HIGH SPREADING ULV FORMULATIONS FOR INSECTICIDES

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 selected from the group of agrochemically applied insecticides, b) an organosilicone based surfactant, c) one or more other formulants, and d) carrier to volume, wherein b) is present in an amount from 0.5 to 15% by weight.

2. The agrochemical formulation according to claim 1, wherein b) is a polyalkyleneoxide modified heptamethyltrisiloxane.

3. The agrochemical formulation according to claim 1, wherein a) is present in an amount from 0.5 to 30% by weight, preferably from 1 to 27.5% by weight, and most preferably from 1.2 to 25% by weight.

4. The agrochemical formulation according to claim 1, wherein the insecticide is selected from the group consisting of spirotetramat, spiromesifen, spidoxamate (IUPAC Name: 1i-(4-chloro-2,6-xylyl)-12-hydroxy-1,4-dioxa-9-azadispiro[4.2.4.2]tetradec-11-en-10-one), flubendiamide, tetraniliprole, deltamethrin, ß-cyfluthrin, imidacloprid, thiacloprid, ethiprole, fipronil, fluopyram and flupyradifurone.

5. The agrochemical formulation according to claim 1, wherein b) is present in an amount from 0.75 to 10% by weight, and more preferably from 1 to 6% by weight.

6. The agrochemical formulation according to claim 1, wherein c) is present in an amount from in 0.5 to 65% by weight, preferably from 1 to 49.5% by weight, and more preferably from 2 to 37.5% by weight.

7. The agrochemical formulation according to claim 1, wherein component c) comprises at least one non-ionic surfactant and/or ionic surfactant.

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

9. The agrochemical formulation according to claim 8, wherein c1) is present in an amount from 2 to 15% by weight, c2) is present in an amount from 0.1 to 20% by weight, c3) is present in an amount from 0.05 to 5% by weight, and c4 is present in an amount from 0.1 to 20% by weight.

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

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

12. The method according to claim 11, wherein the applied amount of a) to the crop is between 2 and 250 g/ha, preferably between 5 and 225 g/ha, and more preferably between 10 and 200 g/ha.

13. The method according to claim 11, wherein the organosilicone-surfactant of b) is preferably applied from 5 g/ha to 150 g/ha, more preferably applied from 7.5 g/ha to 100 g/ha, and most preferably applied 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 insecticidal pests, 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, habitats of the harmful organisms, or hosts of the harmful organisms, such as plants and seed, soil, areas and environments in which the harmful organisms 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 formulation according to claim 1, characterized in that the formulation is applied by an unmanned aerial vehicle (UAV), an unmanned guided vehicle (UGV), or a pulse-width-module (PWM).

Description

FIGURES

[0276] 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)

[0277] 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.

[0278] The invention is illustrated by the following examples.

EXAMPLES

[0279] Method 1: SC Preparation

[0280] 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 polyalkyleneoxide modified heptamethyltrisiloxane (b) 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 (c).

[0281] Method 2: WG Preparation

[0282] 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.

[0283] 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, Bihler, 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).

[0284] 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.

[0285] Likewise, any other spraying process, like e.g. classical spray drying can be used as granulation method.

[0286] 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.

[0287] Method 3: EC Preparation

[0288] 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.

[0289] Method 4: OD Preparation

[0290] 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. 25vol.-% 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 <10p is achieved.

[0291] Method 5: Coverage

[0292] 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 600 (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.

[0293] 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.

[0294] 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.

[0295] Method 6: Insecticide Greenhouse Tests

[0296] Insecticide Greenhouse Tests

[0297] 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).

[0298] 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.

[0299] The application was conducted with track sprayer onto upper side of leaves with 300 1/ha or 10 1/ha application volume. Nozzles used: Lechler's TeeJet TP8003E (for 300 1/ha) and Lechler's 652.246 together with a pulse-width-module (PWM) (for 10 1/ha). For each single dose applied, usually 2 to 5 replicates were simultaneously treated.

[0300] 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.

[0301] The following table shows pests and crops used in the tests.

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

TABLE-US-00004 TABLE 1 Exemplified trade names and CAS-No's of preferred organosilicone compounds (b) Product Chemical name Cas No. Supplier Silwet ® L77 3-(2-methoxyethoxy)propyl-methyl- 27306-78-1 Momentive 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 ® 3-[methyl- 134180-76-0 Evonik S240 bis(trimethylsilyloxy)silyl]propan-1- ol;2-methyloxirane;oxirane Break-thru ® 3-(2-methoxyethoxy)propyl-methyl- 27306-78-1 Evonik S278 bis(trimethylsilyloxy)silane Silwet ® HS Polyalkylenoxide Silane Momentive 312 Silwet ® HS Polyalkylenoxide Silane Momentive 604 BreakThru ® Siloxanes and Silicones, cetyl Me, di- 191044-49-2 Evonik OE 444 Me BreakThru 3-[methyl- 134180-76-0 Evonik SD260 bis(trimethylsilyloxy)silyl]propan-1- ol;2-methyloxirane;oxirane BreakThru 3-[methyl- 134180-76-0 Evonik S301 bis(trimethylsilyloxy)silyl]propan-1- ol;2-methyloxirane;oxirane

TABLE-US-00005 TABLE 2 Exemplified trade names and CAS-No's of preferred compounds (c) Product Chemical name Cas No. Supplier Lucramul PS 29 Poly(oxy-1,2-ethanediyl),. 104376-75-2 Levaco alpha.-phenyl-.omega.-hydroxy-, styrenated Lucramul PS 54 Poly(oxy-1,2- 104376-75-2 Levaco ethanediyl), .alpha.- phenyl-.omega.-hydroxy-, styrenated Atlox ® 4913 methyl methacrylate graft 119724-54-8 Croda copolymer with polyethylene glycol Antarox B848 Oxirane, methyl-, polymer with 9038-95-3 Solvay oxirane, monobutyl ether 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 Kaolin W Mica group minerals 12001-26-2 Brenntag Oparyl MT 804 Dibutylnaphthalenesulfonic acid 25417-20-3 Gioavanni sodium salt Bozzetto Pergopak M Urea formaldehyde polymer 9011-05-6 Albermale Polyfon T Lignosulfonic acid, sodium salt 8061-51-6 MeadWestvaco Agnique SLS 90 Sodium dodecyl sulphate 151-21-3 BASF Dispersogen SI Naphthalenesulfonic acid 9084-06-4 Clariant formaldehyde polymer sodium salt NANSA EVM Benzenesulfonic acid, mono- 68953-96-8 Huntsman 40/2NDL C11-13-branched alkyl derivs ., calcium salts Emulsogen EL Castor oil, ethoxylated 61791-12-6 Clariant 400 Atlox 4894 308061-37-2 Croda Soprophor FLK Poly(oxy-1,2-ethanediyl), alpha.- 163436-84-8 Solvay 2,4,6-tris(1- phenylethyl)phenyl-.omega.- hydroxy-, phosphate, potassium salt Morwet D-425 Sodium naphthalene sulphonate 577773-56-9 Akzo Nobel, formaldehyde condensate 68425-94-5 Nouryon 9008-63-3 Rhodasurf 860/P Alcohols, C9-11-iso-, C10-rich, 78330-20-8 Solvay ethoxylated ATLAS ® G Oxirane, methyl-, polymer with 9038-95-3 Croda 5000 oxirane, monobutyl ether Surfynol 440 2,4,7,9-Tetramethyldec-5-yne- 9014-85-1 Evonik 4,7-diol, ethoxylated Synperonic Polyethylene-Polypropylene 9003-11-6 Croda PE/F127 Glycol Mowiol 8-88 Polyvinylalkohol 9002-89-5 Kuraray Urea 57-13-6 Glycerin 56-81-5 Propylene 1,2-Propylene glycol 57-55-6 Glycol RHODOPOL ® Polysaccharide 11138-66-2 Solvay 23 Aerosil R812S Silanamine, 1,1,1-trimethyl-N- 68909-20-6 Evonik (trimethylsilyl)-, hydrolysis products with silica Aerosil R972 Silane, dichlorodimethyl-, 68611-44-9 Evonik reaction products with silica Sipernat 22 S synthetic amorphous silica 112926-00-8 Evonik (silicon 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) Diammonium 7783-28-0 Hydrogen Phosphate Proxel ® GXL 1.2-benzisothiazol-3(2H)-one 2634-33-5 Arch Chemicals Kathon ® 5-chloro-2-methyl-4- 26172-55-4 Dow CG/ICP isothiazolin-3-one plus 2-methyl- plus 4-isothiazolin-3-one 2682-20-4 Dowanol DPM Di(propylene glycol) methyl 34590-94-8 Dow ether Cyclohexanone 108-94-1 Solvesso ® Mixture of aromatic 64742-94-5 ExxonMobil 200ND hydrocarbons (C9-C11), naphtalene depleted

TABLE-US-00006 TABLE 3 Spirotetramat/Spiromesifen SC Formulations Recipe 2 Recipe 4 according according Component Recipe 1 to the Recipe 3 to the (g/L) reference invention reference invention Spirotetramat 75 75 — — Spiromesifen — — 72 72 Lucramul PS 29 40 40 — — Lucramul PS 54 — — 10.5 10.5 Atlox 4913 — — 31.5 31.5 Glycerin 100 100 105 105 Rhodopol 23 3 3 3.6 3.6 Preventol D7 0.8 0.8 0.8 0.8 Proxel GXL 20% 1.2 1.2 1.2 1.2 Silcolapse 426R 1 1 1 1 Citric Acid 1 1 1 1 Silwet HS312 — 40 — 40 — — — — Water (add to 1 To To To To litre) volume volume volume volume

TABLE-US-00007 TABLE 4 Spray dilution droplet size and dose on non-textured leaves. Leaf Organosilicone coverage @ Organosilicone surfactant dose 0°, % surfactant dose % w/v Recipe apple g/ha (g/100 mL) Recipe 1 not 20.2 0 0 according to the invention - 10 l/ha Recipe 1 not 32.7 0 0 according to the invention - 300 l/ha Recipe 2 28.8 40 0.4 according to the invention - 10 l/ha Recipe 2 82.6 40 0.01 according to the invention - 300 l/ha

[0302] Formulations applied at 11/ha.

[0303] The results show that on non-structured leaves the coverage is higher at higher water application volumes.

TABLE-US-00008 TABLE 5 Spray dilution droplet size and dose on textured leaves. indicates data missing or illegible when filed

[0304] Formulations applied at 11/ha.

[0305] The results show that at 10 L/ha spray volume, the recipe illustrative of the invention shows larger deposit sizes than the recipe not according to the invention.

TABLE-US-00009 TABLE 6 Spray dilution droplet size and dose on non-textured leaves. Organo- Leaf Leaf Organo- silicone coverage coverage silicone surfactant @ @ surfactant dose 0°, % 0°, % dose % w/v Recipe soybean barley g/ha (g/100 mL) Recipe 1 not 19.3 19.0 0 0 according to the invention - 10 l/ha Recipe 1 not 67.4 36.6 0 0 according to the invention - 300 l/ha Recipe 2 38.4 39.3 40 0.4 according to the invention - 10 l/ha Recipe 2 89.7 80.6 40 0.01 according to the invention - 300 l/ha Super- Super- spreading spreading surfactant Deposit surfactant dose area mm{circumflex over ( )}2 dose % w/v Recipe apple g/ha (g/100 mL) Recipe 3 not 7.4 0 0 according to the invention - 10 l/ha Recipe 3 not 6.6 0 0 according to the invention - 20 l/ha Recipe 3 not 3.5 0 0 according to the invention - 200 l/ha Recipe 4 12.4 40 0.4 according to the invention - 10 l/ha Recipe 4 11.8 40 0.2 according to the invention - 20 l/ha Recipe 4 6.6 40 0.02 according to the invention - 200 l/ha

TABLE-US-00010 TABLE 7 Spray dilution droplet size and dose on textured leaves. Super- spreading De- De- Super- surfactant Deposit posit posit spreading dose area area area surfactant % w/v mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose (g/100 Recipe soybean rice barley g/ha mL) Recipe 3 not according 3.4 1.8 4.2 0 0 to the invention - 10 l/ha Recipe 3 not according 4.0 2.5 3.2 0 0 to the invention - 20 l/ha Recipe 3 not according 1.9 1.1 2.4 0 0 to the invention - 200 l/ha Recipe 4 according to 191.0 100.6 115.1 40 0.4 the invention - 10 l/ha Recipe 4 according to 194.2 130.6 126.2 40 0.2 the invention - 20 l/ha Recipe 4 according to 8.5 7.4 14.8 40 0.02 the invention - 200 l/ha

[0306] Formulations applied at 11/ha.

[0307] The results show that the recipe illustrative of the invention shows larger deposit sizes at 10 L/ha spray volume than at 200 L/ha, and than the recipe not according to the invention at all water volume uses.

[0308] 2. SPIDOXAMATE OD

TABLE-US-00011 TABLE 8 SPIDOXAMATE OD Formulations Recipe 6 according Recipe 5 to the Component (g/mL) reference invention SPIDOXAMATE 12 12 Antarox B848 20 20 Propylene Glycol 150 150 Aerosil R812S 40 40 Diammonium Hydrogen 20 20 phosphate Silwet HS312 — 40 — — Dowanol DPM (add to 1 To volume To volume litre)

[0309] BOP

[0310] The leaf deposit size was determined according to coverage method.

TABLE-US-00012 TABLE 9 Spray dilution droplet size and dose on non- textured leaves. Super- Super- spreading Deposit spreading surfactant area surfactant dose mm{circumflex over ( )}2 dose % w/v Recipe apple g/ha (g/100 mL) Recipe 5 not according 6.3 0 0 to the invention - 10 l/ha Recipe 5 not according 6.2 0 0 to the invention - 20 l/ha Recipe 5 not according 6.0 0 0 to the invention - 200 l/ha Recipe 6 according to 12.0 40 0.4 the invention - 10 l/ha Recipe 6 according to 7.6 40 0.2 the invention - 20 l/ha Recipe 6 according to 5.7 40 0.02 the invention - 200 l/ha

[0311] Formulations applied at 11/ha.

[0312] The results show that on non-structured leaves the deposit size is similar or lower at higher water application volumes.

TABLE-US-00013 TABLE 10 Spray dilution droplet size and dose on textured leaves. Super- spreading De- De- Super- surfactant Deposit posit posit spreading dose area area area surfactant % w/v mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose (g/100 Recipe soybean rice barley g/ha mL) Recipe 5 not according 3.4 6.6 4.5 0 0 to the invention - 10 l/ha Recipe 5 not according 2.9 4.1 3.0 0 0 to the invention - 20 l/ha Recipe 5 not according 2.1 2.4 2.5 0 0 to the invention - 200 l/ha Recipe 6 according to 255.7 142.5 123.9 40 0.4 the invention - 10 l/ha Recipe 6 according to 141.0 103.1 119.9 40 0.2 the invention - 20 l/ha Recipe 6 according to 7.4 10.1 12.1 40 0.02 the invention - 200 l/ha

[0313] Formulations applied at 11/ha.

[0314] The results show that the recipe illustrative of the invention shows larger deposit sizes at 10 L/ha spray volume than at 200 L/ha, and than the recipe not according to the invention at all water volume uses.

[0315] 3 Flubendiamide, Tetraniliprole SC recipes

TABLE-US-00014 TABLE 11 Flubendiamide, Tetraniliprole SC recipes Recipe 8 Recipe 9 Recipe 10 according according according Component Recipe 7 to the to the to the (g/L) reference invention invention invention Tetraniliprole 40.0 40.0 — — Flubendiamide — — 120 120 Atlox 4913 40.0 40.0 — — Morwet IP 10.0 10.0 — — Synperonic 15.0 15.0 — — PE/F127 Lucramul PS 54 — — 12 12 Atlox 4913 — — 37 37 Citric Acid 1.0 1.0 — — Rhodopol 23 3.0 3.0 3.6 3.6 Sipernat 22 S 7.5 7.5 9 9 Silwet ® HS 312 — 40 — 40 — — — — Kathon CG/ICP 0.8 0.8 1 1 Proxel GXL 1.2 1.2 1.5 1.5 Glycerin 100.0 100.0 122 122 SAG1572 1.5 1.5 1.8 1.8 Water (add to 1 fill fill fill fill litre)

[0316] BOP

[0317] The leaf deposit size was determined according to coverage method.

TABLE-US-00015 TABLE 12 Spray dilution droplet size and dose on non-textured leaves. Organo- Leaf Leaf Organo- silicone coverage coverage silicone surfactant @ @ surfactant dose 0°, % 0°, % dose % w/v Recipe apple abutilon g/ha (g/100 mL) Recipe 7 not 11.7 7 0 0 according to the invention - 10 l/ha Recipe 7 not 30.1 23.1 0 0 according to the invention - 200 l/ha Recipe 8 14.2 23.0 40 0.4 according to the invention - 10 l/ha Recipe 8 74.4 55.1 40 0.02 according to the invention - 200 l/ha

[0318] Formulations applied at 11/ha.

[0319] The results show that on non-structured leaves the coverage is higher at higher water application volumes.

TABLE-US-00016 TABLE 13 Spray dilution droplet size and dose on textured leaves Organo- Leaf Leaf Leaf Organo- silicone coverage coverage coverage silicone surfactant @ @ @ surfactant dose 0°, % 0°, % 0°, % dose % w/v Recipe soybean barley rice g/ha (g/100 mL) Recipe 7 not 6.3 5.2 5.8 0 0 according to the invention - 10 l/ha Recipe 7 not 23.3 14.7 9.2 0 0 according to the invention - 200 l/ha Recipe 8 23 30.6 27 40 0.4 according to the invention - 10 l/ha Recipe 8 35.2 42.2 35 40 0.02 according to the invention - 200 l/ha

[0320] The results show that at 10 L/ha spray volume, the recipe illustrative of the invention shows larger deposit sizes than the recipe not according to the invention.

TABLE-US-00017 TABLE 14 Spray dilution droplet size and dose on non-textured leaves. Organosilicone Deposit Organosilicone surfactant dose area mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple g/ha (g/100 mL) Recipe 9 not according 4.4 0 0 to the invention - 10 l/ha Recipe 9 not according 3.1 0 0 to the invention - 200 l/ha Recipe 10 not 11.0 40 0.4 according to the invention - 10 l/ha Recipe 10 according to 7.5 40 0.02 the invention - 200 l/ha

[0321] Formulations applied at 11/ha.

[0322] The results show that on non-structured leaves the deposit size is similar at both water application volumes.

TABLE-US-00018 TABLE 15 Spray dilution droplet size and dose on textured leaves. Organosilicone Deposit Organosilicone surfactant dose area mm{circumflex over ( )}2 surfactant dose % w/v Recipe soybean g/ha (g/100 mL) Recipe 9 not according 1.6 0 0 to the invention - 10 l/ha Recipe 9 not according 1.6 0 0 to the invention - 200 l/ha Recipe 10 not 196.5 40 0.4 according to the invention - 10 l/ha Recipe 10 according to 6.1 40 0.02 the invention - 200 l/ha

[0323] The results show that the recipe illustrative of the invention shows larger deposit sizes at 10 L/ha spray volume than at 200 L/ha, and than the recipe not according to the invention at all water volume uses.

[0324] 4. Fubendiamide WG-recipes

TABLE-US-00019 TABLE 16 Flubendiamide WG recipes Recipe 12 Recipe 13 Recipe according according Component (% 11 to the to the w/w) standard invention invention Flubendiamide 24.0 22.8 23.8 Kaolin W 44.0 41.8 43.6 Oparyl MT 804 2.0 1.9 1.9 Pergopak M 5.0 4.8 4.9 Polyfon T 25.0 23.7 24.8 Break-thru SD 260 — 5 — Break-thru S 301 — — 1

[0325] BOP

[0326] The leaf deposit size was determined according to coverage method.

TABLE-US-00020 TABLE 17 Spray dilution droplet size and dose on non-textured leaves. Leaf Organosilicone coverage @ Organosilicone surfactant dose 0°, % surfactant dose % w/v Recipe apple g/ha (g/100 mL) Recipe 11 not 17.9 0 0 according to the invention—10 l/ha Recipe 11 not 39.7 0 0 according to the invention—200 l/ha Recipe 12 15.9 8.3 0.08 according to the invention—10 l/ha Recipe 12 22.8 8.3 0.004 according to the invention—200 l/ha Recipe 13  9.3 1.7 0.017 according to the invention—10 l/ha Recipe 13 23.9 1.7 0.00085 according to the invention—200 l/ha

[0327] Formulations applied at 40 g ai/ha or 166 g WG/ha.

TABLE-US-00021 TABLE 18 Spray dilution droplet size and dose on textured leaves. Organo- Leaf Leaf Organo- silicone coverage coverage silicone surfactant @ @ surfactant dose 0°, % 0°, % dose % w/v Recipe soybean barley g/ha (g/100 mL) Recipe 11 not 4.3 4.6 0 0 according to the invention—10 l/ha Recipe 11 2.9 1.4 0 0 not according to the invention—200 l/ha Recipe 12 7.8 8.3 8.3 0.08 according to the invention—10 l/ha Recipe 12 5.1 3.4 8.3 0.004 according to the invention—200 l/ha Recipe 13 8.2 20.0  1.7 0.017 according to the invention—10 l/ha Recipe 13 5.4 7.4 1.7 0.00085 according to the invention—200 l/ha

[0328] Formulations applied at 40 g ai/ha or 166 g WG/ha.

[0329] The results show that the recipes illustrative of the invention show larger deposit sizes on textured leaves at 10 L/ha spray volume than at 200 L/ha, and than the recipe not according to the invention at all water volume uses.

[0330] 5. Deltamethrin, beta-cyfluthrin SC recipes

TABLE-US-00022 TABLE 19 Deltamethrin, beta-cyfluthrin SC recipes Recipe 15 Recipe 17 according Recipe according Recipe 14 to the 16 to the Component (g/L) reference invention reference invention 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 Silwet ® HS 312 — 40 — 40 — — — — 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)

[0331] BOP

[0332] The leaf deposit size was determined according to coverage method.

TABLE-US-00023 TABLE 20 Spray dilution droplet size and dose on non-textured leaves. Deposit Organosilicone area Organosilicone surfactant dose mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple g/ha (g/100 mL) Recipe 14 not 6.0 0 0 according to the invention—10 l/ha Recipe 14 not 5.0 0 0 according to the invention—20 l/ha Recipe 14 not 2.4 0 0 according to the invention—200 l/ha Recipe 14 not 1.6 0 0 according to the invention—300 l/ha Recipe 15 according to 12.6 20 0.2 the invention—10 l/ha Recipe 15 according to 14.2 20 0.1 the invention—20 l/ha Recipe 15 according to 10.4 20 0.01 the invention—200 l/ha Recipe 15 according to 8.5 20 0.007 the invention—300 l/ha

[0333] Formulations applied at 0.5 1/ha.

[0334] The results show that on non-structured leaves the deposit size is slightly higher at low water application volumes.

TABLE-US-00024 TABLE 21 Spray dilution droplet size and dose on textured leaves. Organo- Organo- silicone Deposit Deposit Deposit silicone surfactant area area area surfactant dose mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose % w/v Recipe soybean rice barley g/ha (g/100 mL) Recipe 14 not 2.2 2.4 4.1 0 0 according to the invention—10 l/ha Recipe 14 not 1.8 1.3 2.5 0 0 according to the invention—20 l/ha Recipe 14 not 0.8 0.5 1.5 0 0 according to the invention—200 l/ha Recipe 14 not 0.6 0.3 0.6 0 0 according to the invention—300 l/ha Recipe 15 232 158 143 20 0.2 according to the invention—10 l/ha Recipe 15 219.3 140 138 20 0.1 according to the invention—20 l/ha Recipe 15 11.4 12.8 14.7 20 0.01 according to the invention—200 l/ha Recipe 15 7.5 8.0 9.46 20 0.007 according to the invention—300 l/ha

[0335] Formulations applied at 0.5 1/ha.

[0336] The results show that the recipes illustrative of the invention show larger deposit sizes at 10 L/ha spray volume than at 200 L/ha, and than the recipe not according to the invention at all water volume uses.

TABLE-US-00025 TABLE 22 Spray dilution droplet size and dose on non-textured leaves. Deposit Organosilicone area Organosilicone surfactant dose mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple g/ha (g/100 mL) Recipe 16 not 6.8 0 0 according to the invention—10 l/ha Recipe 16 not 4.8 0 0 according to the invention—20 l/ha Recipe 16 not 1.6 0 0 according to the invention—200 l/ha Recipe 16 not 2.1 0 0 according to the invention—300 l/ha Recipe 17 according to 13.2 20 0.2 the invention—10 l/ha Recipe 17 according to 12.6 20 0.1 the invention—20 l/ha Recipe 17 according to 10.3 20 0.01 the invention—200 l/ha Recipe 17 according to 7.9 20 0.007 the invention—300 l/ha

[0337] Formulations applied at 0.5 1/ha.

[0338] The results show that on non-structured leaves the deposit size is slightly higher at low water application volumes.

TABLE-US-00026 TABLE 23 Spray dilution droplet size and dose on textured leaves. Organo- Organo- silicone Deposit Deposit Deposit silicone surfactant area area area surfactant dose mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose % w/v Recipe soybean rice barley g/ha (g/100 mL) Recipe 16 not 3.0 3.0 3.4 0 0 according to the invention—10 l/ha Recipe 16 not 3.5 2.6 3.8 0 0 according to the invention—20 l/ha Recipe 16 not 1.2 1.0 1.9 0 0 according to the invention—200 l/ha Recipe 16 not 1.2 0.7 2.1 0 0 according to the invention—300 l/ha Recipe 17 230.0 177.0 93.4 20 0.2 according to the invention—10 l/ha Recipe 17 127.8 101.0 83.5 20 0.1 according to the invention—20 l/ha Recipe 17 11.9 12.3 10.9 20 0.01 according to the invention—200 l/ha Recipe 17 5.9 7.7 8.3 20 0.007 according to the invention—300 l/ha

[0339] Formulations applied at 0.5 1/ha.

[0340] The results show that the recipes illustrative of the invention show larger deposit sizes at 10 L/ha spray volume than at 200 L/ha, and than the recipe not according to the invention at all water volume uses.

[0341] 6. Deltamethrin EC Formulation

TABLE-US-00027 TABLE 24 Deltamethrin EC Formulation Recipe 19 Recipe 18 according to the Component (g/L) reference invention Deltamethrin 48.0 48.0 NANSA EVM 40/2NDL 40.0 40.0 Emulsogen EL 400 40.0 40.0 Citric Acid 1.0 1.0 Silwet 806 — 120.0 Cyclohexanone 100.0 100.0 Solvesso 200 ND 771.0 651.0

[0342] The method of preparation used was according to the EC preparation method.

[0343] BOP

[0344] The leaf deposit size was determined according to coverage method.

TABLE-US-00028 TABLE 25 Spray dilution droplet size and dose on non-textured leaves. Organo- Organo- silicone Deposit Deposit silicone surfactant area area surfactant dose mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose % w/v Recipe apple corn g/ha (g/100 mL) Recipe 18 not 1.4 1.6 0 0 according to the invention—10 l/ha Recipe 18 not 1.6 0.6 0 0 according to the invention—20 l/ha Recipe 18 not 1.6 0.9 0 0 according to the invention—200 l/ha Recipe 19 according to 2.5 9.6 30 0.3 the invention—10 l/ha Recipe 19 according to 4.4 11.6 30 0.15 the invention—20 l/ha Recipe 19 according to 7.0 12.8 30 0.015 the invention—200 l/ha

[0345] Formulations applied at 0.25 1/ha.

[0346] The results show that on non-structured leaves the deposits size is similar or higher at higher water application volume.

TABLE-US-00029 TABLE 26 Spray dilution droplet size and dose on textured leaves. Organo- Organo- silicone Deposit Deposit Deposit silicone surfactant area area area surfactant dose mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose % w/v Recipe soybean rice barley g/ha (g/100 mL) Recipe 18 not 2.1 1.1 1.8 0 0 according to the invention—10 l/ha Recipe 18 not 1.0 0.9 0.8 0 0 according to the invention—20 l/ha Recipe 18 not 1.6 0.1 0.5 0 0 according to the invention—200 l/ha Recipe 19 5.1 4.0 5.4 30 0.3 according to the invention—10 l/ha Recipe 19 18.6 6.2 9.4 30 0.15 according to the invention—20 l/ha Recipe 19 19.8 5.2 5.4 30 0.015 according to the invention—200 l/ha

[0347] Formulations applied at 0.25 1/ha.

[0348] The results show that the recipes illustrative of the invention show larger deposit sizes on textured leaves at 20 L/ha spray volume than at 200 L/ha, and than the recipe not according to the invention at all water volume uses.

[0349] 7. Clothianidin, Imidacloprid, Thiacloprid recipes

TABLE-US-00030 TABLE 27 Clothiandin, Imidacloprid, Thiacloprid SC recipes Rec- Recipe Rec- Recipe Rec- Recipe ipe 21 ipe 23 ipe 25 20 according 22 according 24 according Component refer- to the refer- to the refer- to the (g/L) ence invention ence invention ence invention Clothianidin 100 100 — — — — Imidacloprid — — 50 50 — — Thiacloprid — — — — 120 120 Atlox 4913 70 70 52 52 33 33 Atlox 4894 12 12 — — — — — — — — Lucramul — — 17 17 11 11 PS 54 Rhodopol 23 4 4 4 4 4 4 Sipernat 22 6 6 — — — — S Silwet ® HS — 40 — 40 — 40 312 — — — — — — Proxel GXL 1.2 1.2 1.2 1.2 1.2 1.2 Kathon 0.8 0.8 0.8 0.8 0.8 0.8 CG/ICP 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)

[0350] BOP

[0351] The leaf deposit size was determined according to coverage method.

TABLE-US-00031 TABLE 28 Spray dilution droplet size and dose on non-textured leaves. Super- Super- spreading Deposit spreading surfactant area surfactant dose mm{circumflex over ( )}2 dose % w/v Recipe apple g/ha (g/100 mL) Recipe 20 not 9.2 0 0 according to the invention—10 l/ha Recipe 20 not 8.6 0 0 according to the invention—20 l/ha Recipe 20 not 6.4 0 0 according to the invention—200 l/ha Recipe 21 according to 13.7 40 0.4 the invention—10 l/ha Recipe 21 according to 13.6 40 0.2 the invention—20 l/ha Recipe 21 according to 12.8 40 0.02 the invention—200 l/ha

[0352] Formulations applied at 11/ha.

[0353] The results show that on non-structured leaves the deposit size is similar or slightly higher at low water application volume.

TABLE-US-00032 TABLE 29 Spray dilution droplet size and dose on textured leaves. Super- Super- spreading Deposit Deposit Deposit spreading surfactant area area area surfactant dose mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose % w/v Recipe soybean rice barley g/ha (g/100 mL) Recipe 20 not 5.8 6.1 7.9 0 0 according to the invention—10 l/ha Recipe 20 not 5.0 6.9 7.5 0 0 according to the invention—20 l/ha Recipe 20 not 3.1 2.5 4.2 0 0 according to the invention—200 l/ha Recipe 21 201.7 119.4 102.3 40 0.4 according to the invention—10 l/ha Recipe 21 256.7 138.0 123.8 40 0.2 according to the invention—20 l/ha Recipe 21 25.2 31.1 31.5 40 0.02 according to the invention—200 l/ha

[0354] Formulations applied at 11/ha.

[0355] The results show that the recipes illustrative of the invention show larger deposit sizes at 10 L/ha spray volume than at 200 L/ha, and than the recipe not according to the invention at all water volume uses.

TABLE-US-00033 TABLE 30 Spray dilution droplet size and dose on non-textured leaves. Super- Super- spreading Deposit spreading surfactant area surfactant dose mm{circumflex over ( )}2 dose % w/v Recipe apple g/ha (g/100 mL) Recipe 22 not 4.7 0 0 according to the invention—10 l/ha Recipe 22 not 4.5 0 0 according to the invention—20 l/ha Recipe 22 not 1.7 0 0 according to the invention—200 l/ha Recipe 23 according to 11.9 40 0.4 the invention—10 l/ha Recipe 23 according to 12.8 40 0.2 the invention—20 l/ha Recipe 23 according to 10.3 40 0.02 the invention—200 l/ha

[0356] Formulations applied at 11/ha.

[0357] The results show that on non-structured leaves the deposit size is higher or similar at low water application volume.

TABLE-US-00034 TABLE 31 Spray dilution droplet size and dose on textured leaves. Super- Super- spreading Deposit Deposit Deposit spreading surfactant area area area surfactant dose mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose % w/v Recipe soybean rice barley g/ha (g/100 mL) Recipe 22 not 2.5 1.5 3.8 0 0 according to the invention—10 l/ha Recipe 22 not 1.7 1.6 3.5 0 0 according to the invention—20 l/ha Recipe 22 not 1.1 1.0 2.2 0 0 according to the invention—200 l/ha Recipe 23 179.0 95.7 40 0.4 according to the invention—10 l/ha Recipe 23 236.1 94.6 40 0.2 according to the invention—20 l/ha Recipe 23 10.8 15.9 40 0.02 according to the invention—200 l/ha

[0358] Formulations applied at 11/ha.

[0359] The results show that the recipes illustrative of the invention show larger deposit sizes at 20 L/ha spray volume than at 200 L/ha, and than the recipe not according to the invention at all water volume uses

TABLE-US-00035 TABLE 32 Spray dilution droplet size and dose on non-textured leaves. Super- Super- spreading Deposit spreading surfactant area surfactant dose mm{circumflex over ( )}2 dose % w/v Recipe apple g/ha (g/100 mL) Recipe 24 not 5.3 0 0 according to the invention—10 l/ha Recipe 24 not 5.0 0 0 according to the invention—20 l/ha Recipe 24 not 3.0 0 0 according to the invention—200 l/ha Recipe 25 according to 14.6 40 0.4 the invention—10 l/ha Recipe 25 according to 12.9 40 0.2 the invention—20 l/ha Recipe 25 according to 12.3 40 0.02 the invention—200 l/ha

[0360] Formulations applied at 11/ha.

[0361] The results show that on non-structured leaves the deposit size is higher at higher water application volume.

TABLE-US-00036 TABLE 33 Spray dilution droplet size and dose on textured leaves. Super- spreading De- De- Super- surfactant Deposit posit posit spreading dose area area area surfactant % w/v mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose (g/100 Recipe soybean rice barley g/ha mL) Recipe 24 not 2.7 1.7 4.2 0 0 according to the invention - 10 l/ha Recipe 24 not 2.2 1.2 3.5 0 0 according to the invention - 20 l/ha Recipe 24 not 1.8 0.5 2.5 0 0 according to the invention - 200 l/ha Recipe 25 according to 255.4 121.8 98.8 40 0.4 the invention - 10 l/ha Recipe 25 according to 237.9 105.8 103.5 40 0.2 the invention - 20 l/ha Recipe 25 according to 16.8 22.3 27.7 40 0.02 the invention - 200 l/ha

[0362] Formulations applied at 11/ha.

[0363] The results show that the recipes illustrative of the invention show larger deposit sizes at 10 L/ha spray volume than at 200 L/ha, and than the recipe not according to the invention at all water volume uses

[0364] 8. Ethiprole, Fipronil recipes

TABLE-US-00037 TABLE 34 Ethiprole, Fipronil SC recipes Rec- Recipe Rec- Recipe Rec- Recipe ipe 27 ipe 29 ipe 31 26 according 28 according 30 according Component refer- to the refer- to the refer- to the (g/L) ence invention ence invention ence invention Ethiprole 100 100 — — 100 100 Fipronil — — 50 50 — — Imidacloprid — — — — 100 100 Soprophor 38 38 14 14 — — FLK Morwet — — 14 14 11 11 D425 Rhodasruf — — 5 5 — — 860/P Atlox 4913 — — — — 69 69 Atlas G — — — — 22 22 5000 Citric Acid 0.2 0.2 0.2 0.2 2 2 Rhodopol 23 4 4 4 4 4 4 Van Gel B 5 5 — — — — Veegum R — — — — 6 6 Silwet ® HS — 40 — 40 — 40 312 — — — — — — Kathon 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 Propylene 123 123 51 51 110 110 Glycol SAG1572 3 3 3 3 — — Silcolapse — — — — 3 3 426R Water (add fill fill fill fill fill fill to 1 litre)

[0365] BOP

[0366] The leaf deposit size was determined according to coverage method.

TABLE-US-00038 TABLE 35 Spray dilution droplet size and dose on non-textured leaves. Deposit Organosilicone area Organosilicone surfactant dose mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple g/ha (g/100 mL) Recipe 26 not 4.2 0 0 according to the invention - 10 l/ha Recipe 26 not 5.1 0 0 according to the invention - 20 l/ha Recipe 26 not 2.4 0 0 according to the invention - 200 l/ha Recipe 26 not 2.0 0 0 according to the invention - 300 l/ha Recipe 27 according to 14.7 20 0.2 the invention - 10 l/ha Recipe 27 according to 13.5 20 0.1 the invention - 20 l/ha Recipe 27 according to 11.8 20 0.01 the invention - 200 l/ha Recipe 27 according to 8.6 20 0.006 the invention - 300 l/ha

[0367] Formulations applied at 0.5 1/ha.

[0368] The results show that on non-structured leaves the deposit size is slightly higher at higher water application volume.

TABLE-US-00039 TABLE 36 Spray dilution droplet size and dose on textured leaves. Organos- ilicone De- De- Organo- surfactant Deposit posit posit silicone dose area area area surfactant % w/v mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose (g/100 Recipe soybean rice barley g/ha mL) Recipe 26 not 2.9 2.0 3.9 0 0 according to the invention - 10 l/ha Recipe 26 not 2.6 1.9 4.6 0 0 according to the invention - 20 l/ha Recipe 26 not 1.9 1.0 2.7 0 0 according to the invention - 200 l/ha Recipe 26 not 1.8 0.9 2.3 0 0 according to the invention - 300 l/ha Recipe 27 according to 209.0 136.0 104.0 20 0.2 the invention - 10 l/ha Recipe 27 according to 144.8 88.4 85.2 20 0.1 the invention - 20 l/ha Recipe 27 according to 10.5 13.6 15.6 20 0.01 the invention - 200 l/ha Recipe 27 according to 7.4 9.6 8.7 20 0.006 the invention - 300 l/ha

[0369] Formulations applied at 0.5 1/ha.

[0370] The results show that the recipes illustrative of the invention show larger deposit sizes at 10 L/ha spray volume than at 200 L/ha, and than the recipe not according to the invention at all water volume uses.

TABLE-US-00040 TABLE 37 Spray dilution droplet size and dose on non-textured leaves. Organosilicone Deposit Organosilicone surfactant dose area mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple g/ha (g/100 mL) Recipe 28 not 7.4 0 0 according to the invention - 10 l/ha Recipe 28 not 6.4 0 0 according to the invention - 20 l/ha Recipe 28 not 4.8 0 0 according to the invention - 200 l/ha Recipe 28 not 1.1 0 0 according to the invention - 300 l/ha Recipe 29 according to 12.1 20 0.2 the invention - 10 l/ha Recipe 29 according to 12.0 20 0.1 the invention - 20 l/ha Recipe 29 according to 9.7 20 0.01 the invention - 200 l/ha Recipe 29 according to 9.0 20 0.006 the invention - 300 l/ha

[0371] Formulations applied at 11/ha.

[0372] The results show that on non-structured leaves the deposit size is slightly higher at low water application volumes.

TABLE-US-00041 TABLE 38 Spray dilution droplet size and dose on textured leaves. Organo- silicone De- De- Organo- surfactant Deposit posit posit silicone dose area area area surfactant % w/v mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose (g/100 Recipe soybean rice barley g/ha mL) Recipe 28 not 4.5 3.8 4.8 0 0 according to the invention - 10 l/ha Recipe 28 not 3.7 2.8 4.3 0 0 according to the invention - 20 l/ha Recipe 28 not 2.1 2.0 3.4 0 0 according to the invention - 200 l/ha Recipe 28 not 1.7 1.3 2.2 0 0 according to the invention - 300 l/ha Recipe 29 according to 171.0 165.0 94.2 20 0.2 the invention - 10 l/ha Recipe 29 according to 169.4 113.0 89.1 20 0.1 the invention - 20 l/ha Recipe 29 according to 11.4 18.4 14.5 20 0.01 the invention - 200 l/ha Recipe 29 according to 7.8 14.7 12.3 20 0.006 the invention - 300 l/ha

[0373] Formulations applied at 11/ha.

[0374] The results show that the recipes illustrative of the invention show larger deposit sizes at 10 L/ha spray volume than at 200 L/ha, and than the recipe not according to the invention at all water volume uses.

TABLE-US-00042 TABLE 39 Spray dilution droplet size and dose on non-textured leaves. Deposit Organosilicone area Organosilicone surfactant dose mm{circumflex over ( )}2 surfactant dose % w/v Recipe apple g/ha (g/100 mL) Recipe 30 not 5.5 0 0 according to the invention - 10 l/ha Recipe 30 not 5.5 0 0 according to the invention - 20 l/ha Recipe 30 not 1.0 0 0 according to the invention - 200 l/ha Recipe 30 not 1.0 0 0 according to the invention - 300 l/ha Recipe 31 according to 13.0 20 0.2 the invention - 10 l/ha Recipe 31 according to 12.0 20 0.1 the invention - 20 l/ha Recipe 31 according to 8.9 20 0.01 the invention - 200 l/ha Recipe 31 according to 7.9 20 0.006 the invention - 300 l/ha

[0375] Formulations applied at 0.5 1/ha.

[0376] The results show that on non-structured leaves the deposit size is slightly higher at low water application volumes.

TABLE-US-00043 TABLE 40 Spray dilution droplet size and dose on textured leaves. Organo- silicone De- De- Organo- surfactant Deposit posit posit silicone dose area area area surfactant % w/v mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose (g/100 Recipe soybean rice barley g/ha mL) Recipe 30 not 2.4 1.5 4.1 0 0 according to the invention - 10 l/ha Recipe 30 not 2.1 1.5 3.4 0 0 according to the invention - 20 l/ha Recipe 30 not 1.8 0.9 2.3 0 0 according to the invention - 200 l/ha Recipe 30 not 1.1 0.9 2.3 0 0 according to the invention - 300 l/ha Recipe 31 according to 150.0 141.0 93.9 20 0.2 the invention - 10 l/ha Recipe 31 according to 86.0 73.6 53.9 20 0.1 the invention - 20 l/ha Recipe 31 according to 6.8 10.1 9.4 20 0.01 the invention - 200 l/ha Recipe 31 according to 5.3 5.5 7.4 20 0.006 the invention - 300 l/ha

[0377] Formulations applied at 0.5 1/ha.

[0378] The results show that the recipes illustrative of the invention show larger deposit sizes at 10 L/ha spray volume than at 200 L/ha, and than the recipe not according to the invention at all water volume uses.

[0379] 9. Fluopyram recipes

TABLE-US-00044 TABLE 41 Fluopyram SC recipes Recipe 33 Recipe according Component 32 to the (g/L) reference invention Fluopyram 100 100 Surfynol 4 4 440 Morwet 4 4 D425 Synperonic 44 44 PE/F127 Atlox 4913 3 3 Citric Acid 0.4 0.4 Rhodopol 4 4 23 Silwet ® HS — 40 312 — — Kathon 0.8 0.8 CG/ICP Proxel GXL 1.2 1.2 Propylene 81 81 Glycol SAG1572 3 3 Silcolapse — — 426R Water (add fill fill to 1 litre)

[0380] BOP

[0381] The leaf deposit size was determined according to coverage method.

TABLE-US-00045 TABLE 42 Spray dilution droplet size and dose on non-textured leaves. Super- Super- spreading Deposit spreading surfactant area surfactant dose mm{circumflex over ( )}2 dose % w/v Recipe apple g/ha (g/100 mL) Recipe 32 not 6.4 0 0 according to the invention - 10 l/ha Recipe 32 not 5.5 0 0 according to the invention - 20 l/ha Recipe 32 not 3.6 0 0 according to the invention - 200 l/ha Recipe 33 not 14.0 40 0.4 according to the invention - 10 l/ha Recipe 33 not 11.6 40 0.2 according to the invention - 20 l/ha Recipe 33 according to 8.6 40 0.02 the invention - 200 l/ha

[0382] Formulations applied at 11/ha.

[0383] The results show that on non-structured leaves the deposit size is slightly higher at low water application volumes.

TABLE-US-00046 TABLE 43 Spray dilution droplet size and dose on textured leaves. Super- Super- spreading Deposit spreading surfactant area surfactant dose mm{circumflex over ( )}2 dose % w/v Recipe soybean g/ha (g/100 mL) Recipe 32 not 2.9 0 0 according to the invention - 10 l/ha Recipe 32 not 2.4 0 0 according to the invention - 20 l/ha Recipe 32 not 1.7 0 0 according to the invention - 200 l/ha Recipe 33 according to 135.7 40 0.4 the invention - 10 l/ha Recipe 33 according to 86.1 40 0.2 the invention - 20 l/ha Recipe 33 according to 9.5 40 0.02 the invention - 200 l/ha

[0384] Formulations applied at 11/ha.

[0385] The results show that the recipes illustrative of the invention show larger deposit sizes at 10 L/ha spray volume than at 200 L/ha, and than the recipe not according to the invention at all water volume uses.

[0386] 10. Flupyradifurone recipes

TABLE-US-00047 TABLE 44 Flupyradifurone recipes Recipe 35 Recipe according Component 34 to the (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 Silwet ® HS 312 — 40 — — 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 fill fill litre)

[0387] BOP

[0388] The leaf deposit size was determined according to coverage method.

TABLE-US-00048 TABLE 45 Spray dilution droplet size and dose on non-textured leaves. Super- Super- spreading Deposit spreading surfactant area surfactant dose mm{circumflex over ( )}2 dose % w/v Recipe apple g/ha (g/100 mL) Recipe 34 not 6.5 0 0 according to the invention - 10 l/ha Recipe 34 not 3.5 0 0 according to the invention - 200 l/ha Recipe 35 not 9.9 40 0.4 according to the invention - 10 l/ha Recipe 35 according to 8.3 40 0.02 the invention - 200 l/ha

[0389] Formulations applied at 11/ha.

[0390] The results show that on non-structured leaves the deposit size is slightly higher at low water application volume.

TABLE-US-00049 TABLE 46 Spray dilution droplet size and dose on textured leaves. Super- Super- spreading Deposit spreading surfactant area surfactant dose mm{circumflex over ( )}2 dose % w/v Recipe soybean g/ha (g/100 mL) Recipe 34 not 3.7 0 0 according to the invention - 10 l/ha Recipe 34 not 1.5 0 0 according to the invention - 200 l/ha Recipe 35 not 308.3 40 0.4 according to the invention - 10 l/ha Recipe 35 according to 8.3 40 0.02 the invention - 200 l/ha

[0391] Formulations applied at 11/ha.

[0392] The results show that the recipes illustrative of the invention show larger deposit sizes at 10 L/ha spray volume than at 200 L/ha, and than the recipe not according to the invention at all water volume uses.

[0393] 11. Greenhouse Biology data

[0394] TETRANILIPROLE SC040 formulations

[0395] Test methodology: application onto upperside of pre-infested 1-leaf cabbage plants, BBCH12, for translaminar activity, 2 replicates.

TABLE-US-00050 TABLE 47 Biological efficacy (in % mortality) against mixed population of Myzus persicae on pre-infested cabbage, evaluation 7 days after application Recipe 7 not Recipe 8 Spray Rate according to according to volume of a.i. the the l/ha g/ha invention invention 300 100 0 0 300 20 0 0 300 4 0 0 10 100 85 93 10 20 0 35 10 4 0 0

[0396] The results show that the recipes according to the invention are more efficacious than the reference recipes, and the biological efficacy of the recipes according to the invention is also better at 10 1/ha than at 300 1/ha

[0397] Imidacloprid+Ethiprole SC200 formulation

[0398] Test methodology: application onto upperside of soybeans, BBCH12, for contact and oral uptake, 2 replicates; artificial infestation with 10 Southern green stink bugs nymphs.

TABLE-US-00051 TABLE 48 Biological efficacy (in % mortality) against mixed population of Nezara viridula (N2 nymphs) on soybean, evaluation 3 days after application Rate of a.i. g/ha Rate of a.i. g/ha (delivered as (delivered as Spray recipe 30 not Rate of recipe not volume according to the adjuvant according to the l/ha invention) g/ha % Mortality invention 30) 300 20 0 70 20 300 4 0 20 4 300 0.8 0 5 0.8 10 20 0 80 20 10 4 0 15 4 10 0.8 0 5 0.8 Rate of % Mortality adjuvant Concentration (tank Spray Silwet of adjuvant mix adjuvanted volume HS312 in spray SC200 l/ha g/ha solution (g/l) formulation) 300 30 0.1 75 300 30 0.1 30 300 30 0.1 0 10 30 3 100 10 30 3 80 10 30 3 40

[0399] The results show that the addition of Silwet HS312 improves the biological efficacy of the active ingredients, particularly at 10 1/ha water spray volume