HIGH SPREADING ULV FORMULATIONS FOR FUNGICIDES

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 fungicides, b) one or more organosilicone based surfactants, c) one or more other formulants, and d) water to volume, wherein b) is present in an amount from 5 to 250 g/l.

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 5 to 500 g/l, preferably from 10 to 300 g/l, and most preferred from 20 to 200 g/l.

4: The agrochemical formulation according to claim 1, wherein the fungicide is selected from the group consisting of trifloxistrobin, prothioconazole, tebuconazole, fluopyram, bixafen, isoflucypram, inpyrfluxam, fluoxapiproline, fluopicolide, isotianil, sprioxamin and propamocarb.

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

6: The 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 preferred from 10 to 80 g/l.

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 and/or ionic surfactant (c1), 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 4 to 250 g/l, preferably from 8 to 120 g/l, and most preferred from 10 to 80 g/l, and c2) is present in an amount from 0 to 60 g/l, preferably from 1 to 20 g/l, and most preferred from 2 to 10 g/l, c3) is present in an amount from 0 to 30 g/l, preferably from 0.5 to 20 g/l, and most preferred from 1 to 12 g/l, c4) is present in an amount from 0 to 200 g/l, preferably from 5 to 150 g/l, and most preferred from 10 to 120 g/l, and c5) is present in an amount from 0 to 200 g/l, preferably from 0.1 to 120 g/l, and most preferred from 0.5 to 80 g/l,

10: The agrochemical composition 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 between 2 and 15 l/ha, and more preferably between 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 100 g/ha.

13: The method according to claim 11, wherein the organosilicone based surfactant b) is preferably applied in an amount from 10 g/ha to 100 g/ha, more preferably from 20 g/ha to 80 g/ha, and most preferred from 40 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 fungi, comprising applying the agrochemical formulation according to claim 1, wherein the agrochemical 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 fungi, comprising contacting the harmful fungi, habitats of the harmful fungi, hosts of the harmful fungi, such as plants and seed, soil, areas and environments in which the harmful fungi 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 the harmful fungi that are harmful to plants, with an effective amount of the agrochemical formulation according to claim 1, characterized in that the agrochemical formulation is applied by an unmanned aerial vehicle (UAV), an unmanned guided vehicle (UGV), or a pulse-width-module (PWM).

Description

FIGURES

[0201] 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)

[0202] 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.

[0203] High Spreading ULV Formulations for Fungicides

[0204] The invention is illustrated by the following examples.

EXAMPLES

[0205] Methods

[0206] Method 1: SC Preparation

[0207] 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 was adjusted to 7.0 (+/−0.2) with acid or base (c).

[0208] Method 2: WG Preparation

[0209] The method of the preparation of wettable granule formulations are known in the art and can be produced by known methods familiar to those skilled in the art.

[0210] To produce a fluid bed granule first a water-based technical concentrate has to be prepared. With low shear stirring the active ingredient, safener (a), surfactants (b), dispersants (c), binder (d), antifoam (e), spreader (f) and filler (g) 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, Bühler, Drais, Lehmann) to achieve a particles size D(v,0.9) typically 1 to 15 microns.

[0211] This water-based technical concentrate is then spray-dried in a fluid-bed granulation process to form the wettable granules (WG).

[0212] 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.

[0213] Method 3:

[0214] 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.

[0215] The formulations as shown in the Tables below were obtained by dissolving or mixing the active ingredient, safener (a), surfactants (b), spreader (d) in the organic solvent (c) in a standard apparatus.

[0216] In some cases the dissolving or mixing was facilitated by raising the temperature slightly (not exceeding 60° C.).

[0217] Method 4: Coverage

[0218] Greenhouse plants in the development stage as indicated in tables 1a and 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.

[0219] 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.

[0220] 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.

[0221] Method 5: Fungicide Greenhouse Tests

[0222] 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 I/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 that got attached to the nozzle and the track sprayer device at 30 Hz, opening 8%-100% (10 l-200 l).

[0223] 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.

[0224] 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.

[0225] The practices for inoculation are well known to those skilled in the art.

[0226] The following table shows the diseases and crops used in the tests.

TABLE-US-00003 Abbreviation/ Plant Crop EPPO species Variety Disease English Name 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

[0227] Leaf Surfaces

[0228] In Tables 1a and 1b the contact angle of water on leaf surfaces for textured and non-textured is shown.

TABLE-US-00004 TABLE 1a Plants with textured leaves Contact angle of water ° Plant Species (adaxial) barley Hordeum vulgare 143° (var. Montoya) corn, BBCH-11 Zea mays 150° corn, BBCH-12 Zea mays 149° corn, BBCH-13/14 Zea mays 148° soybean, BBCH-12 Glycine max 149° soybean, BBCH-13 Glycine max 144° rice Oryza sativa 180° wheat, BBCH-12 Triticum aestivum 148° fat-hen Chenopodium album 137° purple crabgrass Digitaria sanguinalis 144°

TABLE-US-00005 TABLE 1b Plants with non-textured leaves Contact angle of water ° Plant Species (adaxial) apple Malus domestica 104° tomato Solanum lycopersicum 106° corn, BBCH-15/16 Zea mays 108° corn, BBCH-17 Zea mays 107° corn, BBCH-18 Zea mays  96° corn, BBCH-19 Zea mays  87° velvetleaf Abutilon theophrasti 103° redroot pigweed Amaranthus retroflexus not measured

[0229] Examples of non-textured crops and plants include tomatoes, peppers, potatoes, carrot, celery, sugar beet, beetroot, spinach, lettuce, beans, peas, clover, apple, pear, peach, apricot, plum, mango, avocado, olive, citrus, orange, lemon, lime, grape, fig, cucumber, melon, water melon, strawberry, raspberry, blueberry, sunflower, pumpkin, soybean (≥GS 16 (BBCH 16)), corn (≥GS 15 (BBCH 15), cotton.

[0230] Examples of textured crops and plants include garlic, onions, leeks, soybean (≤GS 16 (BBCH 16)), oats, wheat, barley, rice, sugarcane, pineapple, banana, linseed, lilies, orchids, corn (≤GS 15 (BBCH 15)), cabbage, brussels sprouts, broccoli, Cauliflower, rye, rapeseed, tulips and peanut.

[0231] Materials

TABLE-US-00006 TABLE 2a Exemplified trade names and CAS-No's of preferred organosilicone compounds (b) Product Chemical name Cas No. Supplier Silwet ® 3-(2-methoxyethoxy)propyl- 27306-78-1 Momentive L77 methyl-bis(trimethylsilyloxy) silane Silwet ® 2-[3-[[dimethyl 67674-67-3 Momentive 408 (trimethylsilyloxy)silyl]oxy- methyl-trimethylsilyloxysilyl] propoxy]ethanol Silwet ® 3-[methyl-bis 134180-76-0 Momentive 806 (trimethylsilyloxy)silyl] propan-1-ol; 2-methyloxirane; oxirane Break-thru ® 3-[methyl-bis 134180-76-0 Evonik S240 (trimethylsilyloxy)silyl] propan-1-ol; 2-methyloxirane; oxirane Break-thru ® 3-(2-methoxyethoxy)propyl- 27306-78-1 Evonik S278 methyl-bis(trimethylsilyloxy) silane Silwet ® Polyalkylenoxide Silane Momentive HS 312 Silwet ® Polyalkylenoxide Silane Momentive HS 604 BreakThru ® Siloxanes and Silicones, 191044-49-2 Evonik OE 444 cetyl Me, di-Me BreakThru 3-[methyl-bis 134180-76-0 Evonik SD260 (trimethylsilyloxy)silyl] propan-1-ol; 2-methyloxirane; oxirane BreakThru 3-[methyl-bis 134180-76-0 Evonik S301 (trimethylsilyloxy)silyl] propan-1-ol; 2-methyloxirane; oxirane

TABLE-US-00007 TABLE 2b Exemplified trade names and CAS-No's of preferred compounds (c) Product Chemical name Cas No. Supplier Morwet ® Naphthalene sulphonate 9008-63-3 New XX D425 formaldehyde condensate Na salt Synperonic ® block-copolymer of 9003-11-6 Croda PE/F127 polyethylene oxide and polypropylene oxide Synperonic ® alcohol ethoxylate 68131-39-5 Croda A7 (C12/C15-EO7) Xanthan Polysaccharide 11138-66-2 Proxel ® GXL 1.2-benzisothiazol- 2634-33-5 Arch 3(2H)-one Chemicals Kathon ® 5-chloro-2-methyl-4- 26172-55-4 Dow CG/ICP isothiazolin-3-one plus plus 2-methyl-4-isothiazolin- 2682-20-4 3-one Propylene glycol 1,2-Propylene glycol 57-55-6 SAG ® 1572 Dimethyl siloxanes and 63148-62-9 Momentive silicones Atlox ® 4913 methyl methacrylate 119724-54-8 Croda graft copolymer with polyethylene glycol ATLAS ® G Oxirane, methyl-, 9038-95-3 Croda 5000 polymer with oxirane, monobutyl ether SILCOLAPSE ® Polydimethylsiloxanes 9016-00-6 BLUESTAR 454 and silica SILICONES RHODOPOL ® Polysaccharide 11138-66-2 Solvay 23 ACTICIDE ® Mixture of 2-methyl- 2682-20-4 Thor GmbH MBS 4-isothiazolin-3-one 2634-33-5 (MIT) and 1,2- benzisothiazolin-3-one (BIT) in water Soprophor ® Poly(oxy-1,2-ethanediyl),. 104376-75-2 Solvay TS54 alpha.-phenyl-.omega.- 99734-09-5 hydroxy-, styrenated

Example 1 Isoflucypram 50 SC

[0232]

TABLE-US-00008 TABLE 3 Recipes 1 and 2. Recipe 2 Recipe 1 according to Component (g/l) reference the invention Isoflucypram (a) 5.0 5.0 Morwet ® D425 (c) 1.0 1.0 Synperonic ® PE/F127 (c) 5.0 5.0 Silwet ® 806 (b) 0.0 50.0 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 (c) 1.5 1.5 (Buffer solution pH = 7) NaH.sub.2PO.sub.4 (c) 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) (C) To volume To volume (~921) (~869)

[0233] The method of preparation used was according to Method 1.

[0234] Results

[0235] Greenhouse

[0236] Efficacy Data

TABLE-US-00009 TABLE 4 Biological efficacy on PUCCRT 2 (ISY 50 SC) Recipe 1 Recipe 2 Spray reference according to volume Rate of SC Rate of Efficacy the invention l/ha applied l/ha a.i. g/ha [%] Efficacy [%] 200 0.5 25 90 100 200 0.1 5 20 80 200 0.05 2.5 10 30 10 0.5 25 40 95 10 0.1 5 30 85 10 0.05 2.5 10 60 Method 5: wheat, protective 1 day before inoculation, evaluation 10 DAT

[0237] The results show that recipe 2 illustrative of the invention shows higher efficacy at 10 l/ha spray volume than 200 l/ha. Furthermore, recipe 2 shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe 1 without the organosilicone super-spreader.

TABLE-US-00010 TABLE 5 Biological efficacy on PYRNTE 2 (ISY 50 SC) Recipe 1 Recipe 2 Spray reference according to volume Rate of SC Rate of Efficacy the invention l/ha applied l/ha a.i. g/ha [%] Efficacy [%] 200 0.5 25 97 100 200 0.1 5 43 100 200 0.05 2.5 29 71 200 0.02 1 14 86 10 0.5 25 93 100 10 0.1 5 71 99 10 0.05 2.5 71 97 10 0.02 1 79 86 Method 5: barley, protective 1 day before inoculation, evaluation 10 DAT

[0238] The results show that recipe 2 illustrative of the invention shows higher efficacy at 10 l/ha spray volume than 200 l/ha. Furthermore, recipe 2 shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe 1 without the organosilicone super-spreader.

Example 3 Isoflucypram 50 SC

[0239]

TABLE-US-00011 TABLE 8 Recipes 5 and 6. Recipe 5 Recipe 6 according Component (g/l) reference to the 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 Silwet ® 806 (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

[0240] The method of preparation used was according to Method 1.

[0241] Spreading—Pipette Spreading Tests on Leaves

[0242] The leaf deposit size was determined according to Method 4 (b) (2 uL).

TABLE-US-00012 TABLE 9 Spray dilution droplet size and dose on non-textured apple leaves and textured soybean and rice leaves. Super- Super- Deposit Deposit Deposit spreading spreading area area area surfactant surfactant mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose dose Recipe apple soybean rice g/ha % w/v Recipe 5 not 5.12 2.45 1.14 0 0 according to the invention - 10 l/ha Recipe 5 not 5.50 2.84 1.79 0 0 according to the invention - 200 l/ha Recipe 6 193.9 355.9 118.3 30 0.3 according to the invention - 10 l/ha Recipe 6 24.97 32.86 22.05 30 0.015 according to the invention - 200 l/ha Formulations applied at 0.5 l/ha.

[0243] The results show that recipe 6 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 5.

Example 4: Fungicide TFS 100 SC

[0244]

TABLE-US-00013 TABLE 11 Recipe 8 Recipe 7 according to Component (g/l) reference the invention Trifloxystrobin (a) 100.0 100.0 Morwet ® D425 (c) 5.0 5.0 Synperonic ® PE/F127 (c) 12.0 12.0 Silwet ® 408 (b) 0.0 50.0 Xanthan (c) 3.0 3.0 Proxel ® GXL (c) 1.8 1.8 Kathon ® CG/ICP (c) 0.8 0.8 Propylene glycol (c) 80.0 80.0 SAG ® 1572 (c) 6.0 6.0 Na.sub.2HPO.sub.4 (Buffer 0.0 1.5 solution pH = 7) NaH.sub.2PO.sub.4 (Buffer 0.0 0.8 solution pH = 7) Water (add to 1 litre) To volume (~822) To volume (~770)

[0245] The method of preparation used was according to Method 1.

[0246] Results

[0247] Spray Coverage Tests on Leaves

[0248] The leaf coverage was determined according to method 4.

TABLE-US-00014 TABLE 12 Spray deposit coverage and dose on non-textured leaves. Organosilicone surfactant Leaf Organosilicone dose in spray coverage % surfactant dose liquid Recipe @ 0° apple g/ha % w/v Recipe 7 not 6.4 0 0 according to the invention - 10 l/ha Recipe 7 not 12.6 0 0 according to the invention - 40 l/ha Recipe 7 not 18.3 0 0 according to the invention - 200 l/ha Recipe 7 not 28.3 0 0 according to the invention - 500 l/ha Recipe 8 according 44.5 25 0.25 to the invention - 10 l/ha Recipe 8 according 25.4 25 0.0625 to the invention - 40 l/ha Recipe 8 according 35.3 25 0.0125 to the invention - 200 l/ha Recipe 8 according 56.8 25 0.0005 to the invention - 500 l/ha Formulations applied at 0.5 l/ha.

[0249] The results show that on non-textured leaves the coverage is generally higher at higher water application volumes.

TABLE-US-00015 TABLE 13 Spray deposit coverage and dose on textured leaves. Organosilicone surfactant Leaf Leaf Leaf Organosilicone dose in spray coverage % coverage % coverage % surfactant dose liquid Recipe @ 0° soybean @ 0° barley @ 0° rice g/ha % w/v Recipe 7 not 3 2 2 0 0 according to the invention - 10 l/ha Recipe 7 not 11.5 6 3.1 0 0 according to the invention - 40 l/ha Recipe 7 not 9.7 1.7 3.5 0 0 according to the invention - 200 l/ha Recipe 7 not 17 1.7 3.8 0 0 according to the invention - 500 l/ha Recipe 8 29.7 23.3 15.6 50 0.25 according to the invention - 10 l/ha Recipe 8 23 17.6 10.4 50 0.0625 according to the invention - 40 l/ha Recipe 8 15.8 6.3 1.2 50 0.0125 according to the invention - 200 l/ha Recipe 8 22.8 4.7 4.1 50 0.0005 according to the invention - 500 l/ha Formulations applied at 0.5 l/ha.

[0250] The results show that recipe 8 illustrative of the invention shows greater coverage at 10 l/ha spray volume than at 200 l/ha and 500 l/ha, and also compared to the reference recipe 7

Example 6: PTZ 20 SC

[0251]

TABLE-US-00016 TABLE 16 Recipes 15 and 16. Recipe 16 Recipe 15 according to Component (g/l) reference the invention Prothioconazole (a) 20.0 20.0 Morwet D425 (c) 2.0 2.0 Synperonic ® PE/F127 (c) 5.0 5.0 Silwet ® 806 (b) 0.0 50.0 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) 2.0 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) To volume To volume (~913) (~863)

[0252] The method of preparation used was according to Method 1.

[0253] Greenhouse

TABLE-US-00017 TABLE 17 Biological efficacy on PUCCRT Rate Recipe 16 Spray of SC Rate Recipe 15 according to volume applied of a.i. reference the invention l/ha l/ha g/ha Efficacy [%] Efficacy [%] 200 5 100 78 94 200 2.5 50 33 78 200 1.25 25 22 56 10 5 100 94 100 10 2.5 50 67 100 10 1.25 25 22 78 Method 5: wheat, 1 day protective, evaluation 9 DAT

[0254] The results show that recipe 16 illustrative of the invention shows higher efficacy at 10 l/ha spray volume than 200 l/ha. Furthermore, recipe 16 shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe 15 without the organosilicone super-spreader.

TABLE-US-00018 TABLE 18 Biological efficacy on PUCCRT Rate Recipe 16 Spray of SC Rate Recipe 15 according to volume applied of a.i. reference the invention l/ha l/ha g/ha Efficacy [%] Efficacy [%] 200 5 100 56 100 200 2.5 50 22 33 200 1.25 25 11 0 10 5 100 94 100 10 2.5 50 78 94 10 1.25 25 33 94 Method 5: wheat, 1 dav protective, evaluation 9 DAT

[0255] The results show that recipe 16 illustrative of the invention shows higher efficacy at 10 l/ha spray volume than 200 l/ha. Furthermore, recipe 16 shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe 15 without the organosilicone super-spreader.

TABLE-US-00019 TABLE 19 Biological efficacy on PHAKPA Rate Recipe 16 Spray of SC Rate Recipe 15 according to volume applied of a.i. reference the invention l/ha l/ha g/ha Efficacy [%] Efficacy [%] 200 0.5 5 98 99 200 0.1 1 56 44 200 0.05 0.5 51 20 10 0.5 5 100 100 10 0.1 1 98 89 10 0.05 0.5 32 53 Method 5: soybean, 1 day preventive, evaluation 7 days after infestation

[0256] The results show that recipe 16 illustrative of the invention shows higher efficacy at 10 l/ha spray volume than 200 l/ha.

TABLE-US-00020 TABLE 20 Biological efficacy on PHAKPA Rate Recipe 16 Spray of SC Rate Recipe 15 according to volume applied of a.i. reference the invention l/ha l/ha g/ha Efficacy [%] Efficacy [%] 200 0.5 5 98 100 200 0.1 1 94 98 200 0.05 0.5 95 98 200 0.01 0.1 58 98 10 0.5 5 100 100 10 0.1 1 98 97 10 0.05 0.5 89 91 10 0.01 0.1 46 72 Method: soybean, 2 days curative, evaluation 7 days after infestation

[0257] The results show that recipe 16 illustrative of the invention shows higher efficacy at 10 l/ha spray volume than 200 l/ha. Furthermore, recipe 16 shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe without the organosilicone super-spreader.

TABLE-US-00021 TABLE 21 Dose rate of organosilicone super-spreader Recipe 16 according to the invention Recipe 15 reference Super- Rate Super- Super- Super- spreader Spray of SC spreader spreader spreader dose volume applied dose dose dose in spray l/ha l/ha g/ha % w/v g/ha liquid % w/v 200 0.25 0 0 12.5 0.00625 200 0.05 0 0 2.5 0.00125 200 0.025 0 0 1.25 0.000625 200 0.005 0 0 0.25 0.000125 10 0.25 0 0 12.5 0.125 10 0.05 0 0 2.5 0.025 10 0.025 0 0 1.25 0.0125 10 0.005 0 0 0.25 0.0025

[0258] the concentration of organosilicone super-spreader at 10 L/ha spray volume gives higher performance than 200 L/ha.

Example 7: TBZ 20 SC

[0259]

TABLE-US-00022 TABLE 23 Recipes 17 and 18 Recipe 18 Recipe 17 according to Component (g/l) reference the invention Tebuconazole (a) 20.0 20.0 Morwet D425 (c) 2.0 2.0 Synperonic ® PE/F127 (c) 5.0 5.0 Silwet ® 806 (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 SAG ® 1572 (c) 2.0 2.0 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 (~913) (~853)

[0260] The method of preparation used was according to Method 1.

[0261] Greenhouse

TABLE-US-00023 TABLE 24 Biological efficacy on PHAKPA Rate Recipe 18 Spray of SC Rate Recipe 17 according to volume applied of a.i. reference the invention l/ha l/ha g/ha Efficacy [%] Efficacy [%] 200 0.25 5 99 100 200 0.050 1 53 58 200 0.025 0.5 25 48 10 0.25 5 100 100 10 0.050 1 86 90 10 0.025 0.5 55 79 Method: soybean, 1 day protective, evaluation 7 dat

[0262] The results show that recipe 18 illustrative of the invention shows higher efficacy at 10 l/ha spray volume than 200 l/ha. Furthermore, recipe 18 shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe without the organosilicone super-spreader.

TABLE-US-00024 TABLE 25 Biological efficacy on PHAKPA Rate Recipe 18 Spray of SC Rate Recipe 17 according to volume applied of a.i. reference the invention l/ha l/ha g/ha Efficacy [%] Efficacy [%] 200 250 5 100 100 200 50 1 62 94 200 25 0.5 35 64 200 5 0.1 17 24 10 250 5 96 99 10 50 1 69 94 10 25 0.5 46 85 10 5 0.1 2 14 Method 5: soybean, 1 day protective, evaluation 7 dat (days after treatment)

[0263] The results show that recipe 18 illustrative of the invention shows higher efficacy at 10 l/ha spray volume than 200 l/ha. Furthermore, recipe 18 shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe 17 without the organosilicone super-spreader.

Example 8: Bixafen 20 SC

[0264]

TABLE-US-00025 TABLE 26 Recipes 19 and 20 Recipe 20 Recipe 19 according to Component (g/l) reference the invention Bixafen (a) 20.0 20.0 Morwet D425 (c) 2.0 2.0 Synperonic ® PE/F127 (c) 5.0 5.0 Silwet ® 806 (b) 0.0 50 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 Na2HPO4 (Buffer (c) 1.5 1.5 solution pH = 7) NaH2PO4 (Buffer (c) 0.8 0.8 solution pH = 7) Water (add to 1 litre) To volume To volume (~913) (~863)

[0265] The method of preparation used was according to Method 1.

[0266] Greenhouse

TABLE-US-00026 TABLE 27 Biological efficacy on ERYSGH Rate Recipe 20 Spray of SC Rate Recipe 19 according to volume applied of a.i. reference the invention l/ha l/ha g/ha Efficacy [%] Efficacy [%] 200 5 100 50 100 200 2.5 50 17 50 200 1.25 25 0 33 10 5 100 17 67 10 2.5 50 0 67 10 1.25 25 0 33 Method 5: barley, 1 day protective, evaluation 7 dat

[0267] The results show that recipe 20 illustrative of the invention shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe 19 without the organosilicone super-spreader.

TABLE-US-00027 Table 28 Biological efficacy on PUCCRT Recipe 19 Recipe 20 Spray reference according to the volume Rate of SC Rate of Efficacy invention l/ha applied l/ha a.i. g/ha [%] Efficacy [%] 200 5 100 80 100 200 2.5 50 30 90 200 1.25 25 0 60 200 0.5 10 0 30 10 5 100 50 70 10 2.5 50 30 80 10 1.25 25 20 50 10 0.5 10 0 30 Method 5: barley, 1 day protective, evaluation 12 dat

[0268] The results show that recipe 20 illustrative of the invention shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe 19 without the organosilicone super-spreader.

TABLE-US-00028 TABLE 29 Biological efficacy on PUCCRT Recipe 19 Recipe 20 Spray reference according to volume Rate of SC Rate of Efficacy the invention l/ha applied l/ha a.i. g/ha [%] Efficacy [%] 200 5 100 50 95 200 2.5 50 30 95 200 1.25 25 30 50 10 5 100 50 90 10 2.5 50 50 80 10 1.25 25 40 80 Method 5: barley, 1 day protective, evaluation 12 dat

[0269] The results show that recipe 20 illustrative of the invention shows higher efficacy at 10 l/ha spray volume than 200 l/ha. Furthermore, recipe 20 shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe 19 without the organosilicone super-spreader.

Example 9: Fluoxapiprolin 5 SC

[0270]

TABLE-US-00029 TABLE 30 Recipes 21 and 22 Recipe 22 Recipe 21 according to Component (g/l) reference the invention Fluoxapiprolin (a) 5.0 5.0 Morwet D425 (c) 1.0 1.0 Synperonic ® PE/F127 (c) 5.0 5.0 Silwet ® 408 (b) 0.0 50 Xanthan (c) 3.6 3.6 Proxel ® GXL (c) 1.5 1.5 Kathon ® CG/ICP (c) 0.8 0.8 Propylene glycol (c) 50.0 50.0 SAG ® 1572 (c) 4.0 4.0 Na.sub.2HPO.sub.4 (Buffer solution (c) 0.0 1.5 pH = 7) NaH.sub.2PO.sub.4 (Buffer solution (c) 0.0 0.8 pH = 7) Water (add to 1 litre) To volume To volume (~929) (~877)

[0271] The method of preparation used was according to Method 1.

[0272] Greenhouse

TABLE-US-00030 TABLE 31 Biological efficacy on PHYTIN Rate of Recipe 21 Recipe 22 Spray SC reference according to volume applied Rate of Efficacy the invention l/ha l/ha a.i. g/ha [%] Efficacy [%] 200 0.5 2.5 83 96 200 0.2 1 59 76 200 0.1 0.5 61 76 10 0.5 2.5 54 96 10 0.2 1 37 53 10 0.1 0.5 24 44 Method 5: tomato, 1 day preventive, evaluation 7 days after infestation

[0273] The results show that recipe 22 illustrative of the invention shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe 21 without the organosilicone super-spreader.

Example 10: Fluoxapiprolin 50 SC

[0274]

TABLE-US-00031 TABLE 32 Recipes 23 and 24 Recipe 24 Recipe 23 according to Component (g/l) reference the invention Fluoxapiprolin (a) 50.0 50.0 Morwet D425 (c) 10.0 10.0 Soprophor ® TS54 (c) 20.0 20.0 Synperonic ® PE/F127 (b) 10.0 10.0 Silwet ® 408 (c) 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 solution (c) 1.5 1.5 pH = 7) NaH.sub.2PO.sub.4 (Buffer solution (c) 0.8 0.8 pH = 7) Water (add to 1 litre) To volume To volume (~896) (~836)

[0275] The method of preparation used was according to Method 1.

[0276] Pipette Spreading Tests on Leaves

[0277] The leaf deposit size was determined according to Method 4 (b) with 2 μL deposits.

TABLE-US-00032 TABLE 33 Spray dilution droplet size and dose on non-textured apple leaves and textured soybean and rice leaves. Super- spreading Super- surfactant Deposit Deposit Deposit spreading dose in area area area surfactant spray mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose liquid Recipe apple soybean rice g/ha % w/v Recipe 23 not 3.68 2.19 1.69 0 0 according to the invention—10 l/ha Recipe 23 not 3.58 2.24 2.23 0 0 according to the invention—200 l/ha Recipe 24 according 156.7 271.2 153.9 60 0.6 to the invention—10 l/ha Recipe 24 according 20.70 36.97 29.11 60 0.03 to the invention—200 l/ha Formulations applied at 0.5 l/ha.

[0278] The results show that recipe 24 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 23. The effect is observed on both textured and non-textured leaf surfaces.

Example 11 Inpyrfluxam 25 SC

[0279]

TABLE-US-00033 TABLE 34 Recipes 25 and 26 Recipe 26 Recipe 25 according to Component (g/l) reference the 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 Silwet ® 806 (b) 0.0 100.0 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 solution (c) 1.5 1.5 pH = 7) NaH.sub.2PO.sub.4 (Buffer solution (c) 0.8 0.8 pH = 7) Water (add to 1 litre) To volume To volume (~901) (~801)

[0280] The method of preparation used was according to Method 1.

[0281] Pipette Spreading Tests on Leaves

[0282] The leaf deposit size was determined according to Method 4 (b) with 2 μL deposits.

TABLE-US-00034 TABLE 35 Spray dilution droplet size and dose on non-textured apple leaves and textured soybean and rice leaves. Super- Super- Deposit Deposit Deposit spreading spreading area area area surfactant surfactant mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose dose Recipe apple soybean rice g/ha % w/v Recipe 25 not 7.28 2.27 1.75 0 0 according to the invention—10 l/ha Recipe 25 not 4.74 3.74 2.46 0 0 according to the invention—200 l/ha Recipe 25 not 3.20 1.34 2.61 0 0 according to the invention—800 l/ha Recipe 26 according 145.1 241.7 149.7 100 1.0 to the invention—10 l/ha Recipe 26 according 85.3 198.4 51.1 100 0.05 to the invention—200 l/ha Recipe 26 according 34.8 59.7 29.1 100 0.0125 to the invention—800 l/ha Formulations applied at 1 l/ha.

[0283] The results show that recipe 26 illustrative of the invention shows larger deposit sizes at 10 l/ha spray volume than at 200 l/ha and 800 l/ha and also compared to the reference recipe 25 at all spray volumes.

Example 12: Fluopicolide 100 SC

[0284]

TABLE-US-00035 TABLE 36 Recipes 27 and 28. Recipe 28 Recipe 27 according to Component (g/l) reference the invention Fluopicolide (a) 100.0 100.0 Morwet—® D425 (c) 10.0 10.0 Soprophor ® FLK (c) 20.0 20.0 Synperonic ® PE/F127 (b) 10.0 10.0 Silwet ® 408 (c) 0.0 40.0 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 solution (c) 1.5 1.5 pH = 7) NaH.sub.2PO.sub.4 (Buffer solution (c) 0.8 0.8 pH = 7) Water (add to 1 litre) To volume To volume (~846) (~806)

[0285] The method of preparation used was according to Method 1.

[0286] Pipette Spreading Tests on Leaves

[0287] The leaf deposit size was determined according to Method 4 (b) with 2 μL deposits.

TABLE-US-00036 TABLE 37 Spray dilution droplet size and dose on non-textured apple leaves and textured soybean and rice leaves. Super- spreading Super- surfactant Deposit Deposit Deposit spreading dose in area area area surfactant spray mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose liquid Recipe apple soybean rice g/ha % w/v Recipe 27 not 5.23 2.77 2.30 0 0 according to the invention—10 l/ha Recipe 27 not 3.49 1.21 1.52 0 0 according to the invention—200 l/ha Recipe 28 according to 57.95 298.5 142.3 40 0.4 the invention—10 l/ha Recipe 28 according to 29.56 64.05 22.63 40 0.02 the invention—200 l/ha Formulations applied at 1.0 l/ha.

[0288] The results show that recipe 28 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 27. The effect is greater on textured leaf surfaces.

Example 13: Fluopyram 200 SC

[0289]

TABLE-US-00037 TABLE 39 Recipes 29 and 30 Recipe 30 Recipe 29 according to Component (g/l) reference the invention Fluopyram (a) 200.0 200.0 Morwet ® D425 (c) 10.0 10.0 Soprophor ® TS54 (c) 20.0 20.0 Synperonic ® PE/F127 (b) 10.0 10.0 Silwet ® 408 (c) 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 solution (c) 1.5 1.5 pH = 7) NaH.sub.2PO.sub.4 (Buffer solution (c) 0.8 0.8 pH = 7) Water (add to 1 litre) To volume To volume (~786) (~726)

[0290] The method of preparation used was according to Method 1

[0291] Pipette Spreading Tests on Leaves

[0292] The leaf deposit size was determined according to Method 4 (b) with 2 μL deposits.

TABLE-US-00038 TABLE 40 Spray dilution droplet size and dose on non-textured apple leaves and textured soybean and rice leaves. Super- spreading Super- surfactant Deposit Deposit Deposit spreading dose in area area area surfactant spray mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose liquid Recipe apple soybean rice g/ha % w/v Recipe 29 not 3.96 1.52 1.64 0 0 according to the invention—10 l/ha Recipe 29 not 3.57 1.59 1.08 0 0 according to the invention—200 l/ha Recipe 30 according to 157.1 266.9 134.0 30 0.3 the invention—10 l/ha Recipe 30 according to 57.28 71.25 24.51 30 0.015 the invention—200 l/ha Formulations applied at 0.5 l/ha.

[0293] The results show that recipe 30 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 29. The effect is greater on textured leaf surfaces.

Example 15 PHC 625 SL

[0294]

TABLE-US-00039 TABLE 48 Recipes 35 and 36 Recipe 36 Recipe 35 according to Component (g/l) reference the invention Propamocarb Hydrochloride (a) 869.5 869.5 71.98% concentrate (aqueous) Silwet ® HS312 (b) 0.0 18.0 Etocas ® 35 (c) 14.0 14.0 SAG ® 1572 (c) 1.0 1.0 Water (add to 1 litre) (c) To volume To volume (~196) (~178)

[0295] The method of preparation used was according to Method 1.

[0296] Pipette Spreading Tests on Leaves

[0297] The leaf deposit size was determined according to coverage method 4.

TABLE-US-00040 TABLE 49 Spray dilution droplet size and dose on non-textured leaves. Deposit Organosilicone area Organosilicone surfactant dose mm{circumflex over ( )}2 surfactant dose in spray liquid Recipe apple g/ha % w/v Recipe 35 not 5.6 0 0 according to the invention—10 l/ha Recipe 35 not 5.31 0 0 according to the invention—200 l/ha Recipe 36 according to 11.4 18 0.18 the invention—10 l/ha Recipe 36 according to 9.0 18 0.009 the invention—200 l/ha Formulations applied at 1 l/ha.

[0298] The results show on non-textured leaves that the coverage is similar at both water application volumes.

TABLE-US-00041 TABLE 50 Spray dilution droplet size and dose on textured leaves. Organo- Organo- silicone Deposit Deposit Deposit silicone surfactant area area area surfactant dose in mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose spray liquid Recipe soybean rice barley g/ha % w/v Recipe 35 not 3.3 2.5 4.0 0 0 according to the invention—10 l/ha Recipe 35 not 1.8 1 2.8 0 0 according to the invention—200 l/ha Recipe 36 18.1 104 37.7 18 0.18 according to the invention—10 l/ha Recipe 36 5.5 7.3 6.9 18 0.009 according to the invention—200 l/ha Formulations applied at 1 l/ha.

[0299] The results show that recipe 36 illustrative of the invention shows greater coverage and larger deposit sizes at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe 35.