HIGH SPREADING AND UPTAKE ULV FORMULATIONS

Abstract

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

Claims

1: An agrochemical formulation comprising a) one or more active ingredients, b) one or more spreading agents, c) one or uptake enhancers, d) one formulants, e) one or more carriers to volume, wherein b) is present in an amount from 5 to 150 g/l.

2: An agrochemical formulation according to claim 1, wherein b) is selected from the group consisting of polyalkyleneoxide modified heptamethyltrisiloxanes and dioctylsulfosuccinate, alcohol ethoxylates, and ethoxylated diacetylene-diols with 1 to 6 EO.

3: An agrochemical formulation according to claim 1, wherein c) is selected selected from the group comprising tris (2-ethylhexyl) phosphate, rapeseed oil methyl esters, ethoxylated coconut alcohols, ethoxylated branched alcohols, propoxy-ethoxylated alcohols, ethoxylated mono- or diesters of glycerine comprising fatty acids with 8-18 carbon atoms and an average of 10-40 EO units, ethoxylated oleic acid and mineral oils.

4: An agrochemical formulation according to claim 1, wherein a) is present in an amount from 5 to 300 g/l, preferably from 10 to 250 g/l, and most preferred from 20 to 210 g/l.

5: An agrochemical formulation according to ene claim 1, wherein b) is present in an amount from 5 to 150 g/l, preferably from 10 to 120 g/l, and most preferred from 15 to 110 g/l.

6: An agrochemical formulation according to claim 1, wherein c) is present in an amount from 10 to 150 g/l, preferably from 25 to 120 g/l, and most preferred from 30 to 110 g/l.

7: An agrochemical formulation according to claim 1, wherein d) is present in an amount from 5 to 250 g/l, preferably from 10 to 150 g/l, and most preferred from 20 to 120 g/l.

8: An agrochemical formulation according to claim 1, wherein the active ingredient is selected from the group consisting of fluopicolide, fluopyram, fluoxapiprolin, inpyrfluxam, isoflucypram, isothianil, tebuconazole, trifloxystrobin, ethiprole, imidacloprid, spirotetramat, tetraniliprole, tembotrione, triafamone and isoxadifen-ethyl.

9: An agrochemical formulation according to claim 1, wherein component d) comprises at least one non-ionic surfactant and/or ionic surfactant (d1), one rheological modifier (d2), and one antifoam substance (d3) and at least one antifreeze agent (d4).

10: An agrochemical formulation according to claim 1, comprising the components a) to e) in the following amounts a) from 5 to 300 g/l, preferably from 10 to 250 g/l, and most preferred from 20 to 210 g/l, b) from, 5 to 150 g/l, preferably from 10 to 120 g/l, and most preferred from 15 to 110 g/l, c) from 10 to 150 g/l, preferably from 25 to 120 g/l, and most preferred from 30 to 110 g/l, d1) from 4 to 250 g/l, preferably from 8 to 120 g/l, and most preferred from 10 to 80 g/l, d2) from 0 to 60 g/l, preferably from 1 to 20 g/l, and most preferred from 2 to 10 g/l, d3) from 0 to 30 g/l, preferably from 0.5 to 20 g/l, and most preferred from 1 to 12 g/l, d4) from 0 to 200 g/l, preferably from 5 to 150 g/l, and most preferred from 10 to 120 g/l, d5) from 0 to 200 g/l, preferably from 0.1 to 120 g/l, and most preferred from 0.5 to 80 g/l, e) carrier to volume.

11: An 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.

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

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

14: The method according to claim 12, wherein b) is preferably applied from 5 g/ha to 150 g/ha, more preferably from 7.5 g/ha to 100 g/ha, and most preferred from 10 g/ha to 60 g/ha.

15: The method according to claim 12, wherein the formulation is applied on plants or crops with textured leaf surfaces.

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

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

Description

EXAMPLES

[0268] Method 1: SC Preparation

[0269] The method of the preparation of suspension concentrate formulations are known in the art and can be produced by known methods familiar to those skilled in the art. A 2% gel of the xanthan (c) in water and the biocides (c) was prepared with low shear stirring. The active ingredient (a), non-ionic and anionic dispersants (c), antifoam (c) and other formulants (c) were mixed with water to form a slurry, first mixed with a high shear rotor-stator mixer (Ultra-Turrax®) to reduce the particle size D(v,0.9) to approximately 50 microns, then passed through one or more bead mills (Eiger® 250 Mini Motormill) to achieve a particles size D(v,0.9) typically 1 to 15 microns. Then the additives (b), (c) and (d) and xanthan gel prepared above were added and mixed in with low shear stirring until homogeneous. Finally, the pH is adjusted if needed with acid or base (e).

[0270] Method 2: WG Preparation

[0271] 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.

[0272] 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, Bühler, 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).

[0273] 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.

[0274] Likewise, any other spraying process, like e.g. classical spray drying can be used as granulation method.

[0275] 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.

[0276] Method 3: EC Preparation

[0277] 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.

[0278] Method 4: OD Preparation

[0279] 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 <10μ is achieved. Alternatively, formulation components are mixed in a bottle followed by addition of approx. 25 vol.-% of 1.0-1.25 mm glass beads. The bottle is then closed, clamped in an agitator apparatus (e.g. Retsch MM301) and treated at 30 Hz for several minutes until a particle size of <10μ is achieved.

[0280] Method 5: Coverage

[0281] 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.

[0282] 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.

[0283] 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.

[0284] Method 6: Insecticide Greenhouse Tests

[0285] 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).

[0286] 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.

[0287] The application was conducted with a tracksprayer onto the upperside of leaves with 300 l/ha or 10 l/ha application volume. Nozzles used: Lechler's TeeJet TP8003E (for 300 l/ha) and Lechler's 652.246 together with a pulse-width-module (PWM) (for 10 l/ha). For each single dose applied, usually 2 to 5 replicates were simultaneously treated.

[0288] After treatment, plants were artificially infested, if needed, and kept during test duration in a greenhouse or climate chamber. The efficacy of the treatments was rated after evaluation of mortality (in general, given in %) and/or plant protection (calculated e.g. from feeding damage in comparison to corresponding controls) at different points of time. Only mean values are reported.

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

[0289] Selected crops were grown under greenhouse conditions in plastic pots containing “peat soil T”. At appropriate crop stage, plants were prepared for the treatments, e.g. by infestation with target pest approximately 2 days prior to treatment (table M1).

[0290] 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.

[0291] The application was conducted with tracksprayer onto upperside of leaves with 300 l/ha or 10 l/ha application volume. Nozzles used: Lechler's TeeJet TP8003E (for 300 l/ha) and Lechler's 652.246 together with a pulse-width-module (PWM) (for 10 l/ha). For each single dose applied, usually 2 to 5 replicates were simultaneously treated.

[0292] 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.

[0293] Method 7: Cuticle Wash-Off

[0294] A disc from an apple cuticle was fixed with the outside surface facing upwards to a glass microscope slide with a thin layer of medium viscosity silicone oil. To this 0.9 μl drops of the different formulations diluted at the spray dilution in deionised water containing 5% CIPAC C water were applied with a micropipette and left to dry for 1 hour. Each deposit was examined in an optical transmission microscope fitted with crossed polarising filters and an image recorded. The slide containing the cuticle with the dried droplets of the formulations was held under gently running deionised water (flow rate approximately 300 ml/minute at a height 10 cm below the tap outlet) for 15 s. The glass slide was allowed to dry and the deposits were re-examined in the microscope and compared to the original images. The amount of active ingredient washed off was visually estimated and recorded in steps of 10%. Three replicates were measured and the mean value recorded.

[0295] Method 8: Leaf Wash-Off

[0296] Apple or corn leaf sections were attached to a glass microscope slide. To this 0.9 μl drops of the different formulations diluted at the spray dilution in deionised water containing 5% CIPAC C water and a small amount of fluorescent tracer (Tinopal OB as a micron sized aqueous suspension) were applied with a micropipette and left to dry for 1 hour. Under UV illumination (365 nm) the leaf deposits were imaged by a digital camera. The leaf sections were then held under gently running deionised water (flow rate approximately 300 ml/minute at a height 10 cm below the tap outlet) for 15 s. The leaf sections were allowed to dry and the deposits were re-imaged and compared to the original images. The amount of active ingredient washed off was visually estimated between 5 with most remaining and 1 with most removed. Three or more replicates were measured and the mean value recorded.

[0297] Method 9: Suspo-Emulsion Preparation

[0298] The method of the preparation of suspo-emulsion formulations are known in the art and can be produced by known methods familiar to those skilled in the art. A 2% gel of the xanthan in water and the biocides (e) was prepared with low shear stirring. The active ingredient spiroxamine (a), oils (b/c) and antioxidant (e) were mixed and added to an aqueous dispersion comprising a portion of the non-ionic dispersants (c) under high shear mixing with a rotor-stator mixer until an oil in water emulsion was formed with a droplet size D(v,0.9) typically 1 to 5 microns. The active ingredient (a), the remaining non-ionic and anionic dispersants (c/e) and other remaining formulants (c/e) were mixed with the remaining water to form a slurry, first mixed with a high shear rotor-stator mixer to reduce the particle size D(v,0.9) to approximately 50 microns, then passed through one or more bead mills to achieve a particles size D(v,0.9) typically 1 to 15 microns as required for the biological performance of the active ingredient(s). Those skilled in the art will appreciate that this can vary for different active ingredients. The oil in water emulsion, polymer dispersion (c/d) and xanthan gel were added and mixed in with low shear stirring until homogeneous.

[0299] Method 10: Description for Herbicide Greenhouse Tests

[0300] Seeds of crops and monocotyledonous and dicotyledonous harmful plants are laid out in sandy loam in plastic pots, covered with soil and cultivated in a greenhouse under optimum growth conditions. Two to three weeks after sowing, the test plants are treated at the one- to two-leaf stage. The test herbicide formulations are prepared with different concentrations and sprayed onto the surface of the green parts of the plants using different water application rates: 200 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 is TeeJet DG 95015 EVS. The ULV application rate is achieved by using a pulse-width-modulation (PWM)-system that gets attached to the nozzle and the track sprayer device. After application, the test plants were left to stand in the greenhouse for 3 to 4 weeks under optimum growth conditions. Then, the activity of the herbicide formulation is scored visually (for example: 100% activity=the whole plant material is dead, 0% activity=plants are similar to the non-treated control plants).

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

[0301] Method 11: Description for Fungicide Greenhouse Tests

[0302] 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 450 angle as this reflected best the spray conditions in the field for cereals. The ULV application rate was achieved by using a pulse-width-modulation (PWM) system attached to the nozzle and the track sprayer device at 30 Hz, opening 8-100% (10 l/ha-200 l/ha spray volume).

[0303] 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.

[0304] 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.

[0305] The practices for inoculation are well known to those skilled in the art.

TABLE-US-00005 TABLE M3 Diseases and crops used in the tests. Abbreviation/ Plant Crop EPPO Code species Variety Disease English Name 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

[0306] Method 12: Cuticle Penetration Test

[0307] The cuticle penetration test is a further developed and adapted version of the test method SOFU (simulation of foliar uptake) originally described by Schönherr and Baur (Schönherr, J., Baur, P. (1996), Effects of temperature, surfactants and other adjuvants on rates of uptake of organic compounds. In: The plant cuticle—an integrated functional approach, 134-155. Kerstiens, G. (ed.), BIOS Scientific publisher, Oxford); it is well suited for systematic and mechanistic studies on the effects of formulations, adjuvants and solvents on the penetration of agrochemicals.

[0308] Apple leaf cuticles were isolated from leaves taken from trees growing in an orchard as described by Schönherr and Riederer (Schönherr, J., Riederer, M. (1986), Plant cuticles sorb lipophilic compounds during enzymatic isolation. Plant Cell Environ. 9, 459-466). Only the astomatous cuticular membranes of the upper leaf surface lacking stomatal pores were obtained. Discs having diameters of 18 mm were punched out of the leaves and infiltrated with an enzymatic solution of pectinase and cellulase. The cuticular membranes were separated from the digested leaf cell broth, cleaned by gently washing with water and dried. After storage for about four weeks the permeability of the cuticles reaches a constant level and the cuticular membranes are ready for the use in the penetration test.

[0309] The cuticular membranes were applied to diffusion vessels. The correct orientation is important: the inner surface of the cuticle should face to the inner side of the diffusion vessel. A spray was applied in a spray chamber to the outer surface of the cuticle. The diffusion vessel was turned around and carefully filled with acceptor solution. Aqueous mixture buffered to pH 5.5 was used as acceptor medium to simulate the apoplast as natural desorption medium at the inner surface of the cuticle.

[0310] The diffusion vessels filled with acceptor and stirrer were transferred to a temperature-controlled stainless steel block which ensures not only a well-defined temperature but also a constant humidity at the cuticle surface with the spray deposit. The temperature at the beginning of experiments was 25° C. or 30° C. and changes to 350 24 h after application at constantly 60% relative humidity.

[0311] An autosampler took aliquots of the acceptor in regular intervals and the content of active ingredient is determined by HPLC (DAD or MS). All data points were finally processed to obtain a penetration kinetic. As the variation in the penetration barrier of the cuticles is high, five to ten repetitions of each penetration kinetic were made.

[0312] Materials

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

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

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

TABLE-US-00009 TABLE MAT4 Exemplified trade names and CAS-No’s of preferred compounds (e) TABLE I1 Exemplified trade names and CAS-No’s of preferred compounds (e) for Insecticide Examples Product Chemical name Cas No. Supplier Lucramul PS 29 Poly(oxy-1,2-ethanediyl),. alpha.- 104376-75-2 Levaco phenyl-.omega. -hydroxy-, styrenated Atlox ® 4913 methyl methacrylate graft 119724-54-8 Croda copolymer with polyethylene glycol Morwet IP Naphthalenesulfonic acid, bis(1- 68909-82-0 Akzo Nobel methylethyl)-, Me derivs., sodium salts Synperonic ® block-copolymer of polyethylene 9003-11-6 Croda PE/F127 oxide and polypropylene oxide Morwet D425 Sodium naphthalene sulphonate 577773-56-9 Akzo Nobel, formaldehyde condensate 68425-94-5 Nouryon 9008-63-3 ATLAS ® G Oxirane, methyl-, polymer with 9038-95-3 Croda 5000 oxirane, monobutyl ether Glycerin 56-81-5 Propylene 1,2-Propylene glycol 57-55-6 Glycol RHODOPOL ® Polysaccharide 11138-66-2 Solvay 23 Sipernat 22 S synthetic amorphous silica 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) Proxel ® GXL 1.2-benzisothiazol-3(2H)-one 2634-33-5 Arch Chemicals Kathon ® 5-chloro-2-methyl-4-isothiazolin- 26172-55-4 plus Dow CG/ICP 3-one plus 2-methyl-4- 2682-20-4 isothiazolin-3-one

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

FUNGICIDES EXAMPLES

Example FN1: Trifloxystrobin 20 SC

[0313]

TABLE-US-00011 TABLE FN1 Recipes FN1 and FN2. Recipe FN2 Recipe FN1 according to the Component (g/l) reference invention Trifloxystrobin (a) 20.0  20.0  Morwet ® D425 (d) 2.0 2.0 Synperonic ® PE/F127 (d) 5.0 5.0 Silwet ® 806 (b) 0   60.0  Lucramol ® Hot 5902 (c) 0   100.0   Xanthan (d) 3.0 3.0 Proxel ® GXL (d) 1.5 1.5 Kathon ® CG/ICP (d) 0.8 0.8 Propylene glycol (d) 60.0  60.0  SAG ® 1572 (d) 2.0 2.0 NaH.sub.2PO.sub.4 (d) 1.5 1.5 (Buffer solution pH = 7) NaH.sub.2PO.sub.4 (d) 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) (d) To volume To volume (~913) (~753)

[0314] The method of preparation used was according to Method 1.

[0315] Greenhouse

TABLE-US-00012 TABLE FN2 Biological efficacy on soybean Recipe FN2 Spray Recipe FN1 according to the volume Rate of SC Rate of reference invention l/ha applied l/ha a.i. g/ha Efficacy [%] Efficacy [%] 200 0.25 5 56 80 200 0.05 1 17 24  10 0.25 5 14 78  10 0.05 1  0 32

[0316] Method 11: soybean, 1 day preventive, evaluation 7 days after infestation

[0317] Example: The results show that recipe FN2 illustrative of the invention shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe FN1 without the spreading agent.

[0318] Pipette Spreading Tests on Leaves

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

TABLE-US-00013 TABLE FN3 Spray dilution droplet size and dose on non-textured apple leaves and textured soybean and rice leaves. High- Deposit Deposit Deposit High- spreading area area area spreading agent dose in mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 agent dose spray liquid Recipe apple soybean Rice g/ha % w/v Recipe FN1 not  4.14   1.68   1.75  0 0   according to the invention-10 l/ha Recipe FN1 not  3.26   1.69   2.04  0 0   according to the invention-200 l/ha Recipe FN2 14.11 218.0  167.3  60 0.6 according to the invention-10 l/ha Recipe FN2 according to the 14.02  27.45  18.29 60  0.03 invention-200 l/ha

[0320] Formulations applied at 1.0 l/ha.

[0321] The results show that recipe FN2 illustrative of the invention shows greater deposit sizes compared to the reference recipe FN 1. The effect is greater at 10 l/ha than 200 l/ha, and greater on textured soybean and rice leaves.

Example FN2: Prothioconazole 20 SC

[0322]

TABLE-US-00014 TABLE FN4 Recipes FN3 and FN4. Recipe FN4 Recipe FN3 according to the reference invention Prothioconazole (a) 20.0  20.0  Morwet ® D425 (d) 2.0 2.0 Synperonic ® PE/F127 (d) 5.0 5.0 Silwet ® 806 (b) 0   45.0  Synperonic ® A7 (c) 0   80.0  Xanthan (d) 3.0 3.0 Proxel ® GXL (d) 1.5 1.5 Kathon ® CG/ICP (d) 0.8 0.8 Propylene glycol (d) 60.0  60.0  SAG ® 1572 (d) 2.0 5.0 NaH.sub.2PO.sub.4 (d) 1.5 1.5 (Buffer solution pH = 7) NaH.sub.2PO.sub.4 (d) 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) (d) To volume To volume (~913) (~785)

[0323] The method of preparation used was according to Method 1.

[0324] Greenhouse

TABLE-US-00015 TABLE FN5 Biological efficacy on PHAKPA/soybean Recipe FN4 according Recipe FN3 to the Spray volume Rate of SC Rate of reference invention l/ha applied l/ha a.i. g/ha Efficacy [%] Efficacy [%] 200 0.05 1   37 89 200 0.025 0.5 19 57  15 0.05  1   41 48  15 0.025 0.5 18 26

[0325] Method 11: soybean, 1 day preventive, evaluation 7 days after infestation.

[0326] The results show that recipe FN4 illustrative of the invention shows higher efficacy at 15 l/ha spray volume than the reference recipe FN3. Furthermore, recipe FN4 shows higher efficacy at 15 l/ha than recipe FN3 at 200 l/ha.

Example FN3 Inpyrfluxam 25 SC

[0327]

TABLE-US-00016 TABLE FN6 Recipes FN5 and FN6. Recipe FN6 Recipe FN5 according to the Component (g/l) reference invention Inpyrfluxam (a) 25.0  25.0  Morwet ® D425 (d) 5.0 5.0 Atlox ® 4913 (d) 10.0  10.0  Synperonic ® PE/F127 (d) 5.0 5.0 Silwet ® 806 (b) 0   75.0  Crovol ® CR70G (c) 0   50.0  Xanthan (d) 3.6 3.6 Proxel ® GXL (d) 1.5 1.5 Kathon ® CG/ICP (d) 0.8 0.8 Propylene glycol (d) 60.0  60.0  SAG ® 1572 (d) 6.0 6.0 NaH.sub.2PO.sub.4 (d) 1.5 1.5 (Buffer solution pH = 7) NaH.sub.2PO.sub.4 (d) 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) (d) To volume To volume (~901) (~776)

[0328] The method of preparation used was according to Method 1.

[0329] Pipette Spreading Tests on Leaves

[0330] The leaf deposit size was determined according to method 5 (b) (2 μL droplet).

TABLE-US-00017 TABLE FN7 Spray dilution droplet size and dose on non-textured apple leaves and textured soybean and rice leaves. High- High- Deposit Deposit Deposit spreading spreading area area area agent agent dose in mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose spray liquid Recipe apple soybean rice g/ha % w/v Recipe FN5 not 7.28   2.27   1.75  0 0      according to the invention-10 l/ha Recipe FN5 not 4.74   3.74   2.46  0 0      according to the invention-200 l/ha Recipe FN5 not 3.20   1.34   2.61  0 0      according to the invention-800 l/ha Recipe FN6 26.0 174.5  133.3  75 0.75   according to the invention-10 1/ha Recipe FN6 24.1 92.3 48.6 75 0.0375 according to the invention-200 l/ha Recipe FN6 13.4 28.4 18.0 75 0.0094 according to the invention-800 l/ha

[0331] Formulations applied at 1 l/ha.

[0332] The results show that recipe FN6 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 FN5.

Example FN4 Inpyrfluxam 100 SC

[0333]

TABLE-US-00018 TABLE FN8 Recipes FN7 and FN8. Recipe FN8 Recipe FN7 according to the Component (g/l) reference invention Inpyrfluxam (a) 100.0   100.0   Morwet ® D425 (d) 5.0 5.0 Atlox ® 4913 (d) 10.0  10.0  Synperonic ® PE/F127 (d) 5.0 5.0 Silwet ® 806 (b) 0   50.0  Alkamuls ® A (c) 0   80.0  Xanthan (d) 3.6 3.6 Proxel ® GXL (d) 1.5 1.5 Kathon ® CG/ICP (d) 0.8 0.8 Propylene glycol (d) 60.0  60.0  SAG ® 1572 (d) 6.0 6.0 NaH.sub.2PO.sub.4 (d) 1.5 1.5 (Buffer solution pH = 7) NaH.sub.2PO.sub.4 (d) 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) (d) To volume To volume (~866) (~736)

[0334] The method of preparation used was according to Method 1.

[0335] Cuticle Penetration

[0336] The penetration through apple leaf cuticles was determined according to cuticle penetration test method 12.

TABLE-US-00019 TABLE FN9 Cuticle penetration for inpyrfluxam SC formulations. Pene- Pene- Uptake Uptake enhancing tration tration enhancing surfactant dose % % surfactant in spray Recipe 24h 48h dose g/ha liquid % w/v Recipe FN7 not 17.0 46.9  0 0   according to the invention-10 l/ha Recipe FN7 not 24.0 50.7  0 0   according to the invention-200 l/ha Recipe FN8 66.3 85.3 40 0.4 according to the invention-10 l/ha Recipe FN8 40.9 57.8 40  0.02 according to the invention-200 l/ha

[0337] Formulations tested at 0.5 l/ha.

[0338] The results show that recipe FN8 illustrative of the invention has a higher cuticle penetration at 10 l/ha than at 200 l/ha, and also greater than the reference recipe FN7 at both 10 l/ha and 200 l/ha.

[0339] These results demonstrate that the combination of high-spreading formulation additives and uptake enhancing additives according to the invention deliver both enhanced spreading and coverage on the target crop leaves and enhanced uptake of active ingredient into the leaves at low spray volumes.

Example FN5 Isoflucypram 50 SC

[0340]

TABLE-US-00020 TABLE FN10 Recipes FN9 and FN10. Recipe FN10 Recipe FN9 according to the Component (g/l) reference invention Isoflucypram (a) 50.0  50.0  Morwet ® D425 (d) 10.0  10.0  Soprophor ® FLK (d) 20.0  20.0  Synperonic ® PE/F127 (d) 10.0  10.0  Break-Thru ® Vibrant (b) 0.0 80.0  Crovol ® CR70G (c) 0.0 80.0  Xanthan (d) 3.0 3.0 Proxel ® GXL (d) 1.5 1.5 Kathon ® CG/ICP (d) 0.8 0.8 Propylene glycol (d) 60.0  60.0  SAG ® 1572 (d) 6.0 6.0 NaH.sub.2PO.sub.4 (d) 1.5 1.5 (Buffer solution pH = 7) NaH.sub.2PO.sub.4 (d) 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) (d) To volume To volume (~896) (~736)

[0341] The method of preparation used was according to Method 1.

[0342] Pipette Spreading Tests on Leaves

[0343] The leaf deposit size was determined according to method 5 (b) (2 μL droplet).

TABLE-US-00021 TABLE FN 11 Spray dilution droplet size and dose on non-textured apple leaves and textured soybean and rice leaves. High- Deposit Deposit Deposit High- spreading area area area spreading agent dose in mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 agent dose spray liquid Recipe apple soybean rice g/ha % w/v Recipe FN9 not 5.12  2.45   1.14  0 0   according to the invention-10 l/ha Recipe FN9 not 5.50  2.84   1.79  0 0   according to the invention-200 l/ha Recipe FN10 7.47 10.64 106.2  40 0.4 according to the invention-10 l/ha Recipe FN10 4.57  6.64   9.40 40  0.02 according to the invention-200 l/ha

[0344] Formulations applied at 0.5 l/ha.

[0345] The results show that recipe FN 10 illustrative of the invention shows significantly greater deposit sizes on textured leaves, especially rice, at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe FN9.

Example FN6: Fluopicolide 100 SC

[0346]

TABLE-US-00022 TABLE FN12 Recipes FN11 and FN12. Recipe FN12 Recipe FN11 according to the Component (g/l) reference invention Fluopicolide (a) 100.0   100.0   Morwet ® D425 (d) 10.0  10.0  Soprophor ® FLK (d) 20.0  20.0  Synperonic ® PE/F127 (d) 10.0  10.0  Silwet ® 408 (b) 0.0 40.0  Crovol ® CR70G (c) 0.0 60.0  Xanthan (d) 3.0 3.0 Proxel ® GXL (d) 1.5 1.5 Kathon ® CG/ICP (d) 0.8 0.8 Propylene glycol (d) 60.0  60.0  SAG ® 1572 (d) 6.0 6.0 NaH.sub.2PO.sub.4 (d) 1.5 1.5 (Buffer solution pH = 7) NaH.sub.2PO.sub.4 (d) 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) (d) To volume To volume (~846) (~746)

[0347] The method of preparation used was according to Method 1.

[0348] Pipette Spreading Tests on Leaves

[0349] The leaf deposit size was determined according to method 5 (b) (2 μL droplet).

TABLE-US-00023 TABLE FN13 Spray dilution droplet size and dose on non-textured apple leaves and textured soybean and rice leaves. High- High- Deposit Deposit Deposit spreading spreading area area area agent agent dose in mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose spray liquid Recipe apple soybean rice g/ha % w/v Recipe FN11 not  5.23   2.77   2.30  0 0   according to the invention-10 l/ha Recipe FN11 not  3.49   1.21   1.52  0 0   according to the invention-200 l/ha RecipeFN12 12.31 176.4  149.4  40 0.4 according to the invention-10 l/ha Recipe FN12 10.71  32.00  32.84 40  0.02 according to the invention-200 l/ha

[0350] Formulations applied at 0.5 l/ha.

[0351] The results show that recipe FN12 illustrative of the invention shows greater deposit sizes compared to the reference recipe FN11. The effect is greater at 10 l/ha than 200 l/ha, and greater on textured soybean and rice leaves.

Example FN7: Fluopyram 200 SC

[0352]

TABLE-US-00024 TABLE FN14 Recipes FN13 and FN14. Recipe Recipe FN14 FN13 according to Component (g/l) reference the invention Fluopyram (a) 200.0 200.0 Morwet ® D425 (d) 10.0 10.0 Soprophor ® TS54 (d) 20.0 20.0 Synperonic ® PE/F127 (d) 10.0 10.0 Silwet ® 408 (b) 0.0 60.0 Crovol ® CR70G (c) 0 80.0 Xanthan (d) 3.0 3.0 Proxel ® GXL (d) 1.5 1.5 Kathon ® CG/ICP (d) 0.8 0.8 Propylene glycol (d) 60.0 60.0 SAG ® 1572 (d) 6.0 6.0 Na.sub.2HPO.sub.4 (Buffer solution (d) 1.5 1.5 pH = 7) NaH.sub.2PO.sub.4 (Buffer solution (d) 0.8 0.8 pH = 7) Water (add to 1 litre) (d) To volume To volume (~786) (~646)

[0353] The method of preparation used was according to Method 1.

[0354] Pipette Spreading Tests on Leaves

[0355] The leaf deposit size was determined according to method 5 (b) (2 μL droplet).

TABLE-US-00025 TABLE FN15 Spray dilution droplet size and dose on non-textured apple leaves and textured soybean and rice leaves. High- spreading High- agent Deposit Deposit Deposit spreading dose in area area area agent spray mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose liquid Recipe apple soybean rice g/ha % w/v Recipe FN13 not 3.96 1.52 1.64 0 0 according to the invention—10 l/ha RecipeFN13X not 3.57 1.59 1.08 0 0 according to the invention—200 l/ha Recipe FN14 18.27 243.9 151.2 40 0.4 according to the invention—10 l/ha Recipe FN14 11.66 49.95 33.05 40 0.02 according to the invention—200 l/ha

[0356] Formulations applied at 0.5 l/ha.

[0357] The results show that recipe FN 14 illustrative of the invention shows greater deposit sizes compared to the reference recipe FN13. The effect is greater at 10 l/ha than 200 l/ha, and greater on textured soybean and rice leaves.

Example FN8: Fluoxapiprolin 50 SC

[0358]

TABLE-US-00026 TABLE FN16 Recipes FN15 and FN16. Recipe Recipe FN16 FN15 according to Component (g/l) reference the invention Fluoxapiprolin (a) 50.0 50.0 Morwet ® D425 (d) 10.0 10.0 Soprophor ® TS54 (d) 20.0 20.0 Synperonic ® PE/F127 (d) 10.0 10.0 Agnique ® PG8107G (b) 80.0 80.0 Lucramol ® HOT 5902 (c) 0 80.0 Xanthan (d) 3.0 3.0 Proxel ® GXL (d) 1.5 1.5 Kathon ® CG/ICP (d) 0.8 0.8 Propylene glycol (d) 60.0 60.0 SAG ® 1572 (d) 6.0 6.0 Na.sub.2HPO.sub.4 (Buffer solution (d) 1.5 1.5 pH = 7) NaH.sub.2PO.sub.4 (Buffer solution (d) 0.8 0.8 pH = 7) Water (add to 1 litre) (d) To volume To volume (~896) (~736)

[0359] The method of preparation used was according to Method 1.

[0360] Pipette Spreading Tests on Leaves

[0361] The leaf deposit size was determined according to method 5 (b) (2 μL droplet).

TABLE-US-00027 TABLE FN17 Spray dilution droplet size and dose on non-textured apple leaves and textured soybean and rice leaves. High- High- spreading Deposit Deposit Deposit spreading agent dose area area area agent in spray mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose liquid Recipe apple soybean rice g/ha % w/v Recipe FN15 not 3.68 2.19 1.69 0 0 according to the invention—10 l/ha Recipe FN15 not 3.58 2.24 2.23 0 0 according to the invention—200 l/ha Recipe FN16 6.04 6.40 77.38 40 0.4 according to the invention—10 l/ha Recipe FN16 5.77 2.54 8.24 40 0.02 according to the invention—200 l/ha

[0362] Formulations applied at 0.5 l/ha.

[0363] The results show that recipe FN 16 illustrative of the invention shows greater deposit sizes compared to the reference recipe FN15. The effect is greater at 10 l/ha than 200 l/ha, and greater on textured rice leaves.

Example FN9: Fluoxapiprolin 10 SC

[0364]

TABLE-US-00028 TABLE FN18 Recipes FN17 and FN18. Recipe Recipe FN18 FN17 according to Component (g/l) reference the invention Fluoxapiprolin (a) 10.0 10.0 Morwet ® D425 (d) 5.0 5.0 Soprophor ® FLK (d) 10.0 10.0 Synperonic ® PE/F127 (d) 5.0 5.0 Silwet ® 806 (b) 70.0 70.0 Alkamuls ® A (c) 0.0 70.0 Xanthan (d) 3.0 3.0 Proxel ® GXL (d) 1.5 1.5 Kathon ® CG/ICP (d) 0.8 0.8 Propylene glycol (d) 60.0 60.0 SAG ® 1572 (d) 6.0 6.0 Na.sub.2HPO.sub.4 (Buffer solution (d) 1.5 1.5 pH = 7) NaH.sub.2PO.sub.4 (Buffer solution (d) 0.8 0.8 pH = 7) Water (add to 1 litre) (d) To volume To volume (~906) (~766)

[0365] The method of preparation used was according to Method 1.

[0366] Pipette Spreading Tests on Leaves

[0367] The leaf deposit size was determined according to method 5 (b) (2 μL droplet).

TABLE-US-00029 TABLE FN19 Spray dilution droplet size and dose on non-textured apple leaves and textured soybean and rice leaves. High-High- High- spreading Deposit Deposit spreading agent dose area area agent in spray mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose liquid Recipe apple soybean g/ha % w/v Recipe FN17 not 6.15 4.02 0 0 according to the invention—10 l/ha Recipe FN17 not 4.31 2.95 0 0 according to the invention—200 l/ha Recipe FN18 according 21.00 149.1 21 0.21 to the invention—10 l/ha Recipe FN18 according 10.43 26.25 21 0.0105 to the invention~200 l/ha

[0368] Formulations applied at 0.3 l/ha.

[0369] The results show that recipe FN18 illustrative of the invention shows significantly greater deposit sizes, especially on textured soybean leaves at 10 l/ha spray volume compared to 200 l/ha spray volume and also compared to the reference recipe FN17 at both 10 l/ha and 200 l/ha spray volumes.

Example FN10: Isothianil 100 SC

[0370]

TABLE-US-00030 TABLE FN20 Recipes FN19, Fn20 and FN21. Recipe Recipe FN20 FN21 Recipe according according FN19 to the to the Component (g/l) reference invention invention Isothianil (a) 100.0 100.0 100.0 Morwet ® D425 (d) 10.0 10.0 10.0 Synperonic ® PE/F127 (d) 10.0 10.0 10.0 Soprophor ® TS54 (d) 20.0 20.0 20.0 Silwet ® 408 (b) 0.0 25.0 0.0 Crovol ® CR70G (c) 0.0 80.0 80.0 Xanthan (d) 3.0 3.0 3.0 Proxel ® GXL (d) 1.5 1.5 1.5 Kathon ® CG/ICP (d) 0.8 0.8 0.8 Propylene glycol (d) 60.0 60.0 60.0 SAG ® 1572 (d) 6.0 6.0 6.0 Na.sub.2HPO.sub.4 (Buffer solution (d) 1.5 1.5 1.5 pH = 7) NaH.sub.2PO.sub.4 (Buffer solution (d) 0.8 0.8 0.8 pH = 7) Water (add to 1 litre) (d) To volume To volume To volume (~846) (~741) (~766)

[0371] The method of preparation used was according to Method 1.

[0372] Pipette Spreading Tests on Leaves

[0373] The leaf deposit size was determined according to method 5 (b) (2 μL droplet).

TABLE-US-00031 TABLE FN21 Spray dilution droplet size and dose on non-textured apple leaves and textured soybean and rice leaves. High- High- spreading High- agent Deposit Deposit Deposit spreading dose in area area area agent spray mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose liquid Recipe apple soybean Rice g/ha % w/v Recipe FN19 not 3.98 1.72 2.49 0 0 according to the invention—10 l/ha Recipe FN19 not 4.67 1.83 2.38 0 0 according to the invention—200 l/ha Recipe FN20 according 8.72 19.45 60.54 25 0.25 to the invention—10 l/ha Recipe FN20 according 8.50 11.68 13.37 25 0.0125 to the invention—200 l/ha Recipe FN21 not 6.36 1.93 6.36 0 0 according to the invention—10 l/ha Recipe FN21 not 4.77 1.76 4.77 0 0 according to the invention—200 l/ha

[0374] Formulations applied at 1.0 l/ha.

[0375] The results show that recipe FN20 illustrative of the invention shows greater deposit sizes compared to the reference recipe FN 19. The effect is greater at 10 l/ha than 200 l/ha, and greater on textured soybean and rice leaves.

Example FN11: Tebuconazole 150 SC

[0376]

TABLE-US-00032 TABLE FN22 Recipes FN22 and FN23. Recipe FN23 Recipe according FN22 to the Component (g/l) reference invention Tebuconazole (a) 150.0 150.0 Morwet ® D425 (d) 10.0 10.0 Synperonic ® PE/F127 (d) 20.0 20.0 Soprophor ® FLK (d) 20.0 20.0 Geropon ® DOS 70PG (b) 0.0 40.0 Genapol ® C100 (c) 0.0 70.0 Xanthan (d) 3.0 3.0 Proxel ® GXL (d) 1.5 1.5 Kathon ® CG/ICP (d) 0.8 0.8 Propylene glycol (d) 60.0 60.0 SAG ® 1572 (d) 6.0 6.0 Na.sub.2HPO.sub.4 (Buffer solution (d) 1.5 1.5 pH = 7) NaH.sub.2PO.sub.4 (Buffer solution (d) 0.8 0.8 pH = 7) Water (add to 1 litre) (d) To volume To volume (~796) (~686)

[0377] The method of preparation used was according to Method 1.

[0378] Pipette Spreading Tests on Leaves

[0379] The leaf deposit size was determined according to method 5 (b) (2 μL droplet).

TABLE-US-00033 TABLE FN23 Spray dilution droplet size and dose on non-textured apple leaves and textured soybean and rice leaves. High- High- spreading Deposit Deposit Deposit spreading agent dose area area area agent in spray mm{circumflex over ( )}2 mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose liquid Recipe apple soybean rice g/ha % w/v Recipe FN22 not 6.80 4.53 4.09 0 0 according to the invention—10 l/ha Recipe FN22 not 5.24 4.66 3.01 0 0 according to the invention—200 l/ha Recipe FN23 11.08 36.39 177.3 40 0.4 according to the invention—10 l/ha Recipe FN23 8.05 23.58 59.94 40 0.02 according to the invention—200 l/ha

[0380] Formulations applied at 1.0 l/ha.

[0381] The results show that recipe FN23 illustrative of the invention shows greater deposit sizes compared to the reference recipe FN22. The effect is greater at 10 l/ha than 200 l/ha, and with textured leaf surfaces, especially rice.

INSECTICIDE EXAMPLES

[0382] All examples were prepared according to the relevant methods described above

Example I1 Spirotetramat SC Formulations

[0383]

TABLE-US-00034 TABLE 12 Recipes Spirotetramat SC Formulations. Component Recipe I1 Recipe I2 according (g/L) reference to the invention Spirotetramat 75 75 Lucramul PS 29 40 40 Glycerin 100 100 Rhodopol 23 3 3 Preventol D7 0.8 0.8 Proxel GXL 20% 1.2 1.2 Silcolapse 426R 1 1 Citric Acid 1 1 Silwet HS312 — 40 Crovol CR70 — 50 Water (add to 1 To volume To volume litre)

[0384] Pipette Spreading Tests on Leaves

[0385] The leaf deposit size was determined according to the coverage method 5.

TABLE-US-00035 TABLE 13 Spray dilution droplet size and dose on non-textured leaves. High- spreading Deposit Spreading agent dose in area agent spray liquid mm{circumflex over ( )}2 dose % w/v Recipe apple g/ha (g/100 mL) Recipe I1not according 5.6 0 0 to the invention—10 l/ha Recipe I1not according 4.8 0 0 to the invention—200 l/ha Recipe I2 according to 7.6 40 0.4 the invention—10 l/ha Recipe I2 according to 5.9 40 0.02 the invention—200 l/ha

[0386] Formulations applied at 1 l/ha.

[0387] The results show that on non-structured leaves the deposit size is slightly higher at lower water application volume.

TABLE-US-00036 TABLE 14 Spray dilution droplet size and dose on textured leaves. High- spreading Deposit Spreading agent dose in area agent spray liquid mm{circumflex over ( )}2 dose % w/v Recipe soybean g/ha (g/100 mL) Recipe I1not according 2.6 0 0 to the invention—10 l/ha Recipe I1not according 1.2 0 0 to the invention—200 l/ha Recipe I2according to 7.4 40 0.4 the invention—10 l/ha Recipe I2according to 3.8 40 0.02 the invention—200 l/ha

[0388] Formulations applied at 1 l/ha.

[0389] The results show that recipe I2 illustrative of the invention shows larger deposit sizes at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe I1.

Example I2 Tetraniliprole SC Formulations

[0390]

TABLE-US-00037 TABLE 15 Recipes Tetraniliprole SC Formulations. Recipe 14 Recipe 17 Recipe according Recipe Recipe according Component 13 to the 15 16 to the (g/l) reference invention reference reference invention Tetraniliprole 40.0 40.0 80.0 80.0 80.0 Atlox 4913 40.0 40.0 9.6 9.6 9.6 Morwet IP 10.0 10.0 2.4 2.4 2.4 Synperonic 15.0 15.0 3.6 3.6 3.6 PE/F127 Citric Acid 1.0 1.0 — — — Rhodopol 23 3.0 3.0 3.5 3.5 3.5 Sipernat 22 S 7.5 7.5 Silwet ® — — — 60.0 HS-312 Geropon DOS — 20 — — — RME EW 500 — 100 — — — Alkamuls A — — — 80 80 Kathon 0.8 0.8 0.8 0.8 0.8 CG/ICP Proxel GXL 1.2 1.2 1.8 1.8 1.8 Glycerin 100.0 100.0 Propylene — — 70.0 70.0 70.0 Glycol SAG1572 1.5 1.5 7.0 6.0 6.0 Water (add to fill fill fill fill fill 1 litre)

[0391] Pipette Spreading Tests on Leaves

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

TABLE-US-00038 TABLE 16 Spray dilution droplet size and dose on non-textured leaves. High- spreading Deposit Spreading agent dose in area agent spray liquid mm{circumflex over ( )}2 dose % w/v Recipe apple g/ha (g/100 mL) Recipe 13 not 6.7 0 0 according to the invention—10 l/ha Recipe 13 not 4.5 0 0 according to the invention—200 l/ha Recipe 14 according to 10.4 20 0.2 the invention—10 l/ha Recipe 14 according to 6.1 20 0.01 the invention—200 l/ha

[0393] Formulations applied at 1 l/ha.

[0394] The results show that on non-structured leaves the deposit size is slightly higher at lower water application volume.

TABLE-US-00039 TABLE I7 Spray dilution droplet size and dose on textured leaves. High- spreading agent dose in Deposit Spreading spray liquid area mm{circumflex over ( )}2 agent dose % w/v Recipe soybean g/ha (g/100 mL) Recipe I3 not 2.2 0 0 according to the invention-10 l/ha Recipe I3 not 1.8 0 0 according to the invention-200 l/ha Recipe I4 according to 61.5 20 0.2 the invention-10 l/ha Recipe I4 according to 4.7 20 0.01 the invention-200l/ha

[0395] Formulations applied at 1 l/ha.

[0396] The results show that recipe I4 illustrative of the invention shows larger deposit sizes at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe I3.

[0397] Pipette Spreading Tests on Leaves

[0398] The leaf deposit size was determined according to method 5 (b) (2 μL droplet).

TABLE-US-00040 TABLE I8 Spray dilution droplet size and dose on non-textured apple leaves and textured soybean and rice leaves. High- High- Deposit Deposit spreading spreading area area agent agent dose in mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose spray liquid Recipe apple soybean g/ha % w/v Recipe I5 not 2.4 1.5 0 0 according to the invention-10 l/ha Recipe I5 not 2.9 1.7 0 0 according to the invention-200 l/ha Recipe I7 according to 5.9 4.6 30 0.3 the invention-10 l/ha Recipe I7 according to 5.5 3.0 30 0.015 the invention-200 l/ha

[0399] Formulations applied at 0.5 l/ha.

[0400] The results show that recipe I7 illustrative of the invention shows larger deposit compared to the reference recipe I5.

Example I3 Ethiprole+Imidacloprid SC Formulations

[0401]

TABLE-US-00041 TABLE I9 Recipes Ethiprole + Imidacloprid SC Formulations Recipe 19 according Component Recipe 18 to the (g/l) reference invention Ethiprole 100 100 Imidacloprid 100 100 Morwet 11 11 D425 Atlox 4913 69 69 Atlas G 22 22 5000 Citric Acid 2 2 Rhodopol 23 4 4 Veegum R 6 6 Break-Thru — 50 Vibrant Antarox — 50 B848 Kathon 0.8 0.8 CG/ICP Proxel GXL 1.2 1.2 Propylene 110 110 Glycol Silcolapse 3 3 426R Water (add fill fill to 1 litre)

HERBICIDE EXAMPLES

Example HB1: SC

[0402]

TABLE-US-00042 TABLE HB1a Recipes HB1, HB2, HB3 and HB4 Recipe Recipe HB2 Recipe HB3 Recipe HB4 Component HB1 according to according to according to (g/l) reference the invention the invention the invention TEMBOTRIONE (a) 100.00 100.00 100.00 100.00 ISOXADIFEN-ETHYL (a) 50.00 50.00 50.00 50.00 Silwet HS-604 (b) 0.00 52.50 52.50 52.50 Rapseed oil methylester (c) 0.00 105.00 0.00 0.00 Disflamoll TOF (c) 0.00 0.00 105.00 0.00 Genapol X-060 (c) 0.00 0.00 0.00 100.00 ATLAS G 5000 (d) 10.50 10.50 10.50 10.50 SILCOLAPSE 454 (d) 2.10 2.10 2.10 2.10 SYNPERONIC A7 (d) 10.50 10.50 10.50 10.50 ATLOX 4913 (d) 31.50 31.50 31.50 31.50 RHODOPOL 23 (d) 0.18 0.18 0.18 0.18 ACTICIDE MBS (d) 2.10 2.10 2.10 2.10 1,2-PROPYLENE GLYCOL (d) 52.50 52.50 52.50 52.50 WATER (add to 1 litre) to volume to volume to volume to volume

TABLE-US-00043 TABLE HB1b HB5, HB6 and HB7 Recipe HB5 Recipe HB6 Recipe HB7 Component according to the according to the according to the (g/l) invention invention invention TEMBOTRIONE (a) 100.00 100.00 100.00 ISOXADIFEN-ETHYL (a) 50.00 50.00 50.00 Geropon DOS PG (b) 52.50 52.50 52.50 Rapseed oil methylester (c) 105.00 0.00 0.00 Disflamoll TOF (c) 0.00 105.00 0.00 Genapol X-060 (c) 0.00 0.00 100.00 ATLAS G 5000 (d) 10.50 10.50 10.50 SILCOLAPSE 454 (d) 2.10 2.10 2.10 SYNPERONIC A7 (d) 10.50 10.50 10.50 ATLOX 4913 (d) 31.50 31.50 31.50 RHODOPOL 23 (d) 0.18 0.18 0.18 ACTICIDE MBS (d) 2.10 2.10 2.10 1,2-PROPYLENE GLYCOL (d) 52.50 52.50 52.50 WATER (add to 1 litre) to volume to volume to volume

[0403] Pipette Spreading Tests on Leaves

[0404] The leaf deposit size was determined according to the coverage method 5 (b).

TABLE-US-00044 TABLE HB2 Spray dilution droplet size and dose on non-textured leaves. High- High- Deposit spreading spreading area agent agent dose in mm{circumflex over ( )}2 dose spray liquid Recipe apple g/ha % w/v Recipe HB1 not 7.3 0 0 according to the invention-10 l/ha Recipe HB1 not 7.1 0 0 according to the invention-200 l/ha Recipe HB2 according 7.7 52.5 0.52 to the invention-10 l/ha Recipe HB2 according 4.9 52.5 0.026 to the invention-200 l/ha Recipe HB3 according 12.4 52.5 0.52 to the invention-10 l/ha Recipe HB3 according 6.7 52.5 0.026 to the invention-200 l/ha Recipe HB4 according 9.2 52.5 0.52 to the invention-10 l/ha Recipe HB4 according 9.0 52.5 0.026 to the invention-200 l/ha Recipe HB5 according 15.4 52.5 0.52 to the invention-10 l/ha Recipe HB5 according 8.0 52.5 0.026 to the invention-200 l/ha Recipe HB6 according 22.6 52.5 0.52 to the invention-10 l/ha Recipe HB6 according 8.2 52.5 0.026 to the invention-200 l/ha Recipe HB7 according 13.2 52.5 0.52 to the invention-10 l/ha Recipe HB7 according 9.6 52.5 0.026 to the invention-200 l/ha

[0405] Formulations applied at 1 l/ha.

[0406] The results show that on non-structured leaves the deposit size is similar or slightly higher at lower water application volume.

TABLE-US-00045 TABLE HB3 Spray dilution droplet size and dose on textured leaves. High- High- Deposit spreading spreading area agent agent dose in mm{circumflex over ( )}2 dose spray liquid Recipe soybean g/ha % w/v Recipe HB1 not 11.7 0 0 according to the invention-10 l/ha Recipe HB1 not 4.55 0 0 according to the invention-200 l/ha Recipe HB2 according 26.7 52.5 0.52 to the invention-10 l/ha Recipe HB2 according 6.8 52.5 0.026 to the invention-200 l/ha Recipe HB3 according 38.0 52.5 0.52 to the invention-10 l/ha Recipe HB3 according 7.6 52.5 0.026 to the invention-200 l/ha Recipe HB4 according 67.1 52.5 0.52 to the invention-10 l/ha Recipe HB4 according 11.0 52.5 0.026 to the invention-200 l/ha Recipe HB5 according 66.0 52.5 0.52 to the invention-10 l/ha Recipe HB5 according 10.5 52.5 0.026 to the invention-200 l/ha Recipe HB6 according 22.4 52.5 0.52 to the invention-10 l/ha Recipe HB6 according 7.9 52.5 0.026 to the invention-200 l/ha Recipe HB7 according 41.5 52.5 0.52 to the invention-10 l/ha Recipe HB7 according 27.5 52.5 0.026 to the invention-200 l/ha

[0407] Formulations applied at 1 l/ha.

[0408] The results show that recipes HB2-HB7 illustrative of the invention show larger deposit sizes at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe HB1.

[0409] Cuticle Penetration

[0410] The penetration through apple leaf cuticles was determined according to cuticle penetration test method 12.

TABLE-US-00046 TABLE HB4 Cuticle penetration for Tembotrione SC formulations HB1-HB7. Uptake Uptake enhancing enhancing Penetration Penetration surfactant surfactant % % dose dose Recipe 24 h 37 h g/ha % w/v Recipe HB1 not 4.6 6.0 0 0 according to the invention-10 l/ha Recipe HB1 not 1.5 1.9 0 0 according to the invention-200 l/ha Recipe HB2 according 5.8 7.6 105 1.05 to the invention-10 l/ha Recipe HB2 according 2.1 2.9 105 0.05 to the invention-200 l/ha Recipe HB3 according 22.1 27.7 105 1.05 to the invention-10 l/ha Recipe HB3 according 6.5 7.7 105 0.05 to the invention-200 l/ha Recipe HB4 according 18.2 26.6 100 1.0 to the invention-10 l/ha Recipe HB4 according 3.3 5.1 100 0.05 to the invention-200 l/ha Recipe HB5 according 16.0 27.4 105 1.05 to the invention-10 l/ha Recipe HB5 according 19.3 31.0 105 0.05 to the invention-200 l/ha Recipe HB6 according 15.5 22.0 105 1.05 to the invention-10 l/ha Recipe HB6 according 4.8 8.6 105 0.05 to the invention-200 l/ha Recipe HB7 according 22.6 32.4 100 1.0 to the invention-10 l/ha Recipe HB7 according 20.8 29.7 100 0.05 to the invention-200 l/ha

[0411] The results show that recipes HB2-HB7 illustrative of the invention have a higher cuticle penetration at 10 l/ha than at 200 l/ha, and also greater than the reference recipe HB1 at both 10 l/ha and 200 l/ha.

Example HB2: SC

[0412]

TABLE-US-00047 TABLE HB5 Recipes HB8, HB9, HB 10 and HBI 1 Recipe HB9 Recipe HB10 Recipe HB11 Recipe HB8 according to according to according to Component (g/l) reference the invention the invention the invention TRIAFAMONE (a) 70.00 70.00 70.00 70.00 Silwet L 77 (b) 0.00 40.00 40.00 40.00 Genapol X060 (c) 0.00 60.00 0.00 0.00 Disflamol TOF(c) 0.00 0.00 60.00 0.00 Rapseed oil methylester (c) 0.00 0.00 0.00 60.00 ATLOX 4913 (d) 32.40 32.40 32.40 32.40 ATLOX 4894 (d) 21.60 21.60 21.60 21.60 1,2-PROPYLENE GLYCOL (d) 54.00 54.00 54.00 54.00 Silcolapse 454 (d) 2.16 2.16 2.16 2.16 Proxel GXL (d) 1.94 1.94 1.94 1.94 Kathon CG/ICP (d) 0.86 0.86 0.86 0.86 RHODOPOL 23 (d) 4.32 4.32 4.32 4.32 Na.sub.2HPO.sub.4 (Buffer solution pH = 7) 1.5 1.5 1.5 1.5 (d) NaH.sub.2PO.sub.4 (Buffer solution pH = 7) 0.8 0.8 0.8 0.8 (d) WATER (add to 1 litre) to volume to volume to volume to volume

[0413] Cuticle Penetration

[0414] The penetration through apple leaf cuticles was determined according to cuticle penetration test method 12.

TABLE-US-00048 TABLE HB6 Cuticle penetration for Triafamone SC formulations. Uptake Uptake enhancing enhancing surfactant surfactant Penetration Penetration dose dose Recipe % 12 h % 95 h g/ha % w/v Recipe HB8 not 2.0 10.0 0 0 according to the invention-10 l/ha Recipe HB8 not 1.6 8.5 0 0 according to the invention-200 l/ha Recipe HB9 according 7.4 24.2 60 0.6 to the invention-10 l/ha Recipe HB9 according 6.3 20.8 60 0.03 to the invention-200 l/ha

[0415] Formulations tested at 1 l/ha.

[0416] The results show that recipe HB9 illustrative of the invention has a higher cuticle penetration at 10 l/ha than at 200 l/ha, and also greater than the reference recipe HB8 at both 10 l/ha and 200 l/ha.

[0417] Pipette Spreading Tests on Leaves

[0418] The leaf deposit size was determined according to the coverage method 5.

TABLE-US-00049 TABLE HB7 Spray dilution droplet size and dose on non-textured leaves. High- High- Deposit spreading spreading area agent agent dose in mm{circumflex over ( )}2 dose spray liquid Recipe apple g/ha % w/v Recipe HB8 not 9.0 0 0 according to the invention-10 l/ha Recipe HB8 not 6.5 0 0 according to the invention-200 l/ha Recipe HB9 according to 20.4 20 0.2 the invention-10 l/ha Recipe HB9 not 9.2 20 0.01 according to the invention-200 l/ha Recipe HB10 according 17.9 20 0.2 to the invention-10 l/ha Recipe HB10 according 6.0 20 0.01 to the invention-200 l/ha Recipe HB11 according 19.0 20 0.2 to the invention-10 l/ha Recipe HB11 according 5.4 20 0.01 to the invention-200 l/ha

[0419] Formulations applied at 0.5 l/ha.

[0420] The results show that on non-structured leaves the deposit size is higher at lower water application volume.

TABLE-US-00050 TABLE HB8 Spray dilution droplet size and dose on textured leaves. High- High- Deposit spreading spreading area agent agent dose in mm{circumflex over ( )}2 dose spray liquid Recipe soybean g/ha % w/v Recipe HB8 not 10.1 0 0 according to the invention-10 l/ha Recipe HB8 not 5.7 0 0 according to the invention-200 l/ha Recipe HB9 according to 81.7 20 0.2 the invention-10 l/ha Recipe HB9 not 10.9 20 0.01 according to the invention-200 l/ha Recipe HB10 according 69.9 20 0.2 to the invention-10 l/ha Recipe HB10 according 5.4 20 0.01 to the invention-200 l/ha Recipe HB11 according 73.3 20 0.2 to the invention-10 l/ha Recipe HB11 according 3.9 20 0.01 to the invention-200 l/ha

[0421] Formulations applied at 0.5 l/ha.

[0422] The results show that recipes HB9, HB10 and HB11 illustrative of the invention show larger deposit sizes at 10 L/ha spray volume than at 200 L/ha, and also greater than the reference recipe HB8 at 10 l/ha and 200 l/ha.

Example HB3: SC

[0423]

TABLE-US-00051 TABLE HB9 Recipes HB8, HB12, HB13 and HB14 Recipe Recipe HB12 Recipe HB13 Recipe HB14 HB8 according to according to according to Component (g/l) reference the invention the invention the invention TRIAFAMONE (a) 70.00 70.00 70.00 70.00 Geropon DOS (b) 0.00 50.00 50.00 50.00 Genapol X060 (c) 0.00 60.00 0.00 0.00 Disflamol TOF (c) 0.00 0.00 60.00 0.00 RME (c) 0.00 0.00 0.00 60.00 ATLOX 4913 (d) 32.40 32.40 32.40 32.40 ATLOX 4894 (d) 21.60 21.60 21.60 21.60 1,2-PROPYLENE GLYCOL (d) 54.00 54.00 54.00 54.00 Silcolapse 454 (d) 2.16 2.16 2.16 2.16 Proxel ® GXL (d) 1.94 1.94 1.94 1.94 Kathon ® CG/ICP (d) 0.86 0.86 0.86 0.86 RHODOPOL ® 23 (d) 4.32 4.32 4.32 4.32 Na.sub.2HPO.sub.4 (Buffer solution pH = 7) 1.5 1.5 1.5 1.5 (d) NaH.sub.2PO.sub.4 (Buffer solution pH = 7) 0.8 0.8 0.8 0.8 (d) WATER (add to 1 litre) to volume to volume to volume to volume

[0424] Pipette Spreading Tests on Leaves

[0425] The leaf deposit size was determined according to the coverage method 5.

TABLE-US-00052 TABLE HB10 Spray dilution droplet size and dose on non-textured leaves. High- High- Deposit spreading spreading area agent agent dose in mm{circumflex over ( )}2 dose spray liquid Recipe apple g/ha % w/v Recipe HB8 not 9.0 0 0 according to the invention-10 l/ha Recipe HB8 not 6.5 0 0 according to the invention-200 l/ha Recipe HB12 according 16.4 25 0.25 to the invention-10 l/ha Recipe HB12 not 8.1 25 0.013 according to the invention-200 l/ha Recipe HB13 according 11.8 25 0.25 to the invention-10 l/ha Recipe Hb13 according 6.5 25 0.013 to the invention-200 l/ha Recipe Hb14 according 22.8 25 0.25 to the invention-10 l/ha Recipe HB14 according 6.5 25 0.013 to the invention-200 l/ha

[0426] Formulations applied at 0.5 l/ha.

[0427] The results show that on non-structured leaves the deposit size is higher at lower water application volume.

TABLE-US-00053 TABLE HB11 Spray dilution droplet size and dose on textured leaves. High- High- Deposit spreading spreading area agent agent dose in mm{circumflex over ( )}2 dose spray liquid Recipe soybean g/ha % w/v Recipe HB8 not 10.1 0 0 according to the invention-10 l/ha Recipe HB8 not 5.7 0 0 according to the invention-200 l/ha Recipe HB12 according 65.3 25 0.25 to the invention-10 l/ha Recipe HB12 not 16.8 25 0.013 according to the invention-200 l/ha Recipe HB13 according — 25 0.25 to the invention-10 l/ha Recipe Hb13 according 4.8 25 0.013 to the invention-200 l/ha Recipe Hb14 according 81.3 25 0.25 to the invention-10 l/ha Recipe HB14 according 3.4 25 0.013 to the invention-200 l/ha

[0428] Formulations applied at 0.5 l/ha.

[0429] The results show that recipes HB12, HB13 and HB14 illustrative of the invention show larger deposit sizes at 10 L/ha spray volume than at 200 L/ha.