ULV FORMULATIONS WITH ENHANCED UPTAKE

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, 10 weeds or diseases, in particular on waxy leaves.

Claims

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

2: The agrochemical formulation according to claim 1, wherein b) is selected from the group consisting of sunflower oil, rapeseed oil, corn oil, soybean oil, rice bran oil, olive oil; ethylhexyl oleate, ethylhexyl palmitate, ethylhexyl myristate/laurate, ethylhexyl laurate, ethylhexyl caprylate/caprate, iso-propyl myristate, iso-propyl palmitate, methyl oleate, methyl palmitate, ethyl oleate, rape seed oil methyl ester, soybean oil methyl ester, rice bran oil methyl ester, Mineral oils and white oil; tris-alkyl-phosphate esters, preferably tris (2-ethylhexyl) phosphate, i. ethoxylated branched alcohols with 2-20 EO units; ii. methyl end-capped, ethoxylated branched alcohols comprising 2-20 EO units; iii. ethoxylated coconut alcohols comprising 2-20 EO units; iv. ethoxylated C12/15 alcohols comprising 2-20 EO units; v. propoxy-ethoxylated alcohols, branched or linear, vi. propoxy-ethoxylated fatty acids, Me end-capped, vii. alkyl ether citrate surfactants; viii. ethoxylated mono- or diesters of glycerine comprising fatty acids with 8-18 carbon atoms and an average of 10-40 EO units; ix. castor oil ethoxylates comprising an average of 5-40 EO units, x. ethoxylated oleic acid comprising 2-20 EO units; and xi. ethoxylated sorbitan fatty acid esters comprising fatty acids with 8-18 carbon atoms and an average of 10-50 EO units.

3: The agrochemical formulation according to claim 1, wherein b) is selected from the group consisting of 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: The agrochemical formulation according to claim 1, wherein a) is present in an amount from 5 to 300 g/l, preferably from 10 to 280 g/l, and most preferred from 10 to 250 g/l.

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

6: The agrochemical formulation according to claim 1, wherein c) is present in 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 the active ingredient is selected from the group consisting of bixafen, fluoxapiprolin, inpyrfluxam, isoflucypram, prothioconazole, tebuconazole, trifloxystrobin, ethiprole, imidacloprid, spidoxamat, spirotetramat, tetraniliprole, thiencarbazone-methyl, triafamone, isoxadifen-ethyl and mefenpyr-diethyl.

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 at least one antifreeze agent (c4).

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

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 an agrochemical formulation according to claim 1, onto crops, comprising applying the formulation at a spray volume of between 1 and 20 l/ha, preferably 2 and 15 l/ha, and more preferably 5 and 15 l/ha.

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

13: The method according to claim 11, wherein the uptake enhancer 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.

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

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

16: A method of controlling harmful organisms, comprising contacting the harmful organisms, their habitat, their hosts, such as plants and seed, and the soil, the area and the environment in which they grow or could grow, but also of 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 an agrochemical formulation according to claim 1, characterized in that the composition is applied by an unmanned aerial vehicle (UAV), an unmanned guided vehicle (UGV), or a pulse-width-module (PWM).

Description

EXAMPLES

Method 1: SC Preparation

[0160] 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).

Method 2: WG Preparation

[0161] 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.

[0162] 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).

[0163] 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.

[0164] Likewise, any other spraying process, like e.g. classical spray drying can be used as granulation method.

[0165] 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.

Method 3: EC Preparation

[0166] 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.

Method 4: OD Preparation

[0167] 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.

Method 5: Coverage

[0168] Greenhouse plants in the development stage as indicated in Tables 1a& 1b were used for these experiments. Single leaves were cut just before the spraying experiment, placed into petri dishes and attached by tape at both tips at 0° (horizontally) or at 60° (so that 50% of leaf area can be sprayed). The leaves were carried with caution to avoid damage of the wax surface. These horizontally orientated leaves were either a) placed into a spay chamber where the spray liquid was applied via a hydraulic nozzle or b) a 4 μl drop of spray liquid was pipetted on top without touching the leaf surface.

[0169] 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.

[0170] 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.

Method 6: Insecticide Greenhouse Tests

[0171] 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).

[0172] 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.

[0173] 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.

[0174] 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 oral 5 plants treatment viridula N2-N3 uptake in pot cabbage BBCH12, prior to Myzus green peach mixed translaminar 1-leaf treatment persicae aphid population activity

[0175] 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).

[0176] 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.

[0177] 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.

[0178] 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.

Method 7: Cuticle Wash-Off

[0179] 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.

Method 8: Leaf Wash-Off

[0180] 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.

Method 9: Suspo-Emulsion Preparation

[0181] 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.

Method 10: Description for Herbicide Greenhouse Tests

[0182] Seeds of crops and monocotyledonous and dicotyledonous harmful plants are laid out in sandy loam in plastic pots, covered with soil and cultivated in a greenhouse under optimum growth conditions. Two to three weeks after sowing, the test plants are treated at the one- to two-leaf stage. The test herbicide formulations are prepared with different concentrations and sprayed onto the surface of the green parts of the plants using different water application rates: 200 l/ha as a standard conventional rate and 10 l/ha as an ultra-low-volume (ULV) application rate. The nozzle type used for all applications is TeeJet DG 95015 EVS. The ULV application rate is achieved by using a pulse-width-modulation (PWM) system that gets attached to the nozzle and the track sprayer device. After application, the test plants were left to stand in the greenhouse for 3 to 4 weeks under optimum growth conditions. Then, the activity of the herbicide formulation is scored visually (for example: 100% activity=the whole plant material is dead, 0% activity=plants are similar to the non-treated control plants).

TABLE-US-00004 TABLE M2 Plant species used in the tests. Abbreviation/ Crop Plant species EPPO 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

Method 11: Description for Fungicide Greenhouse Tests

[0183] Seeds were laid out in “peat soil T” in plastic pots, covered with soil and cultivated in a greenhouse under optimum growth conditions. Two to three weeks after sowing, the test plants were treated at the one- to two-leaf stage. The test fungicide formulations were prepared with different concentrations and sprayed onto the surface of the plants using different water application rates: 200 l/ha as a standard conventional rate and 10 l/ha as an ultra-low-volume (ULV) application rate. The nozzle type used for all applications was TeeJet TP 8003E, used with 0.7-1.5 bar and 500-600 mm height above plant level. Cereal were put in an 45° angle as this reflected best the spray conditions in the field for cereals. The ULV application rate was achieved by using a pulse-width-modulation (PWM) system attached to the nozzle and the track sprayer device at 30 Hz, opening 8%-100% (10 l/ha-200 l/ha spray volume).

[0184] 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.

[0185] 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.

[0186] 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/ EPPO Plant Crop 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

Method 12: Cuticle Penetration Test

[0187] The cuticle penetration test is a further developed and adapted version of the test method SOFU (simulation of foliar uptake) originally described by Schonherr and Baur (Schonherr, 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.

[0188] 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.

[0189] 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.

[0190] The diffusion vessels filled with acceptor and stirrer were transferred to a temperature-controlled stainless steel block which ensures not only a well-defined temperature but also a constant humidity at the cuticle surface with the spray deposit. The temperature at the beginning of experiments was 25° C. or 30° C. and changes to 35° 24 h after application at constantly 60% relative humidity.

[0191] 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.

Materials

[0192]

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) Synergel ® 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 KPH70 Dioctylsulfosuccinate sodium 577-11-7 Nouryon salt (65-70% in propylene glycol) Enviomet EM Dioctylsulfosuccinate sodium 577-11-7 Innospec 5669 salt (65-70% in propylene glycol) Surfynol ® S420 2,4,7,9-Tetramethyl-5-Decyne- 9014-85-1 Evonik 4,7-Diol ethoxylate (1 mole) Surfynol ® S440 2,4,7,9-Tetramethyl-5-Decyne- 9014-85-1 Evonik 4,7-Diol ethoxylate (3.5 moles) Surfynol ® S465 2,4,7,9-Tetramethyl-5-Decyne- 9014-85-1 Evonik 4,7-Diol ethoxylate (10 moles) Surfynol ® S485 2,4,7,9-Tetramethyl-5-Decyne- 9014-85-1 Evonik 4,7-Diol ethoxylate (30 moles) Break-Thru ® Not disclosed Evonik Vibrant Genapol ® EP C10-12 alcohol alkoxylate Clariant 0244 (PO + EO) Synergen ® W06 C11 alcohol alkoxylate (PO + EO) Clariant Genapol ® EP C12-15 alcohol alkoxylate Clariant 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 ® S240 3-[methyl-bis 134180-76-0 Evonik (trimethylsilyloxy)silyl]propan- 1-ol;2-methyloxirane;oxirane Break-thru ® S278 3-(2-methoxyethoxy) 27306-78-1 Evonik propyl-methyl- bis(trimethylsilyloxy)silane Silwet ® HS 312 Silwet ® HS 604 BreakThru ® OE Siloxanes and Silicones, cetyl 191044-49-2 Evonik 444 Me, di-Me

TABLE-US-00007 TABLE MAT2 Exemplified trade names and CAS-No's of preferred uptake enhancing compounds (b) Product Chemical name Cas No. Supplier Emulsogen ® EL 400 Ethoxylated Castor Oil 61791-12-6 Clariant with 40 EO ETOCAS ® 10 Ethoxylated Castor 61791-12-6 Croda Oil with 10 EO Crovol ® CR70G fats and glyceridic oils, 70377-91-2 Croda vegetable, ethoxylated Synperonic ® A3 alcohol ethoxylate 68131-39-5 Croda (C12/C15-EO3) Synperonic ® A7 alcohol ethoxylate 68131-39-5 Croda (C12/C15-EO7) Genapol ® X060 alcohol ethoxylate 9043-30-5 Clariant (iso-C13-EO6) Alkamuls ® A Oleic acid, ethoxylated 9004-96-0 Solvay Lucramul ® HOT alcohol ethoxylate-propoxylate 64366-70-7 Levaco 5902 (C8-PO8/EO6) Antarox B/848 Butyl alcohol 9038-95-3 Solvay propoxylate/ethoxylate Tween ® 80 Sorbitan monooleate, 9005-65-6 Croda ethoxylated (20EO) Tween ® 85 Sorbitan trioleate, 9005-70-3 Croda ethoxylated (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 ® 7129 ethylhexyl palmitate 29806-73-3 Oleon NV, BE Crodamol ® OP Croda, UK Radia ® 7331 ethylhexyl oleate 26399-02-0 Oleon NV, BE Radia ® 7128 ethylhexyl myristate/ 29806-75-5 Oleon NV, BE laurate C12/C14 Radia ® 7127 ethylhexyl laurate 20292-08-4 Oleon NV, BE Radia ® 7126 ethylhexyl caprylate/ 63321-70-0 Oleon NV, BE caprate C8/10 Estol ® 1514 iso-propyl myristate 110-27-0 Croda Radia ® 7104 Caprylic, capric 73398-61-5. Oleon NV, BE triglycerides, 65381-09-1 neutral vegetable oil

TABLE-US-00008 TABLE MAT3 Exemplified trade names of preferred wash-off reducing materials (d) Product Chemical name Tg MFFT Supplier Atplus ® FA Aqueous styrene acrylic <30° C. Croda co-polymer emulsion dispersion Acronal ® V215 aqueous acrylate −43° C. BASF Acronal ® V115 co-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 dispersion +12° C. Acronal ® V 212 −40° C. Acronal ® DS 3502  +4° C. Acronal ® S 400  −8° C. Licomer ® ADH205 aqueous acrylic <30° C. Michelman Licomer ® ADH203 ester co-polymer dispersion containing carboxylic groups. Primal ® CM-160 Aqueous acrylic DOW Primal ® CM-330 copolymer emulsion polymer Axilat ® Aqueous acrylic −15° C. 0° C. Synthomer UltraGreen 5500 emulsion polymer Povol ® 26/88 Polyvinyl alcohol Kuraray

[0193] Table MAT4: Exemplified Trade Names and CAS-No's of Preferred Compounds (e)

TABLE-US-00009 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),. 104376-75-2 Levaco alpha.-phenyl-. omega.-hydroxy-, styrenated Atlox ® 4913 methyl methacrylate graft 119724-54-8 Croda copolymer with polyethylene glycol Morwet IP Naphthalenesulfonic acid, 68909-82-0 Akzo Nobel bis(1-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 ® Oxirane, methyl-, polymer 9038-95-3 Croda G 5000 with 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 9016-00-6 BLUESTAR 426R and silica SILICONES SAG ® 1572 Dimethyl siloxanes and 63148-62-9 Momentive silicones Citric Acid 77-92-9 (anhydrous); 5949-29-1 (Monohydrate) Proxel ® GXL 1.2-benzisothiazol-3(2H)-one 2634-33-5 Arch Kathon ® 5-chloro-2-methyl-4-isothiazolin- 26172-55-4 plus Chemicals CG/ICP 3-one plus 2-methyl-4- 2682-20-4 Dow 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- 26172-55-4 Dow 3-one plus 2-methyl-4- plus isothiazolin-3-one 2682-20-4 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-methy1-4-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 ® Tristyrylphenol ethoxylate sulfate 119432-41-6 Solvay 4 D 384 (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 112926-00-8 Evonik (silicon dioxide) 7631-86-9 RHODACAL ® Calcium- 26264-06-2 Solvay 60 BE dodecylbenzenesulphonate in 104-76-7 2-Ethylhexanol Emulsogen ® Ethoxylated Castor Oil 61791-12-6 Clariant EL 400 with 40 EO Solvesso ® 200ND Mixture of aromatic hydrocarbons 64742-94-5 ExxonMobil (C9-C11), naphtalene depleted

FUNGICIDES EXAMPLES

Example FN1: Isoflucypram SC

[0194]

TABLE-US-00011 TABLE FN1 Recipes FN1, FN2 and FN3. Recipe Recipe FN2 FN3 Recipe according according FN1 to the to the Component (g/l) reference invention invention Isoflucypram (a) 50.0 50.0 50.0 Morwet ® D425 (c) 5.0 5.0 5.0 Synperonic ® (c) 12.0 12.0 12.0 PE/F127 Etocas ® 10-LQ (b) 0.0 50.0 0.0 Lucramol ® (b) 0.0 0.0 50.0 HOT5902 Xanthan (c) 3.0 3.0 3.0 Proxel ® GXL (c) 1.8 1.8 1.8 Kathon ® CG/ICP (c) 0.8 0.8 0.8 Propylene glycol (c) 80.0 80.0 80.0 SAG ® 1572 (c) 6.0 6.0 6.0 Water (add (c) To volume To volume To volume to 1 litre) (~862) (~812) (~812) The method of preparation used was according to Method 1.

Cuticle Penetration

[0195] The penetration through apple leaf cuticles was determined according to cuticle penetration test method 12.

TABLE-US-00012 TABLE FN2 Cuticle penetration for isoflucypram SC formulations. Uptake enhancing Uptake surfactant enhancing dose surfactant in spray Penetration Penetration dose liquid Recipe % 24 h % 61 h g/ha % w/v Recipe FN1 not according 3.1 33.2 0 0 to the invention-10 l/ha Recipe FN1 not according 4.4 29.6 0 0 to the invention-200 l/ha Recipe FN2 according to 6.8 80.8 50 0.5 the invention-10 l/ha Recipe FN 2according to 10.3 90.5 50 0.025 the invention-200 l/ha Recipe FN3 according to 7.9 70.9 50 0.5 the invention-10 l/ha Recipe FN3 according to 7.3 56.6 50 0.025 the invention-200 1/ha Formulations tested at 1.0 /ha.

[0196] The recipe FN3 illustrative of the invention shows higher penetration of the active ingredient at 10 l/h than at 200 l/ha. The recipe FN2 illustrative of the invention shows high penetration at both 10 l/ha and 200 l/ha, with 200 l/ha a little greater. Both FN3 and FN2 show significantly greater penetration than the reference FN1 at both 10 l/ha and 200 l/ha.

Example FN2: Isoflucypram SC

[0197]

TABLE-US-00013 TABLE FN3 Recipes FN4 and FN5. Recipe FN5 Recipe according FN4 to the Component (g/l) reference invention Isoflucypram (a) 50.0 50.0 Morwet ® D425 (c) 1.0 1.0 Synperonic ® PE/F127 (c) 5.0 5.0 Crovol ® CR70G (b) 0.0 100.0 Xanthan (c) 3.6 3.6 Proxel ® GXL (c) 1.8 1.8 Kathon ® CG/ICP (c) 0.8 0.8 Propylene glycol (c) 60.0 60.0 SAG ® 1572 (c) 6.0 6.0 Water (add to (c) To volume To volume 1 litre) (~917) (~817) The method of preparation used was according to Method 1.

Greenhouse

Efficacy Data

[0198]

TABLE-US-00014 TABLE FN4 Biological efficacy on PYRNTE Recipe FN5 Recipe according Rate FN4 to the Spray of SC Rate reference invention volume applied of a.i. Efficacy Efficacy l/ha l/ha g/ha [%] [%] 200 0.5 25 97 100 200 0.1 5 43 100 200 0.05 2.5 29 97 10 0.5 25 93 100 10 0.1 5 71 100 10 0.05 2.5 71 100 Method 11: wheat, protective 1 day before inoculation evaluation 10 DAT The results show that recipe FNS shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe FN4 without the uptake enhancing additive (b).

Example FN3: Tebuconazole 20 SC

[0199]

TABLE-US-00015 TABLE FN5 Recipes FN6 and FN7. Recipe FN7 Recipe according FN6 to the Component (g/l) reference invention Tebuconazole (a) 20.0 20.0 Morwet ® D425 (c) 2.0 2.0 Synperonic ® PE/F127 (c) 5.0 5.0 Crovol ® CR70G (b) 0.0 100 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 2.0 Na.sub.2HPO.sub.4 (c) 1.5 1.5 (Buffer solution pH = 7 ) Na.sub.2HPO.sub.4 (c) 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) (c) To volume To volume (~913) (~773) The method of preparation used was according to Method 1.

Greenhouse

Efficacy Data

[0200]

TABLE-US-00016 TABLE FN6 Biological efficacy on PHAKPA Recipe FN7 Recipe according Rate FN6 to the Spray of SC Rate reference invention volume applied of a.i. Efficacy Efficacy l/ha l/ha g/ha [%] [%] 200 0.25 5 99 100 200 0.05 1 53 79 200 0.025 0.5 25 19 10 0.25 5 100 100 10 0.05 1 86 100 10 0.025 0.5 55 81 Method 11: soybean, 1 day protective, evaluation 7 dat

[0201] The results show that recipe FN7 illustrative of the invention shows higher efficacy at 10 l/ha spray volume than 200 l/ha. Furthermore, recipe Y shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe FN6 without the uptake enhancing additive (b).

Greenhouse

[0202]

TABLE-US-00017 TABLE FN7 Biological efficacy on PHAKPA Recipe FN7 Recipe according Rate FN6 to the Spray of SC Rate reference invention volume applied of a.i. Efficacy Efficacy l/ha l/ha g/ha [%] [%] 200 0.5 10 100 100 200 0 5 62 100 200 0.05 1 35 6 10 0.5 10 96 100 10 0.1 5 69 100 10 0.05 1 46 77 Method 11: soybean, 1 day protective, evaluation 7 dat

[0203] The results show that recipe FN7 illustrative of the invention shows higher efficacy at 10 l/ha spray volume than 200 l/ha. Furthermore, recipe FN7 shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe FN6 without the uptake enhancing additive (b).

Example FN4: Bixafen 20 SC

[0204]

TABLE-US-00018 TABLE FN8 Recipes FN8 and FN9. Recipe FN9 Recipe according Component FN8 to the (g/l) reference invention Bixafen (a) 20.0 20.0 Morwet ® D425 (c) 2.0 2.0 Synperonic ® PE/F127 (c) 5.0 5.0 Crovol ® CR70G (b) 0.0 140 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 2.0 Na.sub.2HPO.sub.4 (Buffer (c) 1.5 1.5 solution pH = 7) Na.sub.2HPO.sub.4 (Buffer (c) 0.8 0.8 solution pH = 7) Water (c) To volume To volume (add to 1 litre) (~913) (~773) The method of preparation used was according to Method 1.

Greenhouse

[0205]

TABLE-US-00019 TABLE FN9 Biological efficacy on ERYSGH Recipe FN9 Spray Recipe FN8 according to volume Rate of SC Rate of reference the invention l/ha applied l/ha a.i. g/ha Efficacy [%] Efficacy [%] 200 5 100 50 100 200 2.5 50 17 100 200 1.25 25 0 100 200 0.5 10 17 33 10 5 100 17 67 10 2.5 50 0 67 10 1.25 25 0 67 10 0.5 10 0 50 Method 11: barley, 1 day protective, evaluation 7 dat

[0206] The results show that recipe FN9 illustrative of the invention shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe FN8 without the uptake enhancing additive (b).

Example FN5: Prothioconazole 20 SC

[0207]

TABLE-US-00020 TABLE FN10 Recipes FN10 and FN11. Recipe Recipe FN11 FN10 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 Crovol ® CR7OG (b) 0.0 100 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 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) (~813) The method of preparation used was according to Method 1.

Greenhouse

[0208]

TABLE-US-00021 TABLE FN11 Biological efficacy on PUCCRT Recipe FN11 Spray Recipe FN10 according to volume Rate of SC Rate of reference the invention l/ha applied l/ha a.i. g/ha Efficacy [%] Efficacy [%] 200 5 100 78 100 200 2.5 50 33 89 200 1.25 25 22 78 10 5 100 94 100 10 2.5 50 67 100 10 1.25 25 22 94 Method 11: wheat, 1 day protective, evaluation 9 DAT

[0209] The results show that recipe FN11 illustrative of the invention shows higher efficacy at 10 l/ha spray volume than 200 l/ha. Furthermore, recipe FN11 shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe FN10 without the uptake enhancing additive (b).

TABLE-US-00022 TABLE FN12 Biological efficacy on PHAKPA Recipe FN11 Spray Recipe FN10 according to volume Rate of SC Rate of reference the invention l/ha applied l/ha a.i. g/ha Efficacy [%] Efficacy [%] 200 0.25 5 98 100 200 0.05 1 94 99 200 0.025 0.5 95 95 200 0.005 0.1 58 73 10 0.25 5 100 100 10 0.05 1 98 100 10 0.025 0.5 89 98 10 0.005 0.1 46 92 Method 11: soybean, 2 days curative, evaluation 7 days after infestation

[0210] The results show that recipe FN11 illustrative of the invention shows higher efficacy at 10 l/ha spray volume than 200 l/ha. Furthermore, recipe FN11 shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe FN10 without the uptake enhancing additive (b).

Example FN6: Fluoxapiprolin 5 SC

[0211]

TABLE-US-00023 TABLE FN13 Recipes FN12 and FN13. Recipe FN13 Recipe according FN12 to the Component (g/l) reference invention Fluoxapiprolin (a) 5.0 5.0 Morwet ® D425 (c) 1.0 1.0 Synperonic ® PE/F127 (c) 5.0 5.0 Crovol ® CR70G (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) 50.0 50.0 SAG ® 1572 (c) 4.0 4.0 Water (add to 1 litre) (c) To volume To volume (~930) (~830) The method of preparation used was according to Method 1.

Greenhouse

[0212]

TABLE-US-00024 TABLE FN14 Biological efficacy on PHYTIN Recipe FN13 Spray Recipe FN12 according to volume Rate of SC Rate of reference the invention l/ha applied l/ha a.i. g/ha Efficacy [%] Efficacy [%] 200 0.5 2.5 83 96 200 0.2 1 59 95 200 0.1 0.5 61 91 10 0.5 2.5 54 81 10 0.2 1 37 69 10 0.1 0.5 24 53 Method 11: tomato, 1 day preventive, evaluation 7 days after infestation

[0213] Recipe FN13 shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe FN12 without the uptake enhancing additive (b).

Example FN7: Trifloxystrobin 20 SC

[0214]

TABLE-US-00025 TABLE FN15 Recipes X and Y. Recipe Recipe FN15 FN14 according to Component (g/l) reference the invention Trifloxystrobin (a) 20 20 Morwet ® D425 (c) 2 2 Synperonic ® PE/F127 (c) 5 5 Crovol ® CR70G (b) 140 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 60 SAG ® 1572 (c) 2 2 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) (~773) The method of preparation used was according to Method 1.

Greenhouse

[0215]

TABLE-US-00026 TABLE FN17 Biological efficacy on PHAKPA Recipe Recipe FN15 Spray FN14 according to volume Rate of SC Rate of reference the invention l/ha applied l/ha a.i. g/ha Efficacy [%] Efficacy [%] 200 0.5 10 71 94 200 0.1 5 27 84 200 0.05 1 10 56 10 0.5 10 79 98 10 0.1 5 38 83 10 0.05 1 25 73 Method 11: soybean, 1 day protective, evaluation 7 dat

[0216] The results show that recipe FN15 illustrative of the invention shows higher efficacy at both 200 l/ha and 10 l/ha spray volumes than the reference recipe FN14 without the uptake enhancing additive (b).

Example FNB: Inpyrfluxam 100 SC

[0217]

TABLE-US-00027 TABLE FN18 Recipes FN16 and FN17. Recipe Recipe FN17 FN16 according to Component (g/l) reference the invention Inpyrfluxam (a) 100.0 100.0 Morwet ® D425 (c) 5.0 5.0 Atlox ® 4913 (c) 10.0 10.0 Synperonic ® PE/F127 (c) 5.0 5.0 Alkamuls ® A (b) 0.0 80.0 Xanthan (c) 3.6 3.6 Proxel ® GXL (c) 1.5 1.5 Kathon ® CG/ICP (c) 0.8 0.8 Propylene glycol (c) 60.0 60.0 SAG ® 1572 (c) 6.0 6.0 Na.sub.2HPO.sub.4 (Buffer (c) 1.5 1.5 solution pH = 7) NaH.sub.2PO.sub.4 (Buffer (c) 0.8 0.8 solution pH = 7) Water (add to 1 litre) (c) To volume To volume (~866) (~765) The method of preparation used was according to Method 1.

Penetration Tests

[0218] The penetration through apple leaf cuticles was determined according to cuticle penetration test method 12.

TABLE-US-00028 TABLE FN19 Cuticle penetration for inpyrfluxam SC formulations. Uptake Uptake enhancing enhancing surfactant surfactant dose Penetration Penetration dose in spray liquid Recipe 24 h 48 h g/ha % w/v Recipe FN16 not 17.0 46.9 0 0 according to the invention-10 l/ha Recipe FN16 not 24.0 50.7 0 0 according to the invention-200 l/ha Recipe FN17 73.7 97.3 40 0.4 according to the invention-10 l/ha Recipe FN17 36.6 57.8 40 0.02 according to the invention-200 l/ha Formulations tested at 0.5 l/ha.

[0219] The results show that recipe FN17 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 FN16 at both 10 l/ha and 200 l/ha.

Example FN9: Fungicide Isoflucypram 50 SC

[0220]

TABLE-US-00029 TABLE FN20 Recipes FN18, FN19, FN20 and FN21. Recipe Recipe FN19 FN21 Recipe according Recipe according FN18 to the FN20 to the Component (g/l) reference invention reference invention Isoflucypram (a) 50.0 50.0 50.0 50.0 Morwet ® D425 (c) 5.0 5.0 5.0 5.0 Synperonic ® (c) 12.0 12.0 17.0 17.0 PE/F127 Crodamol ® OP (b) 0.0 50 0.0 0.0 Crodamol ® PC (b) 0.0 0.0 50 0.0 DAB Exxsol ® D80 (b) 0.0 0.0 0.0 50 Xanthan (c) 3.0 3.0 3.0 3.0 Proxel ® GXL (c) 1.5 1.5 1.5 1.5 Kathon ® CG/ICP (c) 0.8 0.8 0.8 0.8 Propylene glycol (c) 80.0 80.0 80.0 80.0 SAG ® 1572 (c) 6.0 6.0 6.0 6.0 Water (add to 1 litre) (c) To volume To volume To volume To volume (~862) (~807) (~806) (~806) The method of preparation used was according to Method 1.

Penetration Tests

[0221] The penetration through apple leaf cuticles was determined according to method 12.

TABLE-US-00030 TABLE FN21 Cuticle penetration for isoflucypram SC formulations. Uptake Uptake enhancing enhancing surfactant Penetration Penetration surfactant dose in spray Recipe 24 h 61 h dose g/ha liquid % w/v Recipe FN18 not 3.1 33.2 0 0 according to the invention-10 l/ha Recipe FN18 not 4.4 29.6 0 0 according to the invention-200 l/ha Recipe FN19 6.8 61.8 50 0.5 according to the invention-10 l/ha Recipe FN19 10.3 44.0 50 0.025 according to the invention-200 l/ha Recipe FN20 7.9 59.4 50 0.5 according to the invention-10 l/ha Recipe FN20 7.3 33.4 50 0.025 according to the invention-200 l/ha Recipe FN21 3.9 50.0 50 0.5 according to the invention-10 l/ha Recipe FN21 4.3 30.8 50 0.025 according to the invention-200 l/ha

[0222] The results show that recipes FN19, FN20 and FN21 illustrative of the invention shows greater uptake of the a.i. at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe FN18.

INSECTICIDE EXAMPLES

[0223] All formulations/recipes were prepared/tested according to the methods described above.

Example I1 Spirotetramat SC Formulations

[0224]

TABLE-US-00031 TABLE 12 Recipes Spirotetramat SC Formulations Recipe Recipe I2 Recipe I3 Recipe I4 I25 Recipe according according according according Component I1 to the to the to the to the (g/l) reference invention invention invention invention Spirotetramat 75 75 75 75 75 Lucramul PS 29 40 40 40 40 40 Glycerin 100 100 100 100 100 Rhodopol 23 3 3 3 3 3 Preventol D7 0.8 0.8 0.8 0.8 0.8 Proxel GXL 1.2 1.2 1.2 1.2 1.2 20% Silcolapse 426R 1 1 1 1 1 Citric Acid 1 1 1 1 1 Crovol CR 70 — 50 — — — Genapol X060 — — 50 — — Antarox B848 — — — 50 — RME EW 500 — — — — 100 Water (add to 1 fill fill Fill fill fill litre)

Cuticle Penetration

[0225] The penetration through apple leaf cuticles was determined according to method 12.

TABLE-US-00032 TABLE 13 Cuticle penetration spirotetramat SC Formulations Uptake Uptake % cuticular % cuticular enhancing enhancing penetration penetration surfactant surfactant 24 h after 48 h after dose dose % w/v Recipe application application g/ha (g/100 mL) Recipe I1 not 3.8 6.3 0 0 according to the invention- 10 l/ha Recipe I1 not 1.6 3.7 0 0 according to the invention- 300 l/ha Recipe I2 11.1 17.9 50 0.5 according to the invention- 10 l/ha Recipe I2 6.9 12.5 50 0.016 according to the invention- 300 l/ha Formulations applied at 11/ha.

[0226] The results show that recipe I2 illustrative of the invention shows greater penetration of the a.i. at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe I1.

TABLE-US-00033 TABLE 14 Cuticle penetration spirotetramat SC Formulations Uptake Uptake enhancing % cuticular % cuticular enhancing surfactant penetration penetration surfactant dose 24 h after 48 h after dose % w/v Recipe application application g/ha (g/100 mL) Recipe I1 not 11.4 20.8 0 0 according to the invention- 10 l/ha Recipe I1 not 9.5 23.6 0 0 according to the invention- 200 l/ha Recipe I3 14.4 28.0 50 0.5 according to the invention- 10 l/ha Recipe I3 13.3 30.2 50 0.025 according to the invention- 200 l/ha Recipe I4 20.5 35.8 50 0.5 according to the invention- 10 l/ha Recipe I4 15.8 28.6 50 0.025 according to the invention- 200 l/ha Formulations applied at 11/ha.

[0227] The results show that recipe I3 illustrative of the invention shows greater penetration compared to the reference recipe I1.

[0228] The results show that recipe I4 illustrative of the invention shows greater penetration of the a.i. at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe I1.

TABLE-US-00034 TABLE I5 Cuticle penetration spirotetramat SC Formulations Uptake % Uptake enhancing % cuticular cuticular enhancing surfactant penetration penetration surfactant dose in 24 h after 48 h after dose spray liquid Recipe application application g/ha g/100 mL Recipe I1 not 3.8 6.3 0 0 according to the invention- 10 l/ha Recipe I1 not 1.6 3.7 0 0 according to the invention- 300 l/ha Recipe I25 7.2 12.5 50 0.5 according to the invention- 10 l/ha Recipe I25 2.6 5.5 50 0.025 according to the invention- 300 l/ha Formulations applied at 1 l/ha.

[0229] The results show that recipe I25 illustrative of the invention shows greater penetration of the a.i. at 10 L/ha spray volume than at 200 L/ha. Also, recipe I25 illustrative of the invention shows greater penetration of the a.i@10 L/ha than the standard recipe I1.

Example I2/Spidoxamat OD Formulations

[0230]

TABLE-US-00035 TABLE I6 Recipes/Spidoxamat OD Formulations Recipe I6 Recipe I7 Recipe I8 according according according Recipe I5 to the to the to the Component (g/l) reference invention invention invention SPIDOXAMATE 12 12 12 12 Propylene Glycol 150 150 150 150 Aerosil R812S 40 40 40 40 Diammonium 20 20 20 20 Hydrogen phosphate Antarox B848 20 20 20 50 Crovol CR 70 — 50 — — Genapol X060 — — 50 — Dowanol DPM To volume To volume To volume To volume (add to 1 litre)

Cuticle Penetration

[0231] The penetration through apple leaf cuticles was determined according to method 12.

TABLE-US-00036 TABLE I7 Cuticle penetration/Spidoxamat OD Formulations Uptake enhancing % Uptake surfactant % cuticular cuticular enhancing dose in penetration penetration surfactant spray liquid 24 h after 48 h after dose % w/v Recipe application application g/ha (g/100 mL) Recipe I5 not 14.0 16.0 0 0 according to the invention- 10 l/ha Recipe I5 not 17.4 35.1 0 0 according to the invention- 200 l/ha Recipe I6 60.8 81.7 50 0.5 according to the invention- 10 l/ha Recipe I6 58.0 74.7 50 0.025 according to the invention- 200 l/ha Recipe I8 66.6 80.6 50 0.5 according to the invention- 10 l/ha Recipe I8 71.7 96.1 50 0.025 according to the invention- 200 l/ha Formulations applied at 1 l/ha.

[0232] The results show that recipes I6 and I8 illustrative of the invention shows greater penetration compared to the reference recipe I5.

Example I3 Spirotetramat OD Formulations

[0233]

TABLE-US-00037 TABLE I8 Recipes Spirotetramat OD Formulations Recipe I10 Recipe I11 according according Recipe I9 to the to the Component (g/l) reference invention invention Spirotetramate 75 75 75 Morwet D425 5 5 5 Rhodacal 60/B 5 5 5 Atlox 4914 20 20 20 Soprophor TS/10 50 50 50 Leofat OC-0503M — 100 — Lucramul HOT 5902 — — 100 SILFOAM SC 1132 0.5 0.5 0.5 Citric Acid 2 2 2 Miglyol 812 N (add to To volume To volume To volume 1 litre)

Example I4 Tetraniliprole SC Formulations

[0234]

TABLE-US-00038 TABLE I9 Recipes Tetraniliprole SC Formulations Recipe Recipe Recipe Recipe I13 I14 I15 I24 Recipe according according according according Component I12 to the to the to the to the (g/l) reference invention invention invention invention Tetraniliprole 40.0 40.0 40.0 40.0 40.0 Atlox 4913 40.0 40.0 40.0 40.0 40.0 Morwet IP 10.0 10.0 10.0 10.0 10.0 Synperonic 15.0 15.0 15.0 15.0 15.0 PE/F127 Lucramul PS 54 — — — — — Atlox 4913 — — — — — Citric Acid 1.0 1.0 1.0 1.0 1.0 Rhodopol 23 3.0 3.0 3.0 3.0 3.0 Sipernat 22 S 7.5 7.5 7.5 7.5 7.5 Crovol CR 70 — 50 — — — Genapol X060 — — 50 — — Antarox B848 — — — 50 — RME EW 500 — — — — 100 Kathon CG/ICP 0.8 0.8 0.8 0.8 0.8 Proxel GXL 1.2 1.2 1.2 1.2 1.2 Glycerin 100.0 100.0 100.0 100.0 100.0 SAG1572 1.5 1.5 1.5 1.5 1.5 Water (add to 1 fill fill fill fill fill litre)

Example I5 Tetraniliprole OD Formulations

[0235]

TABLE-US-00039 TABLE I10 Recipes Tetraniliprole OD Formulations Recipe I17 Recipe I18 according according Recipe I16 to the to the Component (g/l) reference invention invention Tetraniliprole 40 40 40 Morwet D425 5 5 5 Rhodacal 60/B 60 60 60 Soprophor BSU 40 40 40 Antarox B848 — 100 — Lucramul HOT 5902 — — 100 SILFOAM SC 1132 0.5 0.5 0.5 Citric Acid 2 2 2 Crodamol DA (add to 1 To volume To volume To volume litre)

Example I6 Ethiprole+Imidacloprid SC Formulations

[0236]

TABLE-US-00040 TABLE I11 Recipes Ethiprole + Imidacloprid SC Formulations Recipe Recipe Recipe Recipe I20 I21 I22 I23 Recipe according according according according Component I19 to the to the to the to the (g/l) reference invention invention invention invention Ethiprole 100 100 100 100 100 Imidacloprid 100 100 100 100 100 Morwet 11 11 11 11 11 D425 Atlox 4913 69 69 69 69 69 Atlas G 22 22 22 22 22 5000 Citric Acid 2 2 2 2 2 Rhodopol 23 4 4 4 4 4 Veegum R 6 6 6 6 6 Crovol CR — 50 — — — 70 Genapol — — 50 — — X060 Antarox — — — 50 — B848 RME EW — — — — 100 500 Kathon 0.8 0.8 0.8 0.8 0.8 CG/ICP Proxel GXL 1.2 1.2 1.2 1.2 1.2 Propylene 110 110 110 110 110 Glycol Silcolapse 3 3 3 3 3 426R Water (add fill fill fill fill fill to 1 litre)

Cuticle Penetration

[0237] The penetration through apple leaf cuticles was determined according to method 12.

TABLE-US-00041 TABLE I12 Cuticle penetration of imidacloprid from Ethiprole + Imidacloprid SC Formulations Uptake enhancing % Uptake surfactant % cuticular cuticular enhancing dose in penetration penetration surfactant spray liquid 24 h after 48 h after dose % w/v Recipe application application g/ha (g/100 mL) Recipe I19 not 16.0 32.8 0 0 according to the invention- 10 l/ha Recipe I19 not 54.2 72.8 0 0 according to the invention- 200 l/ha Recipe I21 33.0 58.2 50 0.5 according to the invention- 10 l/ha Recipe I21 64.4 77.6 50 0.025 according to the invention- 200 l/ha Recipe I22 45.8 69.1 50 0.5 according to the invention- 10 l/ha Recipe I22 97.0 106.1 50 0.25 according to the invention- 200 l/ha Formulations applied at 1 l/ha.

[0238] The results show that recipe I21 illustrative of the invention shows greater penetration of Imidacloprid 48 h after application compared to the reference recipe I19.

[0239] The results show that recipe I22 illustrative of the invention shows greater penetration of Imidacloprid at comparable water volume use rates than the reference recipe I19.

TABLE-US-00042 TABLE I13 Cuticle penetration of ehtiprole from Ethiprole + Imidacloprid SC Formulations Uptake enhancing % Uptake surfactant % cuticular cuticular enhancing dose in penetration penetration surfactant spray liquid 24 h after 48 h after dose % w/v Recipe application application g/ha (g/100 mL) Recipe I19 not 2.7 6.9 0 0 according to the invention- 10 l/ha Recipe I19 not 1.9 4.6 0 0 according to the invention- 200 l/ha Recipe I21 5.7 12.8 50 0.5 according to the invention- 10 l/ha Recipe I21 3.1 7.0 50 0.025 according to the invention- 200 l/ha Recipe I22 8.2 15.5 50 0.5 according to the invention- 10 l/ha Recipe I22 6.3 13.2 50 0.025 according to the invention- 200 l/ha Formulations applied at 1 l/ha.

[0240] The results show that recipes I21 and I22 illustrative of the invention show greater penetration of Ethiprole at 10 L/ha than at 200 L/ha water volume use rates, and also than the reference recipe I19.

Example I7 Greenhouse Testing TETRANILIPROLE SC Formulations

[0241] Test methodology: application onto upperside of pre-infested 1-leaf cabbage plants, BBCH12, for translaminar activity, 2 replicates. Tracksprayer settings: 10 l/ha applied using Lechler's PWM together with nozzle 652.246; 300 l/ha applied using nozzle TeeJet TP8003E.

TABLE-US-00043 TABLE I14 Biological efficacy (in % mortality) against mixed population of Myzus persicae on pre-infested cabbage, evaluation 7 days after application Recipe I13 Recipe I24 according to according to Spray volume Rate of a.i. Recipe I12 the the l/ha g/ha reference invention invention 300 100 0 30 0 300 20 0 0 0 300 4 0 0 0 10 100 85 100 100 10 20 0 65 50 10 4 0 0 0

[0242] The results show that the recipes according to the invention have higher efficacy at 10 l/ha water volume than at 300 l/ha. Additionally, the recipes according to the invention are slightly more efficacious than the recipes not according to the invention.

Example I8 Greenhouse Testing Imidacloprid+Ethiprole SC200 Formulation

[0243] Test methodology: application onto upperside of soybeans, BBCH12, for contact and oral uptake, 2 replicates; artificial infestation with 10 Southern green stink bugs nymphs. Tracksprayer settings: 10 l/ha applied using Lechler's PWM together with nozzle 652.246; 300 l/ha applied using nozzle TeeJet TP8003E.

TABLE-US-00044 TABLE I15 Biological efficacy (in % mortality) against mixed population of Nezara viridula (N2 nymphs) on soybean, evaluation 3 days after application Rate of a.i. g/ha (delivered as Spray recipe I19 not Rate volume according to the of adjuvant l/ha invention) g/ha % Mortality 300 20 0 70 300 4 0 20 300 0.8 0 5 10 20 0 80 10 4 0 15 10 0.8 0 5 Rate % Mortality Concentration Rate of a.i. g/ha of adjuvant (tank mix of adjuvant Spray (delivered as recipe Crovol adjuvanted in spray volume I19 not according CR70G SC200 solution l/ha to the invention) g/ha formulation) (g/l) 300 20 30 100 0.1 300 4 30 30 0.1 300 0.8 30 0 0.1 10 20 30 95 3 10 4 30 85 3 10 0.8 30 30 3

[0244] The results show that the addition of Crovol CR70G improves the biological efficacy of the active ingredients, particularly at 10 l/ha water spray volume

HERBICIDE EXAMPLES

Example HB1: WG

[0245]

TABLE-US-00045 TABLE HB1 Recipes HB1, HB2 and HB3. Recipe HB2 Recipe HB3 Recipe HB1 according to according to Component (g/kg) reference the invention the invention Triafamone (a) 200 200 200 Supragil WP (c) 50 50 50 Morwet D 425 (c) 200 200 200 Sokalan K 30 (c) 20 20 20 Crovol 70 G (b) 0 150 0 Genapol X 60 (b) 0 0 150 Rhodorsil Antim EP 6703 (c) 40 40 40 Sipernat 50 S (c) 100 100 100 Kaolin Tec 1 390 240 240 Dose rate: 0.25 kg/ha The method of preparation used was according to Method 2.

Cuticle Penetration

[0246] The penetration through apple leaf cuticles was determined according to method 12.

TABLE-US-00046 TABLE HB2 Cuticle penetration for HB1, HB2 and HB3. Uptake enhancing % % Uptake surfactant cuticular cuticular enhancing dose in penetration penetration surfactant spray 24 h after 48 h after dose liquid Recipe application application g/ha % w/v Recipe 0.2 0.8 0 0 HB1 not according to the invention- 10 l/ha Recipe 1.3 4.9 0 0 HB1 not according to the invention- 200 l/ha Recipe 2.1 12.7 37.5 0.4 HB2 according to the invention- 10 l/ha Recipe 4.4 12.8 37.5 0.02 HB2 according to the invention- 200 l/ha Recipe HB 2.3 5.8 37.5 0.4 3according to the invention- 10 l/ha Recipe 5.1 12.4 37.5 0.02 HB3 according to the invention- 200 l/ha Formulations applied at 0.25 kg/ha.

[0247] The results show that recipe HB2 illustrative of the invention shows greater penetration of the a.i. Triafamone at 10 L/ha spray volume than at 200 L/ha and also compared to the reference recipe HB1. Also recipe HB3 shows better penetration at low spray volume compared to the reference recipe HB1 at low spray volume.

BOP-CUPET “Uptake” Tests

[0248] The penetration through apple leaf cuticles was determined according to method described as cuticle penetration test.

Example HB2a: SC

[0249]

TABLE-US-00047 TABLE HB3 Recipes HB4, HB5 and HB6. Recipe Recipe HB5 Recipe HB6 HB4 according to according to Component (g/kg) reference the invention the invention TEMBOTRIONE (a) 100.00 100.00 100.00 ISOXADIFEN-ETHYL (a) 50.00 50.00 50.00 ATLOX G 5000 (c) 12.20 12.20 12.20 SYNPERONIC A7 (c) 12.20 12.20 12.20 ATLOX 4913 (c) 36.60 36.60 36.60 Synperonic PE/F 127 (c) 16.00 16.00 16.00 1,2-PROPYLENE 61.00 61.00 61.00 GLYCOL (c) SILICOLAPSE 454 (c) 2.44 2.44 2.44 ACTICIDE MBS (c) 2.44 2.44 2.44 Genapol X0 60 (b) 0.00 100.00 0.00 Tween 80 (b) 0.00 0.00 100.00 RHODOPOL 23 (c) 2.20 2.20 2.20 WATER (add to 1 litre) to volume to volume to volume The method of preparation used was according to Method 1.

Example HB2b: SC

[0250]

TABLE-US-00048 TABLE HB4 Recipes HB7, HB8 and HB9. Recipe HB7 Recipe HB8 Recipe HB9 according to according to according to Component (g/kg) the invention the invention the invention TEMBOTRIONE (a) 100.00 100.00 100.00 ISOXADIFEN-ETHYL (a) 50.00 50.00 50.00 ATLOX G 5000 (c) 12.20 12.20 12.20 SYNPERONIC A7 (c) 12.20 12.20 12.20 ATLOX 4913 (c) 36.60 36.60 36.60 Synperonic PE/F 127 (c) 16.00 16.00 16.00 1,2-PROPYLENE 61.00 61.00 61.00 GLYCOL (c) SILICOLAPSE 454 (c) 2.44 2.44 2.44 ACTICIDE MBS (c) 2.44 2.44 2.44 Triton CG-50 (b) 100.00 0.00 0.00 Sophorphor 796/P (b) 0.00 100.00 0.00 Disflamoll TOF (b) 0.00 0.00 140.00 RHODOPOL 23 (c) 2.20 2.20 2.20 WATER (add to 1 litre) to volume to volume to volume The method of preparation used was according to Method 1.

TABLE-US-00049 TABLE HB5 Cuticle penetration for HB4-HB9 (Tembotrione) Uptake enhancing % % Uptake surfactant cuticular cuticular enhancing dose in penetration penetration surfactant spray 20 h after 53 h after dose liquid Recipe application application g/ha % w/v Recipe HB4 not 4.7 10.0 0 0 according to the invention - 10 l/ha Recipe HB4 not 3.3 6.4 0 0 according to the invention - 200 l/ha Recipe HB5 11.8 23.6 100 1 according to the invention - 10 l/ha Recipe HB5 2.1 6.2 100 0.05 according to the invention - 200 l/ha Recipe HB6 26.8 59.8 100 1 according to the invention - 10 l/ha Recipe HB6 5.0 8.0 100 0.05 according to the invention - 200 l/ha Recipe HB7 14.6 32.7 100 1 according to the invention - 10 l/ha Recipe HB7 8.3 19.3 100 0.05 according to the invention - 200 l/ha Recipe HB8 15.0 29.7 100 1 according to the invention - 10 l/ha Recipe HB8 6.9 16.2 100 0.05 according to the invention - 200 l/ha Recipe HB9 14.7 28.4 140 1.4 according to the invention - 10 l/ha Recipe HB9 8.4 13.4 140 0.07 according to the invention - 200 l/ha Formulations applied at 1 L/ha.

[0251] The results show that recipes HB5-HB9 illustrative of the invention show greater penetration of the Tembotrione at 10 L/ha spray volume compared to the reference recipe HB4 and greater than at 200 L/ha.

Greenhouse

Efficacy Data

[0252]

TABLE-US-00050 TABLE HB6a Additive dose g/ha for each treatment. HB4 reference Spray volume Rate of SC Rate of a.i. Additive dose Additive l/ha applied l/ha g/ha g/ha dose % w/v 200 1 50 + 100 100 0  10 1 50 + 100 100 0

TABLE-US-00051 TABLE HB6b Additive dose g/ha for each treatment HB5, HB6 and HB7 Spray volume Rate of SC Rate of a.i. Additive Additive l/ha applied l/ha g/ha dose g/ha dose % w/v 200 1 50 + 100 100 0.05  10 1 50 + 100 100 1

TABLE-US-00052 TABLE HB7a Biological efficacy on Echinochloa crus-galli (ECHCG). ECHCG HB4 HB5 HB6 HB7 200 l/ha 96 96 96 97 10 l/ha 80 93 97 96

TABLE-US-00053 TABLE HB7b Biological efficacy on Alopecurus myosuroides (ALOMY). ALOMY HB4 HB5 HB6 HB7 200 l/ha 60 78 88 20 10 l/ha  8 73 90 90

TABLE-US-00054 TABLE HB7c Biological efficacy on Amaranthus retroflexus (AMARE). AMARE HB4 HB5 HB6 HB7 200 l/ha 98 100 100  98 10 l/ha 48 100 100 100

TABLE-US-00055 TABLE HB7d Biological efficacy on Abutilon theophrasti (ABUTH). ABUTH HB4 HB5 HB6 HB7 200 l/ha 88 96 90 90 10 l/ha 60 98 90 88

[0253] The results in table HB7a-d show that recipes HB5, HB6 and HB7 illustrative of the invention show greater or same efficacy at 10 L/ha spray volume as at 200 L/ha on different weeds and also compared to the reference recipe HB4.

Example HB3: OD

[0254]

TABLE-US-00056 TABLE HB8 Recipes HB10, HB11, HB12 and HB13 . Recipe HB11 Recipe HB12 Recipe HB13 Recipe HB10 according to according to according to the Component (g/kg) reference the invention the invention invention THIENCARBAZONE- 10 10 10 10 METHYL (a) MEFENPYR-DIETHYL 60 60 60 60 (a) RAPESEED OIL 0 200 0 0 METHYL ESTER (b) GENAPOL X 090 (b) 0 0 200 0 DISFLAMOLL TOF (b) 0 0 0 200 BENTONE 34(c) 20 20 20 20 CALSOGEN AR 100 80 80 80 80 ND (c) EMULSOGEN EL400 60 60 60 60 (c) PROPYLENE CARBONATE (c) 2 2 2 2 SILICOLAPSE 482 1.5 1.5 1.5 1.5 SODIUM 2 2 2 2 CARBONATE (c) SOLVESSO 200ND to volume to volume to volume to volume (add to 1 litre) The method of preparation used was according to Method 4.

TABLE-US-00057 TABLE HB9a Additive dose g/ha for each treatment HB10 reference Additive Additive dose Spray volume Rate ofS C Rate of a.i. dose In spray l/ha applied l/ha g/ha g/ha liquid % w/v 200 1.5 15 + 90 0 0 10 1.5 15 + 90 0 0 200 0.75 7.5 + 45  0 0 10 0.75 7.5 + 45  0 0

TABLE-US-00058 TABLE HB9b Additive dose g/ha for each treatment HB11, HB12 and HB13 Additive Additive dose Spray volume Rate of OD Rate of a.i. dose In spray l/ha applied l/ha g/ha g/ha liquid % w/v 200 1.5 15 + 90 300 0.15 10 1.5 15 + 90 300 3 200 0.75 7.5 + 45  150 0.075 10 0.75 7.5 + 45  150 1.5

TABLE-US-00059 TABLE HB10a Biological efficacy on Setaria viridis (SETVI) @ 7.5 g TCM SETVI HB10 HB11 HB12 HB13 200 l/ha 90 95 90 90 10 l/ha 80 90 90 90

TABLE-US-00060 TABLE HB10b Biological efficacy on Avena fatua (AVEFA) @ 7.5 g TCM AVEFA HB10 HB11 HB12 HB13 200 l/ha 20 80 50 40 10 l/ha 40 80 80 60

TABLE-US-00061 TABLE HB10c Biological efficacy on Hordeum murinum (HORMU) @ 7.5 g TCM HORMU HB10 HB11 HB12 HB13 200 l/ha 20 70 20 30 10 l/ha 40 80 80 60

TABLE-US-00062 TABLE HB10d Biological efficacy on Pharbitis purpurea (PHBPU) @ 15 g TCM PHBPU HB10 HB11 HB12 HB13 200 l/ha 90 90 90 60 10 l/ha 70 90 90 90

TABLE-US-00063 TABLE HB10e Biological efficacy on Abutilon theophrasti (ABUTH) @ 15g TCM ABUTH HB10 HB11 HB12 HB13 200 l/ha 90 80 90 60 10 l/ha 40 90 80 85

[0255] The results in table HB10a-e show that recipes HB11, HB12 and HB13 illustrative of the invention show greater or same efficacy at 10 L/ha spray volume as at 200 L/ha on different weeds and also compared to the reference recipe HB10.