced by known methods familiar to those skilled in the art. In general, EC formulations are obtained by mixing the active ingredient (a) with the rest of the formulation components, which include, amongst others, surfactants (c), spreader (b), a carrier (d) in a vessel equipped with a stirring device. In some cases the dissolving or mixing was facilitated by raising the temperature slightly (not exceeding 60° C.). Stirring is continued until a homogeneous mixture has been obtained.

[0256] Method 4: OD Preparation

[0257] Formulation components (c), carrier (d) active ingredient (a), spreader (b) are weighed in, homogenized with a high-shear device (e.g. Ultraturrax or colloidal mill) and subsequently milled in a bead mill (e.g. Dispermat SL50, 80% filling, 1.0-1.25 mm glass beads, 4000 rpm, circulation grinding) until a particle size of <10p is achieved. Alternatively, formulation components are mixed in a bottle followed by addition of approx. 25 vol.-% of 1.0-1.25 mm glass beads. The bottle is then closed, clamped in an agitator apparatus (e.g. Retsch MM301) and treated at 30 Hz for several minutes until a particle size of <10μ is achieved.

[0258] Method 5: Coverage

[0259] Greenhouse plants in the development stage as indicated in Tables 1a&1b were used for these experiments. Single leaves were cut just before the spraying experiment, placed into petri dishes and attached by tape at both tips at 0° (horizontally) or at 60° (so that 50% of leaf area can be sprayed). The leaves were carried with caution to avoid damage of the wax surface. These horizontally orientated leaves were either a) placed into a spay chamber where the spray liquid was applied via a hydraulic nozzle or b) a 4 μl drop of spray liquid was pipetted on top without touching the leaf surface.

[0260] A small amount of UV dye was added to the spray liquid to visualize the spray deposits under UV light. The concentration of the dye has been chosen such that it does not influence the surface properties of the spray liquid and does not contribute to spreading itself. Tinopal OB as a colloidal suspension was used for all flowable and solid formulation such as WG, SC, OD and SE. Tinopal CBS-X or Blankophor SOL were used for formulations where active ingredient is dissolved such as EC, EW and SL. The Tinopal CBS-X was dissolved in the aqueous phase and the Blankophor SOL dissolved in the oil phase.

[0261] After evaporation of the spray liquid, the leaves were placed into a Camag, Reprostar 3 UV chamber where pictures of spray deposits were taken under visual light and under UV light at 366 nm. A Canon EOS 700D digital camera was attached to the UV chamber and used to acquire images the leaves. Pictures taken under visual light were used to subtract the leaf shape from the background. ImageJ software was used to calculate either a) the percentage coverage of the applied spray for sprayed leaves or b) spread area for pipetted drops in mm.sup.2.

[0262] Method 6: Insecticide Greenhouse Tests

[0263] Selected crops were grown under greenhouse conditions in plastic pots containing “peat soil T”. At appropriate crop stage, plants were prepared for the treatments, e.g. by infestation with target pest approximately 2 days prior to treatment (s. table below).

[0264] Spray solutions were prepared with different doses of active ingredient directly by dilution of formulations with tap water and addition of appropriate amount of additives in tank mix, where required.

[0265] The application was conducted with a tracksprayer onto the upperside of leaves with 300 l/ha or 10 l/ha application volume. Nozzles used: Lechler's TeeJet TP8003E (for 300 l/ha) and Lechler's 652.246 together with a pulse-width-module (PWM) (for 10 l/ha). For each single dose applied, usually 2 to 5 replicates were simultaneously treated.

[0266] After treatment, plants were artificially infested, if needed, and kept during test duration in a greenhouse or climate chamber. The efficacy of the treatments was rated after evaluation of mortality (in general, given in %) and/or plant protection (calculated e.g. from feeding damage in comparison to corresponding controls) at different points of time. Only mean values are reported.

TABLE-US-00003 TABLE M1 Pests and crops used in the tests. crop crop stage infestation pest English name pest life stage test objective soybean BBCH12, after Nezara green stink bug 10x nymphs contact and oral 5 plants treatment viridula N2-N3 uptake in pot cabbage BBCH12, prior to Myzus green peach mixed translaminar 1-leaf treatment persicae aphid population activity

[0267] Selected crops were grown under greenhouse conditions in plastic pots containing “peat soil T”. At appropriate crop stage, plants were prepared for the treatments, e.g. by infestation with target pest approximately 2 days prior to treatment (table M1).

[0268] Spray solutions were prepared with different doses of active ingredient directly by dilution of formulations with tap water and addition of appropriate amount of additives in tank mix, where required.

[0269] The application was conducted with tracksprayer onto upperside of leaves with 300 l/ha or 10 l/ha application volume. Nozzles used: Lechler's TeeJet TP8003E (for 300 l/ha) and Lechler's 652.246 together with a pulse-width-module (PWM) (for 10 l/ha). For each single dose applied, usually 2 to 5 replicates were simultaneously treated.

[0270] After treatment, plants were artificially infested, if needed, and kept during test duration in a greenhouse or climate chamber. The efficacy of the treatments was rated after evaluation of mortality (in general, given in %) and/or plant protection (calculated e.g. from feeding damage in comparison to corresponding controls) at different points of time. Only mean values are reported.

[0271] Method 7: Cuticle Wash-Off

[0272] A disc from an apple cuticle was fixed with the outside surface facing upwards to a glass microscope slide with a thin layer of medium viscosity silicone oil. To this 0.9 μl drops of the different formulations diluted at the spray dilution in deionised water containing 5% CIPAC C water were applied with a micropipette and left to dry for 1 hour. Each deposit was examined in an optical transmission microscope fitted with crossed polarising filters and an image recorded. The slide containing the cuticle with the dried droplets of the formulations was held under gently running deionised water (flow rate approximately 300 ml/minute at a height 10 cm below the tap outlet) for 15 s. The glass slide was allowed to dry and the deposits were re-examined in the microscope and compared to the original images. The amount of active ingredient washed off was visually estimated and recorded in steps of 10%. Three replicates were measured and the mean value recorded.

[0273] Method 8: Leaf Wash-Off

[0274] Apple or corn leaf sections were attached to a glass microscope slide. To this 0.9 μl drops of the different formulations diluted at the spray dilution in deionised water containing 5% CIPAC C water and a small amount of fluorescent tracer (Tinopal OB as a micron sized aqueous suspension) were applied with a micropipette and left to dry for 1 hour. Under UV illumination (365 nm) the leaf deposits were imaged by a digital camera. The leaf sections were then held under gently running deionised water (flow rate approximately 300 ml/minute at a height 10 cm below the tap outlet) for 15 s. The leaf sections were allowed to dry and the deposits were re-imaged and compared to the original images. The amount of active ingredient washed off was visually estimated between 5 with most remaining and 1 with most removed. Three or more replicates were measured and the mean value recorded.

[0275] Method 9: Suspo-Emulsion Preparation

[0276] The method of the preparation of suspo-emulsion formulations are known in the art and can be produced by known methods familiar to those skilled in the art. A 2% gel of the xanthan in water and the biocides (e) was prepared with low shear stirring. The active ingredient spiroxamine (a), oils (b/c) and antioxidant (e) were mixed and added to an aqueous dispersion comprising a portion of the non-ionic dispersants (c) under high shear mixing with a rotor-stator mixer until an oil in water emulsion was formed with a droplet size D(v,0.9) typically 1 to 5 microns. The active ingredient (a), the remaining non-ionic and anionic dispersants (c/e) and other remaining formulants (c/e) were mixed with the remaining water to form a slurry, first mixed with a high shear rotor-stator mixer to reduce the particle size D(v,0.9) to approximately 50 microns, then passed through one or more bead mills to achieve a particles size D(v,0.9) typically 1 to 15 microns as required for the biological performance of the active ingredient(s). Those skilled in the art will appreciate that this can vary for different active ingredients. The oil in water emulsion, polymer dispersion (c/d) and xanthan gel were added and mixed in with low shear stirring until homogeneous.

[0277] Method 10: Description for Herbicide Greenhouse Tests

[0278] Seeds of crops and monocotyledonous and dicotyledonous harmful plants are laid out in sandy loam in plastic pots, covered with soil and cultivated in a greenhouse under optimum growth conditions. Two to three weeks after sowing, the test plants are treated at the one- to two-leaf stage. The test herbicide formulations are prepared with different concentrations and sprayed onto the surface of the green parts of the plants using different water application rates: 200 l/ha as a standard conventional rate and 10 l/ha as an ultra-low-volume (ULV) application rate. The nozzle type used for all applications is TeeJet DG 95015 EVS. The ULV application rate is achieved by using a pulse-width-modulation (PWM)-system that gets attached to the nozzle and the track sprayer device. After application, the test plants were left to stand in the greenhouse for 3 to 4 weeks under optimum growth conditions. Then, the activity of the herbicide formulation is scored visually (for example: 100% activity=the whole plant material is dead, 0% activity=plants are similar to the non-treated control plants).

TABLE-US-00004 TABLE M2 Plant species used in the tests. Abbreviation/ Plant species EPPO Code Crop Variety Setaria viridis SETVI Echinochloa crus-galli ECHCG Alopecurus myosuroides ALOMY Hordeum murinum HORMU Avena fatua AVEFA Lolium rigidum LOLRI Matricaria inodora MATIN Veronica persica VERPE Abutilon theophrasti ABUTH Pharbitis purpurea PHBPU Polygonum convolvulus POLCO Amaranthus retroflexus AMARE Stellaria media STEME Zea mays ZEAMA Aventura Triticum aestivum TRZAS Triso Brassica napus BRSNW Fontan

[0279] Method 11: Description for Fungicide Greenhouse Tests

[0280] Seeds were laid out in “peat soil T” in plastic pots, covered with soil and cultivated in a greenhouse under optimum growth conditions. Two to three weeks after sowing, the test plants were treated at the one- to two-leaf stage. The test fungicide formulations were prepared with different concentrations and sprayed onto the surface of the plants using different water application rates: 200 l/ha as a standard conventional rate and 10 l/ha as an ultra-low-volume (ULV) application rate. The nozzle type used for all applications was TeeJet TP 8003E, used with 0,7-1,5 bar and 500-600 mm height above plant level. Cereal were put in an 45° angle as this reflected best the spray conditions in the field for cereals. The ULV application rate was achieved by using a pulse-width-modulation (PWM) system attached to the nozzle and the track sprayer device at 30 Hz, opening 8%-100% (10 l/ha-200 l/ha spray volume).

[0281] In a protective treatment the test plants were inoculated 1 day after the spray application with the respective disease and left to stand in the greenhouse for 1 to 2 weeks under optimum growth conditions. Then, the activity of the fungicide formulation was assessed visually.

[0282] In curative conditions plants were first inoculated with the disease and treated 2 days later with the fungicide formulations. Visual assessment of the disease was done 5 days after application of formulations.

[0283] The practices for inoculation are well known to those skilled in the art.

TABLE-US-00005 TABLE M3 Diseases and crops used in the tests. Abbreviation/ Plant species Crop Variety Disease English Name EPPO Code disease Soybean Merlin Phakopsora Soybean rust PHAKPA pachyrhizi Wheat Monopol Puccinia triticina Brown rust PUCCRT Barley Gaulois Pyrenophora teres Net blotch PYRNTE Barley Villa Blumeria graminis Powdery mildew ERYSGH Tomato Rentita Phytophtora Late blight PHYTIN infestans

[0284] Method 12: Cuticle Penetration Test

[0285] The cuticle penetration test is a further developed and adapted version of the test method SOFU (simulation of foliar uptake) originally described by Schönherr and Baur (Schönherr, J., Baur, P. (1996), Effects of temperature, surfactants and other adjuvants on rates of uptake of organic compounds. In: The plant cuticle—an integrated functional approach, 134-155. Kerstiens, G. (ed.), BIOS Scientific publisher, Oxford); it is well suited for systematic and mechanistic studies on the effects of formulations, adjuvants and solvents on the penetration of agrochemicals.

[0286] Apple leaf cuticles were isolated from leaves taken from trees growing in an orchard as described by Schonherr and Riederer (Schönherr, J., Riederer, M. (1986), Plant cuticles sorb lipophilic compounds during enzymatic isolation. Plant Cell Environ. 9, 459-466). Only the astomatous cuticular membranes of the upper leaf surface lacking stomatal pores were obtained. Discs having diameters of 18 mm were punched out of the leaves and infiltrated with an enzymatic solution of pectinase and cellulase. The cuticular membranes were separated from the digested leaf cell broth, cleaned by gently washing with water and dried. After storage for about four weeks the permeability of the cuticles reaches a constant level and the cuticular membranes are ready for the use in the penetration test.

[0287] The cuticular membranes were applied to diffusion vessels. The correct orientation is important: the inner surface of the cuticle should face to the inner side of the diffusion vessel. A spray was applied in a spray chamber to the outer surface of the cuticle. The diffusion vessel was turned around and carefully filled with acceptor solution. Aqueous mixture buffered to pH 5.5 was used as acceptor medium to simulate the apoplast as natural desorption medium at the inner surface of the cuticle.

[0288] The diffusion vessels filled with acceptor and stirrer were transferred to a temperature-controlled stainless steel block which ensures not only a well-defined temperature but also a constant humidity at the cuticle surface with the spray deposit. The temperature at the beginning of experiments was 25° C. or 30° C. and changes to 35° 24 h after application at constantly 60% relative humidity.

[0289] An autosampler took aliquots of the acceptor in regular intervals and the content of active ingredient is determined by HPLC (DAD or MS). All data points were finally processed to obtain a penetration kinetic. As the variation in the penetration barrier of the cuticles is high, five to ten repetitions of each penetration kinetic were made.

[0290] Materials

TABLE-US-00006 TABLE MAT1 Exemplified trade names and CAS-No's of preferred super-spreading compounds (b) Product Chemical name Cas No. Supplier Geropon ® DOS- Dioctylsulfosuccinate sodium 577-11-7 Rhodia PG salt (65-70% in propylene glycol) Synergen ® W 10 Dioctylsulfosuccinate sodium 577-11-7 Clariant salt (65-70% in propylene glycol) Aerosol ® OT 70 Dioctylsulfosuccinate sodium 577-11-7 Cytec PG salt (65-70% in propylene glycol) Lankropol KPH70 Dioctylsulfosuccinate sodium 577-11-7 Nouryon salt (65-70% in propylene glycol) Enviomet EM Dioctylsulfosuccinate sodium 577-11-7 Innospec 5669 salt (65-70% in propylene glycol) Surfynol ® S420 2,4,7,9-Tetramethyl-5-Decyne- 9014-85-1 Evonik 4,7-Diol ethoxylate (1 mole) Surfynol ® S440 2,4,7,9-Tetramethyl-5-Decyne- 9014-85-1 Evonik 4,7-Diol ethoxylate (3.5 moles) Surfynol ® S465 2,4,7,9-Tetramethyl-5-Decyne- 9014-85-1 Evonik 4,7-Diol ethoxylate (10 moles) Surfynol ® S485 2,4,7,9-Tetramethyl-5-Decyne- 9014-85-1 Evonik 4,7-Diol ethoxylate (30 moles) Break-Thru ® Not disclosed Evonik Vibrant Genapol ® EP 0244 C10-12 alcohol alkoxylate Clariant (PO + EO) Synergen ® W06 C11 alcohol alkoxylate (PO + EO) Clariant Genapol ® EP 2584 C12-15 alcohol alkoxylate Clariant (PO + EO) Agnique ® PG8107 Oligomeric D-glucopyranose 68515-73-1 BASF decyl octyl glycosides Silwet ® L77 3-(2-methoxyethoxy)propyl- 27306-78-1 Momentive methyl- bis(trimethylsilyloxy)silane Silwet ® 408 2-[3- 67674-67-3 Momentive [[dimethyl(trimethylsilyloxy)silyl]oxy- methyl- trimethylsilyloxysilyl]propoxy]ethanol Silwet ® 806 3-[methyl- 134180-76-0 Momentive bis(trimethylsilyloxy)silyl]propan- 1-ol;2-methyloxirane;oxirane Break-thru ® S240 3-[methyl- 134180-76-0 Evonik bis(trimethylsilyloxy)silyl]propan- 1-ol;2-methyloxirane;oxirane Break-thru ® S278 3-(2-methoxyethoxy)propyl- 27306-78-1 Evonik methyl- bis(trimethylsilyloxy)silane Silwet ® HS 312 Silwet ® HS 604 BreakThru ® OE Siloxanes and Silicones, cetyl 191044-49-2 Evonik 444 Me, di-Me

TABLE-US-00007 TABLE MAT2 Exemplified trade names and CAS-No's of preferred uptake enhancing compounds (b) Product Chemical name Cas No. Supplier Emulsogen ® EL 400 Ethoxylated Castor Oil with 40 EO 61791-12-6 Clariant ETOCAS ®10 Ethoxylated Castor Oil with 10 EO 61791-12-6 Croda Crovol ® CR70G fats and glyceridic oils, vegetable, 70377-91-2 Croda ethoxylated Synperonic ® A3 alcohol ethoxylate (C12/C15-EO3) 68131-39-5 Croda Synperonic ® A7 alcohol ethoxylate (C12/C15-EO7) 68131-39-5 Croda Genapol ® X060 alcohol ethoxylate (iso-C13-EO6) 9043-30-5 Clariant Alkamuls ® A Oleic acid, ethoxylated 9004-96-0 Solvay Lucramul ® HOT 5902 alcohol ethoxylate-propoxylate 64366-70-7 Levaco (C8-PO8/EO6) Antarox B/848 Butyl alcohol propoxylate/ 9038-95-3 Solvay ethoxylate Tween ® 80 Sorbitan monooleate, ethoxylated 9005-65-6 Croda (20EO) Tween ® 85 Sorbitan trioleate, ethoxylated 9005-70-3 Croda (20EO) Tween ® 20 Sorbitan monolaurate, ethoxylated 9005-64-5 Croda (20EO) Sunflower oil Triglycerides from different C14- 8001-21-6 C18 fatty acids, predominantly unsaturated Rapeseed oil Triglycerides from different C14- 8002-13-9 C18 fatty acids, predominantly unsaturated Corn oil Triglycerides from different C14- 8001-30-7 C18 fatty acids, predominantly unsaturated Soybean oil Triglycerides from different C14- 8001-22-7 C18 fatty acids, predominantly unsaturated Rice bran oil Triglycerides from different C14- 68553-81-1 C18 fatty acids, predominantly unsaturated Radia ® 7129 ethylhexyl palmitate 29806-73-3 Oleon NV, BE Crodamol ® OP Croda, UK Radia ® 7331 ethylhexyl oleate 26399-02-0 Oleon NV, BE Radia ® 7128 ethylhexyl myristate/laurate 29806-75-5 Oleon NV, BE C12/C14 Radia ® 7127 ethylhexyl laurate 20292-08-4 Oleon NV, BE Radia ® 7126 ethylhexyl caprylate/caprate 63321-70-0 Oleon NV, BE C8/10 Estol ® 1514 iso-propyl myristate 110-27-0 Croda Radia ® 7104 Caprylic, capric triglycerides, 73398-61-5. Oleon NV, BE neutral vegetable oil 65381-09-1 Radia ® 7732 iso-propyl palmitate 142-91-6 Oleon NV, BE Crodamol ® IPM Croda, UK Radia ® 7060 methyl oleate 112-62-9 Oleon NV, BE Radia ® 7120 methyl palmitate 112-39-0 Oleon NV, BE Crodamol ® EO ethyl oleate 111-62-6 Croda AGNIQUE ME ® 18 Rape seed oil methyl ester 67762-38-3. Clariant RD-F, Edenor ® MESU 85586-25-0 BASF Miglyol 812 N Glycerides, mixed decanoyl and 65381-09-1 octanoly 73398-61-5 Exxsol ® D100 Hydrotreated light distillates 64742-47-8 Exxon Mobil (petroleum) Solvesso ® 200ND Solvent naphtha (petroleum), 64742-94-5 ExxonMobil heavy aromatic, naphthalene depleted Kristol ® M14 White mineral oil (petroleum), 8042-47-5 Carless Marcol ® 82 Ondina ® C14-C30 branched and linear ExxonMobil 917 Shell Exxsol ®D130 White mineral oil (petroleum) 64742-46-7 ExxonMobil Banole ® 50 Total Genera ®-12 White mineral oil (petroleum) 72623-86-0 Total Genera ®-9 White mineral oil (petroleum) 97862-82-3 Total

TABLE-US-00008 TABLE MAT3 Exemplified trade names of preferred wash-off reducing materials (d) Product Chemical name Tg MFFT Supplier Atplus ® FA Aqueous styrene acrylic co- <30° C. Croda polymer emulsion dispersion Acronal ® V215 aqueous acrylate co-polymer −43° C. BASF Acronal ® V115 dispersion containing carboxylic −58° C. Acronal ® A245 groups. −45° C. Acronal ® A240 −30° C. Acronal ® A225 −45° C. Acronal ® A145 −45° C. Acronal ® 500 D aqueous acrylic co-polymer −13° C. BASF Acronal ® S 201 dispersion −25° C. Acronal ® DS 3618 aqueous acrylic ester co- −40° C. BASF Acronal ® 3612 polymer dispersion +12° C. Acronal ® V212 −40° C. Acronal ® DS 3502  +4° C. Acronal ® S 400  −8° C. Licomer ® ADH205 aqueous acrylic ester co- <30° C. Michelman Licomer ® ADH203 polymer dispersion containing carboxylic groups. Primal ® CM-160 Aqueous acrylic copolymer DOW Primal ® CM-330 emulsion polymer Axilat ® UltraGreen Aqueous acrylic emulsion −15° C. 0° C. Synthomer 5500 polymer Povol ® 26/88 Polyvinyl alcohol Kuraray

TABLE-US-00009 TABLE MAT4 Exemplified trade names and CAS-No's of preferred compounds (e) Table I1 Exemplified trade names and CAS-No's of preferred compounds (e) for Insecticide Examples Product Chemical name Cas No. Supplier Lucramul PS 29 Poly(oxy-1,2-ethanediyl),. alpha.- 104376-75-2 Levaco phenyl-.omega.-hydroxy-, styrenated Atlox ® 4913 methyl methacrylate graft 119724-54-8 Croda copolymer with polyethylene glycol Morwet IP Naphthalenesulfonic acid, bis(1- 68909-82-0 Akzo Nobel methylethyl)-, Me derivs., sodium salts Synperonic ® block-copolymer of polyethylene 9003-11-6 Croda PE/F127 oxide and polypropylene oxide Morwet D425 Sodium naphthalene sulphonate 577773-56-9 Akzo Nobel, formaldehyde condensate 68425-94-5 Nouryon 9008-63-3 ATLAS ® G Oxirane, methyl-, polymer with 9038-95-3 Croda 5000 oxirane, monobutyl ether Glycerin 56-81-5 Propylene 1,2-Propylene glycol 57-55-6 Glycol RHODOPOL ® Polysaccharide 11138-66-2 Solvay 23 Sipernat 22 S synthetic amorphous silica (silicon 112926-00-8 Evonik dioxide) 7631-86-9 Veegum R Smectite-group minerals 12199-37-0 SILCOLAPSE ® Polydimethylsiloxanes and silica 9016-00-6 BLUESTAR 426R SILICONES SAG ® 1572 Dimethyl siloxanes and silicones 63148-62-9 Momentive Citric Acid 77-92-9 (anhydrous); 5949-29-1 (Monohydrate) Proxel ® GXL 1.2-benzisothiazol-3(2H)-one 2634-33-5 Arch Chemicals Kathon ® 5-chloro-2-methyl-4-isothiazolin- 26172-55-4 plus Dow CG/ICP 3-one plus 2-methyl-4- 2682-20-4 isothiazolin-3-one

TABLE-US-00010 TABLE MAT5 Exemplified trade names and CAS-No's of preferred compounds (e) Product Chemical name Cas No. Supplier Morwet ® D425 Naphthalene sulphonate 9008-63-3 New XX formaldehyde condensate Na salt Synperonic ® PE/F127 block-copolymer of polyethylene 9003-11-6 Croda oxide and polypropylene oxide Synperonic ® A7 alcohol ethoxylate (C12/C15-EO7) 68131-39-5 Croda Xanthan Polysaccharide 11138-66-2 Proxel ® GXL 1.2-benzisothiazol-3(2H)-one 2634-33-5 Arch Chemicals Kathon ® CG/ICP 5-chloro-2-methyl-4-isothiazolin-3- 26172-55-4 plus Dow one plus 2-methyl-4-isothiazolin-3- 2682-20-4 one Propylene glycol 1,2-Propylene glycol 57-55-6 SAG ® 1572 Dimethyl siloxanes and silicones 63148-62-9 Momentive Atlox ® 4913 methyl methacrylate graft 119724-54-8 Croda copolymer with polyethylene glycol ATLAS ® G 5000 Oxirane, methyl-, polymer with 9038-95-3 Croda oxirane, monobutyl ether SILCOLAPSE ® 454 Polydimethylsiloxanes and silica 9016-00-6 BLUESTAR SILICONES RHODOPOL ® 23 Polysaccharide 11138-66-2 Solvay ACTICIDE ® MBS Mixture of 2-methyl-4-isothiazolin- 2682-20-4 Thor GmbH 3-one (MIT) and 1,2- 2634-33-5 benzisothiazolin-3-one (BIT) in water Sokalan ® K 30 Polyvinylpyrrolidone 9003-39-8 BASF Supragil ® WP Sodium diisopropyl naphthalene 1322-93-6 Solvay sulfonate Morwet ® D-425 Sodium naphthalene sulphonate 577773-56-9 Akzo Nobel, formaldehyde condensate 68425-94-5 Nouryon 9008-63-3 Soprophor ® 4 D 384 Tristyrylphenol ethoxylate sulfate 119432-41-6 Solvay (16 EO) ammonium salt Rhodorsil ® Antim EP absorbed polydimethyl siloxane unknown Solvay 6703 antifoam Kaolin Tec 1 Aluminiumhydrosilicate 1318-74-7 Ziegler & Co. 1332-58-7 GmbH Sipernat ® 22 S synthetic amorphous silica (silicon 112926-00-8 Evonik dioxide) 7631-86-9 RHODACAL ® 60 BE Calcium- 26264-06-2 Solvay dodecylbenzenesulphonate in 2- 104-76-7 Ethylhexanol Emulsogen ® EL 400 Ethoxylated Castor Oil with 40 EO 61791-12-6 Clariant Solvesso ® 200ND Mixture of aromatic hydrocarbons 64742-94-5 ExxonMobil (C9-C11), naphtalene depleted

[0291] Fungicides Examples

Example FN1 Inpyrfluxam 25 SC

[0292]

TABLE-US-00011 TABLE FN1 Inpyrfluxam 25 SC Recipes FN1 and FN2. Recipe FN2 Recipe FN1 according to the Component (g/l) reference invention Inpyrfluxam (a) 25.0 25.0 Morwet ® D425 (c) 5.0 5.0 Atlox ® 4913 (c) 10.0 10.0 Synperonic ® PE/F127 (c) 5.0 5.0 Surfynol ® 440 (b) 0 100.0 Xanthan (c) 3.6 3.6 Proxel ® GXL (c) 1.5 1.5 Kathon ® CG/ICP (c) 0.8 0.8 Propylene glycol (c) 60.0 60.0 SAG ® 1572 (c) 6.0 6.0 Na.sub.2HPO.sub.4 (Buffer (c) 1.5 1.5 solution pH = 7) NaH.sub.2PO.sub.4 (Buffer (c) 0.8 0.8 solution pH = 7) Water (add to 1 litre) (c) To volume To volume (~901) (~801)

[0293] The method of preparation used was according to Method 1.

[0294] Greenhouse

[0295] Efficacy Data

TABLE-US-00012 TABLE FN2 Biological efficacy on PHAKPA/soy Recipe FN2 according Recipe FN1 to the Spray volume Rate of SC Rate of reference invention l/ha applied l/ha a.i. g/ha Efficacy [%] Efficacy [%] 200 0.08 2 81 98 200 0.04 1 75 83 200 0.02 0.5 61 49 15 0.08 2 67 95 15 0.04 1 53 80 15 0.02 0.5 26 65

[0296] Method 11: Soybean, 1 Day Preventive, Evaluation 7 Days after Infestation

[0297] The results show that recipe FN2 illustrative of the invention shows higher efficacy at 15 l/ha spray volume than 200 l/ha. Furthermore, recipe FN2 at 15 l/ha shows comparably or higher efficacy than recipe FN2 at 200 l/ha.

[0298] Pipette Spreading Tests on Leaves

[0299] The leaf deposit size was determined according to method 5 (b) (2 μL droplet).

TABLE-US-00013 TABLE FN3 Spray dilution droplet size and dose on non-textured apple leaves and texture soybean and rice leaves. High- spreading surfactant Deposit Deposit Deposit High- dose in area area area spreading spray mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 surfactant liquid Recipe apple soybean rice dose g/ha % w/v Recipe FN1 not 7.28 2.27 1.75 0 0 according to the invention - 10 l/ha Recipe FN1 not 4.74 3.74 2.46 0 0 according to the invention - 200 l/ha Recipe FN1 not 3.20 1.34 2.61 0 0 according to the invention - 800 l/ha Recipe FN2 16.2 149.2 149.8 100 1.0 according to the invention - 10 l/ha Recipe FN2 7.89 24.8 15.2 100 0.0125 according to the invention - 200 l/ha Recipe FN2 5.95 4.66 17.5 100 0.0125 according to the invention - 800 l/ha Formulations applied at 1 l/ha.

[0300] The results show that recipe FN2 illustrative of the invention shows significantly greater deposit sizes at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe FN1.

Example FN2 Isoflucypram 50 SC

[0301]

TABLE-US-00014 TABLE FN4 Isoflucypram 50 SC Recipes FN3 and FN4. Recipe FN4 Recipe FN3 according to the Component (g/l) reference invention Isoflucypram (a) 50.0 50.0 Morwet ® D425 (c) 10.0 5.0 Soprophor ® FLK (c) 20.0 10.0 Synperonic ® PE/F127 (c) 10.0 5.0 Break-Thru ® Vibrant (b) 0.0 80.0 Xanthan (c) 3.0 3.0 Proxel ® GXL (c) 1.5 1.5 Kathon ® CG/ICP (c) 0.8 0.8 Propylene glycol (c) 60.0 60.0 SAG ® 1572 (c) 6.0 6.0 Na.sub.2HPO.sub.4 (Buffer (c) 1.5 1.5 solution pH = 7) NaH.sub.2PO.sub.4 (Buffer (c) 0.8 0.8 solution pH = 7) Water (add to 1 litre) (c) To volume To volume (~896) (~816)

[0302] The method of preparation used was according to Method 1.

[0303] Pipette Spreading Tests on Leaves

[0304] The leaf deposit size was determined according to method 5 (b) (2 μL droplet).

TABLE-US-00015 TABLE FN5 Spray dilution droplet size and dose on non-textured apple leaves and texture soybean and rice leaves. High- spreading surfactant Deposit Deposit Deposit High- dose in area area area spreading spray mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 surfactant liquid Recipe apple soybean rice dose g/ha % w/v Recipe FN3 not 5.12 2.45 1.14 0 0 according to the invention - 10 l/ha Recipe FN3 not 5.50 2.84 1.79 0 0 according to the invention - 200 l/ha Recipe FN4 13.05 46.26 132.8 40 0.4 according to the invention - 10 l/ha Recipe FN4 5.48 6.16 18.03 40 0.02 according to the invention - 200 l/ha Formulations applied at 0.5 l/ha.

[0305] The results show that recipe FN4 illustrative of the invention shows significantly greater deposit sizes at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe FN3.

Example FN3: Fluopicolide 100 SC

[0306]

TABLE-US-00016 TABLE FN6 Fluopicolide 100 SC Recipes FN5 and FN6. Recipe FN6 Recipe FN5 according to the Component (g/l) reference invention Fluopicolide (a) 100.0 100.0 Morwet ® D425 (c) 10.0 10.0 Soprophor ® FLK (c) 20.0 20.0 Synperonic ® PE/F127 (c) 10.0 10.0 Geropon ® DOS 70PG (b) 0.0 60.0 Xanthan (c) 3.0 3.0 Proxel ® GXL (c) 1.5 1.5 Kathon ® CG/ICP (c) 0.8 0.8 Propylene glycol (c) 60.0 60.0 SAG ® 1572 (c) 6.0 6.0 Na.sub.2HPO.sub.4 (Buffer (c) 1.5 1.5 solution pH = 7) NaH.sub.2PO.sub.4 (Buffer (c) 0.8 0.8 solution pH = 7) Water (add to 1 litre) (c) To volume To volume (~846) (~786)

[0307] The method of preparation used was according to Method 1.

[0308] Pipette Spreading Tests on Leaves

[0309] The leaf deposit size was determined according to method 5 (b) (2 μL droplet).

TABLE-US-00017 TABLE FN7 Spray dilution droplet size and dose on non-textured apple leaves and texture soybean and rice leaves. High- spreading surfactant Deposit Deposit Deposit High- dose in area area area spreading spray mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 surfactant liquid Recipe apple soybean rice dose g/ha % w/v Recipe FN5 not 5.23 2.77 2.30 0 0 according to the invention - 10 l/ha Recipe FN5 not 3.49 1.21 1.52 0 0 according to the invention - 200 l/ha Recipe FN6 18.89 136.2 185.9 40 0.4 according to the invention - 10 l/ha Recipe FN6 9.56 136.5 51.15 40 0.02 according to the invention - 200 l/ha Formulations applied at 1.0 l/ha.

[0310] The results show that recipe FN6 illustrative of the invention shows significantly greater deposit sizes at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe ENS. The effect is greater on textured leaf surfaces.

Example FN4: Fluopyram 200 SC

[0311]

TABLE-US-00018 TABLE FN8 Fluopyram 200 SC Recipes FN7, FN8 and FN9. Recipe FN8 according Recipe FN9 Recipe FN7 to the reference Component (g/l) reference invention (negative) Fluopyram (a) 200.0 200.0 200.0 Morwet ® D425 (c) 10.0 10.0 10.0 Soprophor ® TS54 (c) 20.0 20.0 20.0 Synperonic ® PE/ (c) 10.0 10.0 10.0 F127 Surfynol ® 420 (b) 0.0 60.0 0.0 Surfynol ® 465 (b)? 0.0 0.0 60.0 Xanthan (c) 3.0 3.0 3.0 Proxel ® GXL (c) 1.5 1.5 1.5 Kathon ® CG/ICP (c) 0.8 0.8 0.8 Propylene glycol (c) 60.0 60.0 60.0 SAG ® 1572 (c) 6.0 6.0 6.0 Na.sub.2HPO.sub.4 (Buffer (c) 1.5 1.5 1.5 solution pH = 7) NaH.sub.2PO.sub.4 (Buffer (c) 0.8 0.8 0.8 solution pH = 7) Water (add to 1 litre) (c) To volume To volume To volume (~786) (~726) (~726)

[0312] The method of preparation used was according to Method 1.

[0313] Pipette Spreading Tests on Leaves

[0314] The leaf deposit size was determined according to method 5 (b) (2 μL droplet).

TABLE-US-00019 TABLE FN9 Spray dilution droplet size and dose on non-textured apple leaves and texture soybean and rice leaves. High- spreading surfactant Deposit Deposit Deposit High- dose in area area area spreading spray mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 surfactant liquid Recipe apple soybean rice dose g/ha % w/v Recipe FN7 not 3.96 1.52 1.64 0 0 according to the invention - 10 l/ha Recipe FN7 not 3.57 1.59 1.08 0 0 according to the invention - 200 l/ha Recipe FN8 9.064 117.3 77.87 40 0.4 according to the invention - 10 l/ha Recipe FN8 10.53 27.49 24.85 40 0.02 according to the invention - 200 l/ha Recipe FN9 5.95 5.52 7.92 30 0.3 reference (negative) - 10 l/ha Recipe FN9 6.15 2.54 2.21 30 0.015 reference (negative) - 200 l/ha Formulations applied at 0.5 l/ha.

[0315] The results show that recipe FN8 illustrative of the invention shows significantly greater deposit sizes at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe FN7. The effect is greater on textured leaf surfaces. Recipe FN9 which contains 60 g/L of Surfynol 465 shows comparable wetting to recipe FN7 without additive (b) illustrating that the high wetting only occurs with specific additives (b) and that Surfynol 420 with a lower degree of ethoxylation (1 mole EO) exhibits wetting illustrative of the invention while Surfynol 465 with a higher degree of ethoxylation (10 moles EO) does not.

Example FN5: Fluoxapiprolin 50 SC

[0316]

TABLE-US-00020 TABLE FN10 Fluoxapiprolin 50 SC Recipes FN10, FN11 and FN12. Recipe FN11 according Recipe FN10 to the Component (g/l) reference invention Recipe FN12 Fluoxapiprolin (a) 50.0 50.0 50.0 Morwet ® D425 (d) 10.0 10.0 10.0 Soprophor ® TS54 (d) 20.0 20.0 20.0 Synperonic ® PE/F127 (d) 10.0 10.0 10.0 Agnique ® PG8107 (b) 0.0 120.0 80.0 Xanthan (d) 3.0 3.0 3.0 Proxel ® GXL (d) 1.5 1.5 1.5 Kathon ® CG/ICP (d) 0.8 0.8 0.8 Propylene glycol (d) 60.0 60.0 60.0 SAG ® 1572 (d) 6.0 6.0 6.0 Na.sub.2HPO.sub.4 (Buffer (d) 1.5 1.5 1.5 solution pH = 7) NaH.sub.2PO.sub.4 (Buffer (d) 0.8 0.8 0.8 solution pH = 7) Water (add to 1 litre) (d) To volume To volume To volume (~896) (~776) (~816)

[0317] The method of preparation used was according to Method 1.

[0318] Pipette Spreading Tests on Leaves

[0319] The leaf deposit size was determined according to method 5 (b) (2 μL droplet).

TABLE-US-00021 TABLE FN11 Spray dilution droplet size and dose on non-textured apple leaves and texture soybean and rice leaves. High- spreading surfactant Deposit Deposit Deposit High- dose in area area area spreading spray mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 surfactant liquid Recipe apple soybean rice dose g/ha % w/v Recipe FN10 not 3.68 2.19 1.69 0 0 according to the invention - 10 l/ha Recipe FN10 not 3.58 2.24 2.23 0 0 according to the invention - 200 l/ha Recipe FN11 7.20 7.32 12.98 60 0.6 according to the invention - 10 l/ha Recipe FN11 4.90 2.81 1.76 60 0.03 according to the invention - 200 l/ha Recipe FN12 - 10 6.48 4.60 6.89 40 0.4 l/ha Recipe FN12 - 200 5.06 2.56 2.17 40 0.02 l/ha Formulations applied at 0.5 l/ha.

[0320] The results show that recipe FN11 illustrative of the invention shows greater deposit sizes at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe FN10. The effect is greater on textured leaf surfaces. The effect is dependent on the concentration of additive (b), recipe FN12 which contains 80 g/L of Agnique PG8107 shows a small effect compared to recipe FN11 which contains 120 g/L of Agnique PG8107. At 0.5 l/ha these amount of additive (b) correspond to 0.4 and 0.6% w/v in the spray dilution at 10 l/ha respectively.

[0321] Insecticide Examples

[0322] Examples were prepared and tested according to the relevant methods.

Example I1 Spirotetramat/Spiromesifen SC Formulations

[0323]

TABLE-US-00022 TABLE I1 Spirotetramat/Spiromesifen SC Formulations Recipe I2 Recipe I3 Recipe I4 Recipe I6 according according according according Recipe I1 to the to the to the Recipe I5 to the Component (g/l) reference invention invention invention reference invention Spirotetramat 75 75 75 75 — — Spiromesifen — — — — 72 72 Lucramul PS 29 40 40 40 30 — — Lucramul PS 54 — — — — 10.5 10.5 Atlox 4913 — — — — 31.5 31.5 Glycerin 100 100 100 100 105 105 Rhodopol 23 3 3 3 3 3.6 3.6 Preventol D7 0.8 0.8 0.8 0.8 0.8 0.8 Proxel GXL 20% 1.2 1.2 1.2 1.2 1.2 1.2 Silcolapse 426R 1 1 1 1 1 1 Citric Acid 1 1 1 1 1 1 Geropon DOS — 20 — — — 20 Break-Thru — — 50 — — — Vibrant Surfynol 440 — — — 50 — — Water (add to 1 To To To To To To litre) volume volume volume volume volume volume

[0324] Spray Coverage Tests on Leaves

[0325] The leaf deposit size was determined according to coverage method 5.

TABLE-US-00023 TABLE I2 Spray deposit coverage on non-textured leaves. High- High- spreading spreading surfactant Leaf coverage % surfactant dose % w/v Recipe apple dose g/ha (g/100 mL) Recipe I1 not 20.2 0 0 according to the invention - 10 l/ha Recipe I1 not 32.7 0 0 according to the invention - 300 l/ha Recipe I2 according to 15.0 20 0.2 the invention - 10 l/ha Recipe I2 according to 59.9 20 0.007 the invention - 300 l/ha Recipe I3 according to 9.9 50 0.5 the invention - 10 l/ha Recipe I3 according to 64.2 50 0.017 the invention - 300 l/ha Formulations applied at 1 l/ha.

[0326] The results show that the formulations according to the invention show improved spreading on non-textured leaves @300 l/ha than the formulations not according to the invention

TABLE-US-00024 TABLE I3 Spray deposit coverage, size and dose on textured leaves. High- High- spreading Leaf Leaf spreading surfactant coverage coverage surfactant dose % w/v Recipe % soybean % barley dose g/ha (g/100 mL) Recipe 2019-001462 19.3 19.0 0 0 not according to the invention - 10 l/ha Recipe 2019-001462 67.4 36.6 0 0 not according to the invention - 300 l/ha Recipe I2 according to 8.1 26.8 20 0.2 the invention - 10 l/ha Recipe I2 according to 67.7 56.7 20 0.007 the invention - 300 l/ha Recipe I3 according to 42.4 51.1 50 0.5 the invention - 10 l/ha Recipe I3 according to 61.7 71.4 50 0.017 the invention - 300 l/ha Formulations applied at 1 l/ha.

[0327] The results show that the formulations according to the invention show improved spreading @10 l/ha on barley than the formulations not according to the invention Pipette spreading tests on leaves

TABLE-US-00025 TABLE I4 Spray dilution droplet size and dose on non-textured leaves. High- Deposit High- spreading area spreading surfactant mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple dose g/ha (g/100 mL) Recipe I5 not 7.4 0 0 according to the invention - 10 l/ha Recipe I5 not 6.6 0 0 according to the invention - 20 l/ha Recipe I5 not 3.5 0 0 according to the invention - 200 l/ha Recipe I5 according to 11.1 20 0.2 the invention - 10 l/ha Recipe I5 according to 9.0 20 0.1 the invention - 20 l/ha Recipe I5 according to 4.7 20 0.01 the invention - 200 l/ha Formulations applied at 1 l/ha.

[0328] Formulations applied at 1 l/ha.

[0329] The results show that on non-structured leaves the deposit size is higher at lower water application volumes, and that the recipes according to the invention produce a larger deposit than the recipes not according to the invention.

TABLE-US-00026 TABLE I5 Spray dilution droplet size and dose on textured leaves. High- spread- ing High- Deposit Deposit Deposit surfac- spreading area area area tant surfactant mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose dose % w/v Recipe soybean rice barley g/ha (g/100 mL) Recipe I5 not 3.4 1.8 4.2 0 0 according to the invention - 10 l/ha Recipe I5 not 4.0 2.5 3.2 0 0 according to the invention - 20 l/ha Recipe I5 not 1.9 1.1 2.4 0 0 according to the invention - 200 l/ha Recipe I5 73.4 51.0 71.8 20 0.2 according to the invention - 10 l/ha Recipe I5 39.0 30.1 48.9 20 0.1 according to the invention - 20 l/ha Recipe I5 5.3 5.5 8.1 20 0.01 according to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0330] The results show that recipe I5 illustrative of the invention shows larger deposit sizes at 10 L/ha and 20 L/ha spray volume than at 200 L/ha and also compared to the reference recipe I5.

Example I2/Spidoxamate OD Formulations

[0331]

TABLE-US-00027 TABLE I6 /Spidoxamate OD Formulations Recipe I7 Recipe I8 Recipe I9 according according according Recipe I6 to the to the to the Component (g/l) reference invention invention invention Spidoxamate 12 12 12 12 Antarox B848 20 20 20 20 Propylene Glycol 150  150  150  150  Aerosil R812S 40 40 40 40 Diammonium 20 20 20 20 Hydrogen phosphate — — — — Geropon DOS — 20 — — Break-Thru — — 50 — Vibrant Surfynol 440 — — — 50 Dowanol DPM To volume To volume To volume To volume (add to 1 litre)

[0332] Pipette Spreading Tests on Leaves

[0333] The leaf deposit size was determined according to coverage method 5.

TABLE-US-00028 TABLE I7 Spray dilution droplet size and dose on non-textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple dose g/ha (g/100 mL) Recipe I6 not 6.3 0 0 according to the invention - 10 l/ha Recipe I6 not 6.2 0 0 according to the invention - 20 l/ha Recipe I6 not 6.0 0 0 according to the invention - 200 l/ha Recipe I7 according to 9.1 20 0.2 the invention - 10 l/ha Recipe I7 according to 9.8 20 0.1 the invention - 20 l/ha Recipe I7 according to 4.9 20 0.01 the invention - 200 l/ha Recipe I8 not 10.3 50 0.5 according to the invention - 10 l/ha Recipe I8 not 5.6 50 0.025 according to the invention - 200 l/ha Recipe I9 not 9.8 50 0.5 according to the invention - 10 l/ha Recipe I9 not 3.5 50 0.025 according to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0334] The results show that the recipes according to the invention promote a larger deposit size on non-structured leaves @10 and/or 20 l/ha than the recipes not according to the invention. Additionally, the recipes according to the invention promote a larger deposit size at 10 and/or 20 L/ha than @200 l/ha

TABLE-US-00029 TABLE I8 Spray dilution droplet size and dose on textured leaves. High- spread- ing High- Deposit Deposit Deposit surfac- spreading area area area tant surfactant mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose dose % w/v Recipe soybean rice barley g/ha (g/100 mL) Recipe I6 not 3.4 6.6 4.5 0 0 according to the invention - 10 l/ha Recipe I6 not 2.9 4.1 3.0 0 0 according to the invention - 20 l/ha Recipe I6 not 2.1 2.4 2.5 0 0 according to the invention - 200 l/ha Recipe I7 11.1 33.6 17.1 20 0.2 according to the invention - 10 l/ha Recipe I7 8.6 19.9 12.6 20 0.1 according to the invention - 20 l/ha Recipe I7 3.7 8.6 7.5 20 0.01 according to the invention - 200 l/ha Recipe I8 not 109.5 50 0.5 according to the invention - 10 l/ha Recipe I8 not 2.6 50 0.025 according to the invention - 200 l/ha Recipe I9 not 23.1 50 0.5 according to the invention - 10 l/ha Recipe I9 not 1.9 50 0.025 according to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0335] The results show that recipes I9, I8, I7 illustrative of the invention show larger deposit sizes at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe I6.

Example I3 Example X: Flubendiamide, Tetraniliprole SC Formulations

[0336]

TABLE-US-00030 TABLE I9 Flubendiamide, Tetraniliprole SC Formulations Recipe I11 Recipe I12 Recipe I13 Recipe I14 Recipe I15 according according according according according Recipe I10 to the to the to the to the to the Component (g/l) reference invention invention invention invention invention Tetraniliprole 40.0  40.0  40.0  40.0  — — Flubendiamide — — — — 120 120 Atlox 4913 40.0  40.0  40.0  40.0  — — Morwet IP 10.0  10.0  10.0  10.0  — — Synperonic 15.0  15.0  15.0  15.0  — — PE/F127 Lucramul PS 54 — — — — 12 12 Atlox 4913 — — — — 37 37 Citric Acid 1.0 1.0 1.0 1.0 — — Rhodopol 23 3.0 3.0 3.0 3.0 3.6 3.6 Sipernat 22 S 7.5 7.5 7.5 7.5 9 9 Geropon DOS — 20   — — — 20 Break-Thru — — 50   — — Vibrant Surfynol 440 — — — 50   — Kathon CG/ICP 0.8 0.8 0.8 0.8 1 1 Proxel GXL 1.2 1.2 1.2 1.2 1.5 1.5 Glycerin 100.0  100.0  100.0  100.0  122 122 SAG1572 1.5 1.5 1.5 1.5 1.8 1.8 Water (add to 1 fill fill fill fill fill fill litre)

[0337] Spray Coverage Tests on Leaves

[0338] The leaf deposit size was determined according to coverage method.

TABLE-US-00031 TABLE I10 Spray dilution droplet size and dose on non-textured leaves. High- Leaf Leaf High- spreading coverage coverage spreading surfactant @ 0°, % @ 0°, % surfactant dose % w/v Recipe apple abutilon dose g/ha (g/100 mL) Recipe I10 not 11.7 7 0 0 according to the invention - 10 l/ha Recipe I10 not 30.1 23.1 0 0 according to the invention - 200 l/ha Recipe I11 16.6 9.1 20 0.2 according to the invention - 10 l/ha Recipe I11 51.4 42.0 20 0.01 according to the invention - 200 l/ha Recipe I12 21.3 7.4 50 0.5 according to the invention - 10 l/ha Recipe I12 77.3 38.8 50 0.025 according to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0339] The results show that the formulations according to the invention show on non-textured leaves similar to improved spreading @10 l/ha than the formulations not according to the invention

TABLE-US-00032 TABLE I11 Spray dilution droplet size and dose on textured leaves. High- Leaf Leaf Leaf High- spreading coverage coverage coverage spreading surfactant @ 0°, % @ 0°, % @ 0°, % surfactant dose % w/v Recipe soybean barley rice dose g/ha (g/100 mL) Recipe I10 not according 6.3 5.2 5.8 0 0 to the invention - 10 l/ha Recipe I10 not according 23.3 14.7 9.2 0 0 to the invention - 200 l/ha Recipe I11 according to 20.8 20.8 33 20 0.2 the invention - 10 l/ha Recipe I11 according to 36.3 29.0 24.7 20 0.01 the invention - 200 l/ha Recipe I12 according to 38.0 27.8 18.2 50 0.5 the invention - 10 l/ha Recipe I12 according to 41.1 36.8 38.8 50 0.025 the invention - 200 l/ha Formulations applied at 1 l/ha.

[0340] The results show that recipes I12 and I11 illustrative of the invention show greater coverage at 10 L/ha spray volume than compared to the reference recipe I10.

[0341] Pipette Spreading Tests on Leaves

TABLE-US-00033 TABLE I12 Spray dilution droplet size and dose on non-textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple dose g/ha (g/100 mL) Recipe I14 not 4.4 0 0 according to the invention - 10 l/ha Recipe I14 not 3.1 0 0 according to the invention - 200 l/ha Recipe I15 according 13.9 20 0.2 to the invention - 10 l/ha Recipe I15 according 5.6 20 0.01 to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0342] The results show that on non-structured leaves the deposit size is slightly higher at lower water application volume, and that the recipe according to the invention produces larger deposits than the recipe not according to the invention.

TABLE-US-00034 TABLE I13 Spray dilution droplet size and dose on textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe soybean dose g/ha (g/100 mL) Recipe I14 not 1.6 0 0 according to the invention - 10 l/ha Recipe I14 not 1.6 0 0 according to the invention - 200 l/ha Recipe I15 not 133.2 20 0.2 according to the invention - 10 l/ha Recipe I15 not 4.6 20 0.01 according to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0343] The results show that recipe I14 illustrative of the invention shows greater larger deposit sizes at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe I14.

Example I4 Deltamethrin, Beta-Cyfluthrin SC Formulations

[0344]

TABLE-US-00035 TABLE I14 Deltamethrin, beta-cyfluthrin SC formulations Recipe I19 Recipe I17 according according to the Recipe I16 to the Recipe I18 invention Component (g/l) reference invention reference I19 Deltamethrin 25 25 — — Beta-Cyfluthrin — — 25 25 Agnique SLS 90 0.1 0.1 — — Dispersogen SI 15 15 — — Lucramul PS 29 — — 20 20 Citric Acid 0.2 0.2 0.2 0.2 Rhodopol 23 4 4 4 4 Sipernat 22 S 15 15 30 30 — — — — Geropon DOS — 20 — 20 Kathon CG/ICP 0.8 0.8 1 1 Proxel GXL 1.2 1.2 1.5 1.5 Glycerin 150 150 100 100 SAG1572 0.5 0.5 0.5 0.5 Water (add to 1 fill fill fill fill litre)

[0345] Pipette Spreading Tests on Leaves

[0346] The leaf deposit size was determined according to coverage method 5.

TABLE-US-00036 TABLE I15 Spray dilution droplet size and dose on non-textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple dose g/ha (g/100 mL) Recipe I16 not 6.0 0 0 according to the invention - 10 l/ha Recipe I16 not 5.0 0 0 according to the invention - 20 l/ha Recipe I16 not 2.4 0 0 according to the invention - 200 l/ha Recipe I16 not 1.6 0 0 according to the invention - 300 l/ha Recipe I17 according 13.8 10 0.1 to the invention - 10 l/ha Recipe I17 according 11.5 10 0.05 to the invention - 20 l/ha Recipe I17 according 7.0 10 0.005 to the invention - 200 l/ha Recipe I17 according 5.6 10 0.003 to the invention - 300 l/ha Formulations applied at 1 l/ha.

[0347] The results show that on non-structured leaves the deposit size is slightly higher at lower water application volume, and that the recipe according to the invention produces larger deposits than the recipe not according to the invention.

TABLE-US-00037 TABLE I16 Spray dilution droplet size and dose on textured leaves. High- spread- ing High- Deposit Deposit Deposit surfac- spreading area area area tant surfactant mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose dose % w/v Recipe soybean rice barley g/ha (g/100 mL)) Recipe I16 not 2.2 2.4 4.1 0 0 according to the invention - 10 l/ha Recipe I16 not 1.8 1.3 2.5 0 0 according to the invention - 20 l/ha Recipe I16 not 0.8 0.5 1.5 0 0 according to the invention - 200 l/ha Recipe I16 not 0.6 0.3 0.6 0 0 according to the invention - 300 l/ha Recipe I17 127 88.1 88.1 10 0.1 according to the invention - 10 l/ha Recipe I17 89.3 61.8 69.4 10 0.05 according to the invention - 20 l/ha Recipe I17 13.9 8.8 11.7 10 0.005 according to the invention - 200 l/ha Recipe I17 6.6 7.6 9.0 10 0.003 according to the invention - 300 l/ha Formulations applied at 0.5 l/ha.

[0348] The results show that recipe I17 illustrative of the invention shows larger deposit sizes at 10 L/ha and 20 L/ha spray volume than at 200 L/ha and 300 L/ha and also compared to the reference recipe I16.

TABLE-US-00038 TABLE I17 Spray dilution droplet size and dose on non-textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple dose g/ha (g/100 mL)) Recipe I18 not 6.8 0 0 according to the invention - 10 l/ha Recipe I18 not 4.8 0 0 according to the invention - 20 l/ha Recipe I18 not 1.6 0 0 according to the invention - 200 l/ha Recipe I18 not 2.1 0 0 according to the invention - 300 l/ha Recipe I19 according 8.3 10 0.1 to the invention - 10 l/ha Recipe I19 according 7.8 10 0.05 to the invention - 20 l/ha Recipe I19 according 3.3 10 0.005 to the invention - 200 l/ha Recipe I19 according 3.8 10 0.003 to the invention - 300 l/ha Formulations applied at 0.5 l/ha.

[0349] The results show that on non-textured leaves the deposit size is slightly higher at lower water application volume, and that the recipe according to the invention produces larger deposits than the recipe not according to the invention.

TABLE-US-00039 TABLE I18 Spray dilution droplet size and dose on textured leaves. High- spread- ing High- Deposit Deposit Deposit surfac- spreading area area area tant surfactant mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose dose % w/v Recipe soybean rice barley g/ha (g/100 mL)) Recipe I18 not 3.0 3.0 3.4 0 0 according to the invention - 10 l/ha Recipe I18 not 3.5 2.6 3.8 0 0 according to the invention - 20 l/ha Recipe I18 not 1.2 1.0 1.9 0 0 according to the invention - 200 l/ha Recipe I18 not 1.2 0.7 2.1 0 0 according to the invention - 300 l/ha Recipe I19 8.7 26.6 14.9 10 0.1 according to the invention - 10 l/ha Recipe I19 6.1 19.6 13.3 10 0.05 according to the invention - 20 l/ha Recipe I19 2.4 1.5 2.9 10 0.005 according to the invention - 200 l/ha Recipe I19 2.2 1.5 2.6 10 0.003 according to the invention - 300 l/ha Formulations applied at 0.5 l/ha.

[0350] The results show that recipe I19 illustrative of the invention shows larger deposit sizes at 10 L/ha and 20 L/ha spray volume than at 200 L/ha and 300 L/ha and also compared to the reference recipe I18.

Example I5 Clothianidin, Imidacloprid, Thiacloprid SC Formulations

[0351]

TABLE-US-00040 TABLE I19 Clothianidin, Imidacloprid, Thiacloprid SC formulations Recipe I21 Recipe I23 Recipe I25 according according according Recipe I20 to the Recipe I22 to the Recipe I24 to the Component (g/l) reference invention reference invention reference invention Clothianidin 100  100  — — — — Imidacloprid — — 50 50 — — Thiacloprid — — — — 120 120 Atlox 4913 70  70  52 52 33 33 Atlox 4894 12  12  — — — — — — — — Lucramul PS 54 — — 17 17 11 11 Rhodopol 23 4 4  4  4 4 4 Sipernat 22 S 6 6 — — — — — — — — — — Geropon DOS — 20  — 20 — 20 Proxel GXL   1.2   1.2   1.2   1.2 1.2 1.2 Kathon CG/ICP   0.8   0.8   0.8   0.8 0.8 0.8 Glycerin 116  116  115  115  — — Urea — — — — 111 111 SAG1572 2 2  1  1 1 1 Water (add fill fill fill fill fill fill to 1 litre)

[0352] Pipette Spreading Tests on Leaves

[0353] The leaf deposit size was determined according to coverage method 5.

TABLE-US-00041 TABLE I20 Spray dilution droplet size and dose on non-textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple dose g/ha (g/100 mL) Recipe I20 not 9.2 0 0 according to the invention - 10 l/ha Recipe I20 not 8.6 0 0 according to the invention - 20 l/ha Recipe I20 not 6.4 0 0 according to the invention - 200 l/ha Recipe I21 according 12.7 20 0.2 to the invention - 10 l/ha Recipe I21 according 11.5 20 0.1 to the invention - 20 l/ha Recipe I21 according 6.7 20 0.01 to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0354] The results show that on non-textured leaves the deposit size is slightly higher at lower water application volume, and that the recipe according to the invention produces larger deposits than the recipe not according to the invention.

TABLE-US-00042 TABLE I21 Spray dilution droplet size and dose on textured leaves. High- spread- ing High- Deposit Deposit Deposit surfac- spreading area area area tant surfactant mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose dose % w/v Recipe soybean rice barley g/ha (g/100 mL) Recipe I20 not 5.8 6.1 7.9 0 0 according to the invention - 10 l/ha Recipe I20 not 5.0 6.9 7.5 0 0 according to the invention - 20 l/ha Recipe I20 not 3.1 2.5 4.2 0 0 according to the invention - 200 l/ha Recipe I21 71.3 79.6 82.4 20 0.2 according to the invention - 10 l/ha Recipe I21 40.2 52.9 49.9 20 0.1 according to the invention - 20 l/ha Recipe I21 7.4 2.9 9.0 20 0.01 according to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0355] The results show that recipe I21 illustrative of the invention shows greater coverage and larger deposit sizes at 10 L/ha and 20 L/ha spray volume than at 200 L/ha and also compared to the reference recipe I20.

TABLE-US-00043 TABLE I22 Spray dilution droplet size and dose on non-textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple dose g/ha (g/100 mL) Recipe I22 not 4.7 0 0 according to the invention - 10 l/ha Recipe I22 not 4.5 0 0 according to the invention - 20 l/ha Recipe I22 not 1.7 0 0 according to the invention - 200 l/ha Recipe I23 according 9.1 20 0.2 to the invention - 10 l/ha Recipe I23 according 8.0 20 0.1 to the invention - 20 l/ha Recipe I23 according 3.5 20 0.01 to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0356] The results show that on non-textured leaves the deposit size is slightly higher at lower water application volume, and that the recipe according to the invention produces larger deposits than the recipe not according to the invention.

TABLE-US-00044 TABLE I23 Spray dilutiondroplet size and dose on textured leaves. High- spread- ing High- Deposit Deposit Deposit surfac- spreading area area area tant surfactant mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose dose % w/v Recipe soybean rice barley g/ha (g/100 mL)) Recipe I22 not 2.5 1.5 3.8 0 0 according to the invention - 10 l/ha Recipe I22 not 1.7 1.6 3.5 0 0 according to the invention - 20 l/ha Recipe I22 not 1.1 1.0 2.2 0 0 according to the invention - 200 l/ha Recipe I23 34.4 20 0.2 according to the invention - 10 l/ha Recipe I23 33.7 20 0.1 according to the invention - 20 l/ha Recipe I23 1.8 20 0.01 according to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0357] The results show that recipe I23 illustrative of the invention shows larger deposit sizes at 10 L/ha and 20 L/ha spray volume than at 200 L/ha and also compared to the reference recipe I22.

TABLE-US-00045 TABLE I24 Spray dilution droplet size and dose on non-textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple dose g/ha (g/100 mL) Recipe I24 not 5.3 0 0 according to the invention - 10 l/ha Recipe I24 not 5.0 0 0 according to the invention - 20 l/ha Recipe I24 not 3.0 0 0 according to the invention - 200 l/ha Recipe I25 according 12.3 20 0.2 to the invention - 10 l/ha Recipe I25 according 9.2 20 0.1 to the invention - 20 l/ha Recipe I25 according 4.6 20 0.01 to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0358] The results show that on non-textured leaves the deposit size is slightly higher at lower water application volume, and that the recipe according to the invention produces larger deposits than the recipe not according to the invention.

TABLE-US-00046 TABLE I25 Spray dilution droplet size and dose on textured leaves. High- spread- ing High- Deposit Deposit Deposit surfac- spreading area area area tant surfactant mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose dose % w/v Recipe soybean rice barley g/ha (g/100 mL) Recipe I24 not 2.7 1.7 4.2 0 0 according to the invention - 10 l/ha Recipe I24 not 2.2 1.2 3.5 0 0 according to the invention - 20 l/ha Recipe I24 not 1.8 0.5 2.5 0 0 according to the invention - 200 l/ha Recipe I25 25.9 68.2 54.4 20 0.2 according to the invention - 10 l/ha Recipe I25 31.4 42.8 42.7 20 0.1 according to the invention - 20 l/ha Recipe I25 4.6 2.5 9.8 20 0.01 according to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0359] The results show that recipe I25 illustrative of the invention shows larger deposit sizes at 10 L/ha and 20 L/ha spray volume than at 200 L/ha and also compared to the reference recipe I24.

Example I6 Ethiprole, Fipronil, Imidacloprid SC Formulations

[0360]

TABLE-US-00047 TABLE I26 Ethiprole, Fipronil, Imidacloprid SC formulations Recipe I30 reference Recipe I27 Recipe I29 2019- Recipe I31 Recipe I32 Recipe I33 according according 010494 according according according Recipe I26 to the Recipe I28 to the 2020- to the to the to the reference invention reference invention 00096 invention invention invention 2019- 2019- 2019- 2019- 2020- 2019- 2019- 2020- Component (g/l) 010371 010370 010374 010373 003270 010508 010511 000968 Ethiprole 100 100 — — 100  100  100  100  Fipronil — — 50 50 — — — — Imidacloprid — — — — 100  100  100  100  Soprophor 38 38 14 14 — — — — FLK Morwet — — 14 14 11  11  11  11  D425 Rhodasruf — — 5  5 — — — — 860/P Atlox 4913 — — — — 69  69  69  69  Atlas G 5000 — — — — 22  22  22  22  Citric Acid 0.2 0.2 0.2   0.2 2 2 2 2 Rhodopol 4 4 4  4 4 4 4 4 23 Van Gel B 5 5 — — — — — — Veegum R — — — — 6 6 6 6 — — — — — — — — Geropon — 20 — 20 — 20  — — DOS Break-Thru — — — — — — 50  — Vibrant Surfynol 440 — — — — — — — 50  Kathon 0.8 0.8 0.8   0.8   0.8   0.8   0.8   0.8 CG/ICP Proxel GXL 1.2 1.2 1.2   1.2   1.2   1.2   1.2   1.2 Propylene 123 123 51 51 110  110  110  110  Glycol SAG1572 3 3 3  3 — — — — Silcolapse — — — — 3 3 3 3 426R Water (add fill fill fill fill fill fill fill fill to 1 litre)

[0361] Pipette Spreading Tests on Leaves

[0362] The leaf deposit size was determined according to coverage method 5.

TABLE-US-00048 TABLE I27 Spray dilution droplet size and dose on non-textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple dose g/ha (g/100 mL) Recipe I26 not 4.2 0 0 according to the invention - 10 l/ha Recipe I26 not 5.1 0 0 according to the invention - 20 l/ha Recipe I26 not 2.4 0 0 according to the invention - 200 l/ha Recipe I26 not 2.0 0 0 according to the invention - 300 l/ha Recipe I27 according 9.8 10 0.1 to the invention - 10 l/ha Recipe I27 according 8.0 10 0.05 to the invention - 20 l/ha Recipe I27 according 3.3 10 0.005 to the invention - 200 l/ha Recipe I27 according 5.1 10 0.003 to the invention - 300 l/ha Formulations applied at 0.5 l/ha.

[0363] The results show that on non-structured leaves the deposit size is slightly higher at lower water application volume, and that the recipe according to the invention produces larger deposits than the recipe not according to the invention.

TABLE-US-00049 TABLE I28 Spray dilution droplet size and dose on textured leaves. High- spread- ing High- Deposit Deposit Deposit surfac- spreading area area area tant surfactant mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose dose % w/v Recipe soybean rice barley g/ha (g/100 mL) Recipe I26 not 2.9 2.0 3.9 0 0 according to the invention - 10 l/ha Recipe I26 not 2.6 1.9 4.6 0 0 according to the invention - 20 l/ha Recipe I26 not 1.9 1.0 2.7 0 0 according to the invention - 200 l/ha Recipe I26 not 1.8 0.9 2.3 0 0 according to the invention - 300 l/ha Recipe I27 38.2 62.2 26.6 10 0.1 according to the invention - 10 l/ha Recipe I27 31.6 44.9 15.9 10 0.05 according to the invention - 20 l/ha Recipe I27 13.1 10.5 7.5 10 0.005 according to the invention - 200 l/ha Recipe I27 5.3 7.8 6.5 10 0.003 according to the invention - 300 l/ha Formulations applied at 0.5 l/ha.

[0364] The results show that recipe I27 illustrative of the invention shows larger deposit sizes at 10 L/ha spray and 20 L/ha volume than at 200 L/ha and 300 L/ha and also compared to the reference recipe I26.

TABLE-US-00050 TABLE I29 Spray dilution droplet size and dose on non-textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple dose g/ha (g/100 mL) Recipe I28 not 7.4 0 0 according to the invention - 10 l/ha Recipe I28 not 6.4 0 0 according to the invention - 20 l/ha Recipe I28 not 4.8 0 0 according to the invention - 200 l/ha Recipe I28 not 1.1 0 0 according to the invention - 300 l/ha Recipe I29 according 14.9 20 0.2 to the invention - 10 l/ha Recipe I29 according 10.2 20 0.1 to the invention - 20 l/ha Recipe I29 according 5.4 20 0.01 to the invention - 200 l/ha Recipe I29 according 4.8 20 0.007 to the invention - 300 l/ha Formulations applied at 1 l/ha.

[0365] The results show that on non-textured leaves the deposit size is slightly higher at lower water application volume, and that the recipe according to the invention produces larger deposits than the recipe not according to the invention.

TABLE-US-00051 TABLE I30 Spray dilution droplet size and dose on textured leaves. High- spread- ing High- Deposit Deposit Deposit surfac- spreading area area area tant surfactant mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose dose % w/v Recipe soybean rice barley g/ha (g/100 mL) Recipe I28 not 4.5 3.8 4.8 0 0 according to the invention - 10 l/ha Recipe I28 not 3.7 2.8 4.3 0 0 according to the invention - 20 l/ha Recipe I28 not 2.1 2.0 3.4 0 0 according to the invention - 200 l/ha Recipe I28 not 1.7 1.3 2.2 0 0 according to the invention - 300 l/ha Recipe I29 150.0 152.0 72.2 20 0.2 according to the invention - 10 l/ha Recipe I29 92.1 127.0 55.7 20 0.1 according to the invention - 20 l/ha Recipe I29 3.1 2.3 16.2 20 0.01 according to the invention - 200 l/ha Recipe I29 2.0 1.9 3.2 20 0.007 according to the invention - 300 l/ha Formulations applied at 1 l/ha.

[0366] The results show that recipe I29 illustrative of the invention shows larger deposit sizes at 10 L/ha spray and 20 L/ha volume than at 200 L/ha and 300 L/ha and also compared to the reference recipe I28.

TABLE-US-00052 TABLE I31 Spray dilution droplet size and dose on non-textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple dose g/ha (g/100 mL) Recipe I30 not 5.5 0 0 according to the invention - 10 l/ha Recipe I30 not 5.5 0 0 according to the invention - 20 l/ha Recipe I30 not 1.0 0 0 according to the invention - 200 l/ha Recipe I30 not 1.0 0 0 according to the invention - 300 l/ha Recipe I31 according 8.6 10 0.1 to the invention - 10 l/ha Recipe I31 according 7.9 10 0.05 to the invention - 20 l/ha Recipe I31 according 7.5 10 0.005 to the invention - 200 l/ha Recipe I31 according 3.0 10 0.003 to the invention - 300 l/ha Recipe I32 according 10.4 25 0.25 to the invention - 10 l/ha Recipe I32 according 9.9 25 0.125 to the invention - 20 l/ha Recipe I32 according 7.5 25 0.012 to the invention - 200 l/ha Recipe I32 according 5.9 25 0.008 to the invention - 300 l/ha Formulations applied at 0.5 l/ha.

[0367] The results show that on non-textured leaves the deposit size is slightly higher at lower water application volume, and that the recipe according to the invention produces larger deposits than the recipe not according to the invention.

TABLE-US-00053 TABLE I32 Spray dilution droplet size and dose on textured leaves. High- spread- ing High- Deposit Deposit Deposit surfac- spreading area area area tant surfactant mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose dose % w/v Recipe soybean rice barley g/ha (g/100 mL) Recipe I30 not 2.4 1.5 4.1 0 0 according to the invention - 10 l/ha Recipe I30 not 2.1 1.5 3.4 0 0 according to the invention - 20 l/ha Recipe I30 not 1.8 0.9 2.3 0 0 according to the invention - 200 l/ha Recipe I30 not 1.1 0.9 2.3 0 0 according to the invention - 300 l/ha Recipe I31 6.7 36.3 9.0 10 0.1 according to the invention - 10 l/ha Recipe I31 5.0 19.5 7.4 10 0.05 according to the invention - 20 l/ha Recipe I31 2.5 1.8 4.6 10 0.005 according to the invention - 200 l/ha Recipe I31 2.0 1.8 3.0 10 0.003 according to the invention - 300 l/ha Recipe I32 188.0 144.0 106.0 25 0.25 according to the invention - 10 l/ha Recipe I32 71.9 117.0 54.1 25 0.125 according to the invention - 20 l/ha Recipe I32 2.5 2.7 6.8 25 0.012 according to the invention - 200 l/ha Recipe I32 2.5 2.1 3.0 25 0.008 according to the invention - 300 l/ha Formulations applied at 0.5 l/ha.

[0368] The results show that recipes I31 and I32 illustrative of the invention show larger deposit sizes at 10 L/ha and 20 L/ha spray volume than at 200 L/ha and 300 L/ha also compared to the reference recipe I30.

TABLE-US-00054 TABLE I33 Spray dilution droplet size and dose on non-textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple dose g/ha (g/100 mL) Recipe I30 not 6.3 0 0 according to the invention - 10 l/ha Recipe I30 not 4.5 0 0 according to the invention - 200 l/ha Recipe I33 according 8.2 50 0.5 to the invention - 10 l/ha Recipe I33 according 4.2 50 0.024 to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0369] The results show that on non-textured leaves the deposit size is slightly higher at lower water application volume, and that the recipe according to the invention produces larger deposits than the recipe not according to the invention at lower water application volume.

TABLE-US-00055 TABLE I34 Spray dilution droplet size and dose on textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe soybean dose g/ha (g/100 mL) Recipe I30 not 3.1 0 0 according to the invention - 10 l/ha Recipe I30 not 2.0 0 0 according to the invention - 200 l/ha Recipe I33 according 45.5 50 0.5 to the invention - 10 l/ha Recipe I33 according 1.9 50 0.024 to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0370] The results show that recipe I33 illustrative of the invention shows larger deposit sizes at 10 L/ha spray volume than at 200 L/ha also compared to the reference recipe I30.

Example I7 Fluopyram SC Formulations

[0371]

TABLE-US-00056 TABLE I35 Fluopyram SC formulations Recipe I35 according Recipe I34 to the Component (g/l) reference invention Fluopyram 100 100 Surfynol 440 4 4 Morwet D425 4 4 Synperonic 44 44 PE/F127 Atlox 4913 3 3 Citric Acid 0.4 0.4 Rhodopol 23 4 4 — — Geropon DOS — 20 Kathon CG/ICP 0.8 0.8 Proxel GXL 1.2 1.2 Propylene 81 81 Glycol SAG1572 3 3 Silcolapse — — 426R Water (add Fill fill to 1 litre)

[0372] Pipette Spreading Tests on Leaves

[0373] The leaf deposit size was determined according to coverage method.

TABLE-US-00057 TABLE I36 Spray dilution droplet size and dose on non-textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple dose g/ha (g/100 mL) Recipe I34 not 6.4 0 0 according to the invention - 10 l/ha Recipe I34 not 5.5 0 0 according to the invention - 20 l/ha Recipe I34 not 3.6 0 0 according to the invention - 200 l/ha Recipe I35 not 10.1 20 0.2 according to the invention - 10 l/ha Recipe I35 not 7.9 20 0.1 according to the invention - 20 l/ha Recipe I35 according 5.2 20 0.01 to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0374] The results show that on non-textured leaves the deposit size is slightly higher at lower water application volume, and that the recipe according to the invention produces larger deposits than the recipe not according to the invention.

TABLE-US-00058 TABLE I37 Spray dilution droplet size and dose on textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe soybean dose g/ha (g/100 mL) Recipe I34 not 2.9 0 0 according to the invention - 10 l/ha Recipe I34 not 2.4 0 0 according to the invention - 20 l/ha Recipe I34 not 1.7 0 0 according to the invention - 200 l/ha Recipe I35 according 18.3 20 0.2 to the invention - 10 l/ha Recipe I35 according 15.8 20 0.1 to the invention - 20 l/ha Recipe I35 according 3.7 20 0.01 to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0375] The results show that recipe I35 illustrative of the invention shows larger deposit sizes at 10 L/ha and 20 L/ha spray volume than at 200 L/ha and also compared to the reference recipe I34.

Example I8 Flupyradifurone SC Formulations

[0376]

TABLE-US-00059 TABLE I38 Flupyradifurone SC formulations Recipe I37 according Recipe I36 to the Component (g/l) reference invention Flupyradifurone 200 200 Mowiol 8-88 33 33 Atlox 4894 11 11 Atlox 4913 50 50 Citric Acid 0.5 0.5 Rhodopol 23 2 2 Aerosil R972 7 7 — — Geropon DOS — 20 Kathon CG/ICP 0.8 0.8 Proxel GXL 1.2 1.2 Urea 71 71 SAG1572 11 11 Silcolapse 426R — — Water (add to 1 litre) fill fill

[0377] Pipette Spreading Tests on Leaves

[0378] The leaf deposit size was determined according to coverage method.

TABLE-US-00060 TABLE I39 Spray dilution droplet size and dose on non-textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple dose g/ha (g/100 mL) Recipe I36 not 6.5 0 0 according to the invention - 10 l/ha Recipe I36 not 3.5 0 0 according to the invention - 200 l/ha Recipe I37 not 14.9 20 0.2 according to the invention - 10 l/ha Recipe I37 not 6.7 20 0.01 according to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0379] The results show that on non-textured leaves the deposit size is slightly higher at lower water application volume, and that the recipe according to the invention produces larger deposits than the recipe not according to the invention.

TABLE-US-00061 TABLE I40 Spray dilution droplet size and dose on textured leaves. High- High- spreading Deposit spreading surfactant area mm{circumflex over ( )}2 surfactant dose % w/v Recipe soybean dose g/ha (g/100 mL) Recipe I36 not 3.7 0 0 according to the invention - 10 l/ha Recipe I36 not 1.5 0 0 according to the invention - 200 l/ha Recipe I37 not 361.8 20 0.2 according to the invention - 10 l/ha Recipe I37 not 7.5 20 0.01 according to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0380] The results show that recipe I37 illustrative of the invention shows larger deposit sizes at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe I36.

Example I9 Greenhouse Testing TETRANILIPROLE SC040 Formulations

[0381]

TABLE-US-00062 TABLE I41 Biological efficacy (in % mortality) against mixed population of Myzus persicae on pre-infested cabbage, evaluation 7 days after application Recipe I12 according Recipe I11 to the according invention to the 2019- invention Recipe I10 006010 2019-006008 Spray volume Rate of reference (Break Thru (GEROPON l/ha a.i. g/ha 2019-006112 Vibrant) DOS) 300 100 0 0 0 300 20 0 0 0 300 4 0 0 0 10 100 85 95 93 10 20 0 25 20 10 4 0 0 0 (Test methodology: application onto upperside of pre-infested 1-leaf cabbage plants, BBCH12, for translaminar activity, 2 replicates. Tracksprayer settings: 10 l/ha applied using Lechler's PWM together with nozzle 652.246; 300 l/ha applied using nozzle TeeJet TP8003E.)

[0382] The results show that the recipes according to the invention have higher efficacy at 10 l/ha water volume than at 300 l/ha. Additionally, the recipes according to the invention are slightly more efficacious than the recipes not according to the invention.

[0383] Herbicide Examples

Example HB1

[0384]

TABLE-US-00063 TABLE HB1 Recipes HB1, HB2 and HB3. Recipe HB2 Recipe HB3 according according Recipe HB1 to the to the Component (g/l) reference invention invention Tembotrione (a) 100 100 100 Isoxadifen-ethyl (a) 50 50 50 ATLAS ® G 5000 (c) 10.5 10.5 10.5 Synperonic ® A7 (c) 10.5 10.5 10.5 Atlox ® 4913  © 31.5 31.5 31.5 Silwet ® HS 312 (b) 0 50 0 Silwet ® HS 604 (b) 0 0 40 Xanthan (c) 1.9 1.9 1.9 Acticide ® MBS (c) 2.1 2.1 2.1 Propylene glycol (c) 52.5 52.5 52.5 SILCOLAPSe ®454 (c) 2.44 2.44 2.44 Water (add to volume) to volume to volume to volume Dose rate 1 L/ha. The method of preparation used was according to Method 1.

[0385] Pipette Spreading Tests on Leaves

[0386] The leaf coverage was determined according to coverage method 5.

TABLE-US-00064 TABLE HB2 Spray deposit coverage and dose on non-textured leaves. Leaf Leaf Leaf Organosilicone Organosilicone coverage % coverage % coverage % surfactant surfactant Recipe apple corn abutilon dose g/ha dose % w/v Recipe HB1 not 10.2 17.4 14.6 0 0 according to the invention - 10 l/ha Recipe HB1 not 40.2 34.2 26.6 0 0 according to the invention - 200 l/ha Recipe HB2 30.8 28.8 24.6 50 0.5 according to the invention - 10 l/ha Recipe HB2 47.3 42.2 31 50 0.025 according to the invention - 200 l/ha Recipe HB3 13.8 15.6 16.1 40 0.4 according to the invention - 10 l/ha Recipe HB3 54.9 34.1 33.5 40 0.02 according to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0387] The results show that on non-textured leaves the coverage is higher at higher water application volumes.

TABLE-US-00065 TABLE HB3 Spray deposit coverage and dose on textured leaves. Organo- Organo- Leaf Leaf silicone silicone coverage coverage surfactant surfactant Recipe % barley % soybean dose g/ha dose % w/v Recipe HB1 not 23.7 13.2 0 0 according to the invention - 10 l/ha Recipe HB1 not 12 25.2 0 0 according to the invention - 200 l/ha Recipe HB2 49.1 33.2 50 0.5 according to the invention - 10 l/ha Recipe HB2 29.4 35.3 50 0.025 according to the invention - 200 l/ha Recipe HB3 55.7 39.2 40 0.4 according to the invention - 10 l/ha Recipe HB3 29.6 39.6 40 0.002 according to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0388] The results show that recipes HB2 and HB3 illustrative of the invention show greater or similar coverage at 10 L/ha spray volume than at 200 L/ha on textured leaves and also compared to the reference recipe HB1.

Example HB2

[0389]

TABLE-US-00066 TABLE HB4 Recipes HB4 andHB5 Recipe HB5 Recipe HB4 according to Component (g/l) reference the invention TRIAFAMONE (a) 70.00 70.00 Geropon DOS (b) 0.00 50.00 ATLOX 4913 (c) 32.40 32.40 ATLOX 4894 (c) 21.60 21.60 1.2-PROPYLENE GLYCOL (c) 54.00 54.00 Silcolapse ® 454 (c) 2.16 2.16 Proxel ® GXL (c) 1.94 1.94 Kathon ® CG/ICP (c) 0.86 0.86 RHODOPOL ® 23 (c) 4.32 4.32 Na.sub.2HPO.sub.4 (Buffer solution pH = 7) (c) 1.5 1.5 NaH.sub.2PO.sub.4 (Buffer solution pH = 7) (c) 0.8 0.8 Water (add to volume) (c) to volume to volume Formulations applied at 1 l/ha.

[0390] The method of preparation used was according to Method 1.

[0391] Pipette Spreading Tests on Leaves

[0392] The leaf deposit size was determined according to the coverage method 5.

TABLE-US-00067 TABLE HB4 Spray dilution droplet size and dose on non-textured leaves. High- High- Deposit spreading spreading area mm{circumflex over ( )}2 surfactant surfactant Recipe apple dose g/ha dose % w/v Recipe HB4 not 8.6 0 0 according to the invention - 10 l/ha Recipe HB4 not 6.8 0 0 according to the invention - 200 l/ha Recipe HB5 according 14.3 50 0.5 to the invention - 10 l/ha Recipe HB5 according 11.9 50 0.025 to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0393] The results show that on non-textured leaves the deposit size is higher at lower water application volume.

TABLE-US-00068 TABLE HB5 Spray dilution droplet size and dose on textured leaves. High- High- Deposit spreading spreading area mm{circumflex over ( )}2 surfactant surfactant Recipe soybean dose g/ha dose % w/v Recipe HB4 not 6.4 0 0 according to the invention - 10 l/ha Recipe HB4 not 3.9 0 0 according to the invention - 200 l/ha Recipe HB5 according 105.0 50 0.5 to the invention - 10 l/ha Recipe HB5 according 18.2 50 0.025 to the invention - 200 l/ha Formulations applied at 1 l/ha.

[0394] The results show that recipes HB5 illustrative of the invention show larger deposit sizes at 10 L/ha spray volume than at 200 L/ha and compared to the reference recipe HB4.