AGROCHEMICAL FORMULATION BASED ON EMULSION POLYMERS

Abstract

The present invention relates to agrochemical compositions based on emulsion polymers; their use for foliar application and their application in aqueous crop protection flowable formulations for controlling agricultural pests, weeds or diseases and reducing the wash-off of active ingredients by rainfall.

Claims

1. An agrochemical composition comprising a) an aqueous dispersion of at least one agrochemical active compound, which is solid at room temperature, b) an emulsion polymer system comprising I) stabiliser polymer; and II) core-stabiliser copolymer, wherein the I) stabiliser polymer comprises acid based and hydrophobe monomers having a weight/number ratio of said acid to hydrophobe of 10-90:90-10, a Tg in the range from 30 C. to 300 C., and a molecular weight less than 100,000; and the II) core polymer having a Tg in the range from 100 C. to 10 C. and c) one or more additives selected from the group consisting of non-ionic or anionic surfactants or dispersing aids, d) one or more rheological modifiers, e) and one or more other formulants.

2. An agrochemical composition according to claim 1, further comprising f) One or more penetration promoters, wetting agents, spreading agents and/or retention agents

3. A product comprising the agrochemical composition according to claim 1 for foliar application.

4. A product comprising the agrochemical composition according to claim 1 to combat or control an agricultural pest, weed or disease.

5. A product comprising the agrochemical composition according to claim 1 for application of the agrochemical active compound contained to one or more plants and/or a habitat thereof.

6. A product comprising the agrochemical composition according to claim 1 to improve the rainfastness of an agrochemical active ingredient.

7. A product comprising the agrochemical composition according to claim 1 to improve the resistance to wash-off by rain of an agrochemical active ingredient.

8. A product comprising the agrochemical composition according to claim 1 to reduce off-target losses to the environment of an agrochemical active ingredient.

Description

EXAMPLES

A) Methods

[0186] The rainfastness was determined according to the following method.

[0187] Method 1:

[0188] 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 1 l drops of the different formulations diluted at 0.5% to 1% 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 15s. 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 at the following amounts: >90%, 75%, 50%, 25% and <10%. Two replicates were measured and the mean value of the two replicates recorded.

[0189] The formulations were prepared according to the following methods.

Method 2:

[0190] 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 in water and the biocides (e) was prepared with low shear stirring. The active ingredient(s) (a), non-ionic and anionic dispersants (c) and other formulants (e) were mixed 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 polymer dispersion (b) and xanthan gel were added and mixed in with low shear stirring until homogeneous.

Method 3:

[0191] 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 (e) and antioxidant (e) were mixed and added to an aqueous dispersion comprising a portion (32 g/l) 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 fluopyram (a), the remaining non-ionic and anionic dispersants (c) and other remaining formulants (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 (b) and xanthan gel were added and mixed in with low shear stirring until homogeneous.

[0192] The formulation stability was determined according to the following method.

Method 4:

[0193] The stability of the example formulations was determined by storing one sample at 45 C. for 1 week and storing another sample overnight at 30 C. and room temperature, RT, (22 C.) during the day or overnight at 15 C. and 30 C. during the day for five to eight cycles. They were then examined visually for any thickening and a 1% dilution in water was examined in a microscope for any signs of aggregation of the active ingredient particles. The sieve retention in Example 2 was determined by pouring 50 ml of a 1% suspension of each example formulation through a 150 micron sieve, rinsing with water and visually determining the sieve residue.

Example 1

[0194] Formulations were prepared with the following recipes:

TABLE-US-00003 Component (g/l) Example 1 Fluopyram (a) 500 Non-ionic dispersants (c) 60 Anionic dispersants (c) 15 Rheological modifier (d) 2.4 Biocides (e) 2.6 Additive according to Table 3 (b) 30 Antifreeze (e) 80 Antifoam (e) 2 Water To volume (~498)

[0195] The method of preparation used was according to Method 2 with the wash-off determined according to Method 1 and the stability determined according to Method 4 described previously with the high temperature stability assessed after 1 week at 45 C. and the low temperature stability assessed after 30 C./RT cycling storage.

TABLE-US-00004 TABLE 3 List of additives used in Example 1 and corresponding wash-off and stability results. Additive Stability Stability 30/ (from table 2) % wash-off 1W45 RT (x5) (1) <10 stable stable (2) <10 stable stable (3) 17.5 stable stable (4) <10 stable stable (5) 17.7 stable stable (6) 37.5 stable stable (7) 25 stable stable (8) 75 stable aggregation (9) 25 stable Stable (10) 75 stable stable (11) <10 stable stable (12) 25 stable stable (13) 17.5 stable stable (14) 25 stable stable Atlox Semkote E135 17.5 stable aggregation No additive >75 stable stable

[0196] This example shows that the resin stabilised emulsion polymer additives significantly reduce wash-off of the active ingredient at a level similar to the comparison additive Atlox Semkote E135 and also show better stability in the majority of cases than the comparison example of Atlox Semkote E135.

Example 2

[0197] Suspo-emulsion formulations were prepared with the following recipes:

TABLE-US-00005 Component (g/l) Example 2 Spiroxamine (a) 200 Fluopyram (a) 75 Antioxidant (e) 0.5 Non-ionic dispersants (c) 37 Anionic dispersants (c) 7 Rheological modifier (d) 0.7 Oils (e) 160 Biocides (e) 2.5 Additive from Table 4 (b) 30 Antifreeze (e) 80 Antifoam (e) 2 Water To volume (~435)

[0198] The method of preparation used was according to Method 3 with the wash-off determined according to Method 1 and the stability determined according to Method 4 described previously.

TABLE-US-00006 TABLE 4 List of additives used in Example 2 and corresponding wash-off and sieve retention results. Additive Sieve retention (from table 2) % wash-off (150 microns) (1) 50 0 (2) 82.5 0 (6) 82.5 0 (9) 50 0 (11) 37.5 0 (12) 50 0 (13) 50 0 (14) 62.5 0 Atlox Semkote E135 50 High No additive >90 0

[0199] This example 2 shows that the resin stabilised emulsion polymer additives significantly reduce wash-off of the active ingredient in Suspo-emulsion formulations at a level similar to the comparison additive Atlox Semkote E135 and also show better dilution stability than the comparison example of Atlox Semkote E135 which shows high unacceptable sieve residues.

Example 3

[0200] Formulations were prepared with the following recipes:

TABLE-US-00007 Component (g/l) Example 3 Fluopyram (a) 200 Tebuconazole (a) 200 Non-ionic dispersants (c) 65 Anionic dispersants (c) 8 Rheological modifier (d) 1.7 Biocides (e) 2.6 Additive from table 5 (b) 30 Antifoam (e) 4 Antifreeze (e) 25 Wetting agents (f) 90 Water To volume (~534)

[0201] The method of preparation used was according to Method 2 with the wash-off determined according to Method 1 and the stability determined according to Method 4 described previously.

TABLE-US-00008 TABLE 5 List of additives used in Example 3 and corresponding wash-off and stability results. Additive Stability Stability 30/ (from table 2) % wash-off 1W45 RT x8 cycles (1) 75 stable stable (2) 75 stable stable (3) 75 stable aggregation x8 (4) 75 aggregation stable (5) 75 aggregation Stable (6) 90 aggregation stable (7) 90 aggregation stable (8) 82.5 stable stable (9) 62.5 aggregation stable (10) 82.5 aggregation stable (11) 75 aggregation stable (12) 75 aggregation stable (13) 75 stable aggregation x3 (14) 62.5 stable aggregation x3 No additive 90 stable stable

[0202] This example shows that resin stabilised emulsion polymer additives (1), (2) and (8) have enhanced resistance to wash-off and give stable formulations both at 1W45 and 30/RT (x8) cycling storage testing. It is especially surprising that certain of the resin stabilised emulsion additives reduced wash-off in the presence of wetting agents (f).

Example 4

[0203] Formulations were prepared with the following recipes:

TABLE-US-00009 Component (g/l) Example 4 Isotianil (a) 135 Tebuconazole (a) 180 Trifloxystrobin (a) 90 Non-ionic dispersants (c) 25 Anionic dispersants (c) 20 Rheological modifier (d) 1 Biocides (e) 2.6 Additive from table 6 (b) 30 Antifoam (e) 2.5 Antifreeze (e) 100 Wetting agents (f) 70 Water To volume (~435)

[0204] The method of preparation used was according to Method 2 with the wash-off determined according to Method 1 and the stability determined according to Method 4 described previously.

TABLE-US-00010 TABLE 6 List of additives used in Example 4 and corresponding wash-off and stability results. Additive Stability Stability 30/ (from table 2) % wash-off 1W45 RT (x6) (1) 50 aggregation aggregation (2) 62.5 stable stable (3) 50 stable stable (4) 50 stable stable (5) 50 stable stable (6) 62.5 stable stable (7) 50 stable stable (8) 62.5 stable stable (9) 50 stable stable (10) 62.5 stable stable (11) 50 stable stable (12) 50 stable stable (13) 50 stable stable (14) 50 stable stable Atlox Semkote E135 50 aggregation aggregation No additive 75 stable stable

[0205] This example shows that the resin stabilised emulsion polymer additives have enhanced resistance to wash-off in the example formulation equivalent or similar to the comparison additive Atlox Semkote E135 and importantly give stable formulations both at 1W45 and 30/RT (x6) cycling storage testing while the comparison additive shows aggregation resulting in an unstable and unusable formulation. It is especially surprising that the resin stabilised emulsion additives work in the presence of wetting agents (f).

Example 5

[0206] Formulations were prepared with the following recipes:

TABLE-US-00011 Component (g/l) Example 5 Aclinofen (a) 375 Diflufenican (a) 50 Flufenacet (a) 150 Non-ionic dispersants (c) 61 Anionic dispersants (c) 12.2 Rheological modifiers (d) 8.5 Biocides (e) 3.2 Antifoam (e) 6.1 Antifreeze (e) 61 Additive from table 7 (b) 30 Water To volume (~443)

[0207] The method of preparation used was according to Method 2 described previously, the rheological modifiers were incorporated with a rotor-stator mixer. The wash-off was determined according to Method 1 and the stability determined according to Method 4 described previously.

TABLE-US-00012 TABLE 7 List of additives used in Example 5 and corresponding wash-off and stability results. Additive Stability Stability 30/ (from table 2) % wash-off 1W45 RT (x6) (1) 75 stable stable (2) 62.5 stable stable (6) 62.5 stable stable (9) 75 stable stable (11) 50 stable stable (12) 50 stable stable (13) 62.5 stable stable (14) 50 stable stable Atlox Semkote E135 37.5 stable unstable, aggregation and thick paste like appearance No additive 82.5 stable stable

[0208] This example shows that the resin stabilised emulsion polymer additives reduce wash-off of the active ingredient. The comparison additive Atlox Semkote E135 was completely unstable in the low temperature cycling test while surprisingly the resin stabilised polymer additives were stable.

Example 6

[0209] Formulations were prepared with the following recipes:

TABLE-US-00013 Component (g/l) Example 6 Tetraniliprole (a) 200 Non-ionic dispersants (c) 60.5 Anionic dispersants (c) 11 Rheological modifier (d) 11.33 Biocides (e) 2.2 Antifreeze (e) 110 Antifoam (e) 1.65 Additive from table 8 (b) 30 Water To volume (~702)

[0210] The method of preparation used was according to Method 2 with the wash-off determined according to Method 1 and the stability determined according to Method 4 described previously with the high temperature stability assessed after 2w45 C.

TABLE-US-00014 TABLE 8 List of additives used in Example 6 and corresponding wash-off and stability results. Additive Stability Stability 30/ (from table 2) % wash-off 2W45 RT (x5) (11) 50 stable stable (13) 50 stable stable Atlox Semkote E135 62.5 stable stable No rainfast-additive >90 stable stable

[0211] This example shows that the resin stabilised emulsion polymer additives (11) and (13) significantly reduced wash-off of the active ingredient and at a level greater than the comparison additive Atlox Semkote E135. In this example no differences in stability were observed.

Example 7

[0212] Formulations were prepared with the following recipes:

TABLE-US-00015 Component (g/l) Example 7 Spirodiclofen (a) 240 Non-ionic dispersants (c) 32.4 Rheological modifier (d) 3.7 Biocides (e) 2.3 Antifreeze (e) 108 Antifoam (e) 1.1 pH adjuster (e) 1 Additive from table 9 (b) 40 Water To volume (~648)

[0213] The method of preparation used was according to Method 2 with the wash-off determined according to Method 1 and the stability determined according to Method 4 described previously with the low temperature stability assessed after cycling storage at 15 and +30 C.

TABLE-US-00016 TABLE 9 List of additives used in Example 7 and corresponding wash-off and stability results. Stability Stability 15/ Additive (from table 2) % wash-off 1W45 30 (x5) (20) 50 Stable: fluid Stable: fluid suspension, suspension, particles particles dispersed dispersed No rainfast-additive 70 Stable: fluid Stable: fluid suspension, suspension, particles particles dispersed dispersed

[0214] This example shows that the resin stabilised emulsion polymer additive (20) when included in the formulation resulted in a decrease in the amount of active ingredient washed off. Furthermore, the resin stabilised emulsion polymer did not cause the formulation to become unstable.

Example 8

[0215] Formulations were prepared with the following recipes:

TABLE-US-00017 Component (g/l) Example 8 Spiromesifen (a) 321 Non-ionic dispersants (c) 42.8 Rheological modifier (d) 3.2 Biocides (e) 2.1 Antifreeze (e) 107 Antifoam (e) 1.1 pH adjuster (e) 1.1 Additive from table 10 (b) 40 Water To volume (~592)

[0216] The method of preparation used was according to Method 2 with the wash-off determined according to Method 1 and the stability determined according to Method 4 described previously.

TABLE-US-00018 TABLE 10 List of additives used in Example 8 and corresponding wash-off and stability results. Stability Stability 15/ Additive (from table 2) % wash-off 1W45 30 (x5) (20) 10 Stable: fluid Stable: fluid suspension, suspension, particles particles dispersed dispersed No rainfast-additive 62.5 Stable: fluid Stable: fluid suspension, suspension, particles particles dispersed dispersed

[0217] This example shows that the resin stabilised emulsion polymer additive (20) when included in the formulation resulted in a substantial decrease in the amount of active ingredient washed off. Furthermore, the resin stabilised emulsion polymer did not cause the formulation to become unstable.

Example 9

[0218] Formulations were prepared with the following recipes:

TABLE-US-00019 Component (g/l) Example 9 Ethiprole (a) 100 Non-ionic dispersants (c) 51.5 Anionic dispersants (c) 51.5 Rheological modifier (d) 5.2 Biocides (e) 1.8 Antifreeze (e) 20.6 Antifoam (e) 5.2 Penetration promoter (f) 206 Additive from table 11 (b) 60 Water To volume (~585)

[0219] The method of preparation used was according to Method 2 with the wash-off determined according to Method 1 and the stability determined according to Method 4 described previously.

TABLE-US-00020 TABLE 11 List of additives used in Example 9 and corresponding wash-off and stability results. Stability Stability 15/ Additive % wash-off 1W45 30 (x5) (20) 17.5 Stable: fluid Stable: fluid suspension, suspension, particles particles dispersed dispersed No rainfast-additive 75 Stable: fluid Stable: fluid suspension, suspension, particles particles dispersed dispersed

[0220] This example shows that the resin stabilised emulsion polymer additive (20) when included in the formulation resulted in a substantial decrease in the amount of active ingredient washed off. Furthermore, the resin stabilised emulsion polymer did not cause the formulation to become unstable.

Example 10

[0221] Formulations were prepared with the following recipes:

TABLE-US-00021 Component (g/l) Example 10 Fluopicolide (a) 200 Non-ionic dispersants (c) 12 Anionic dispersants (c) 6 Rheological modifier (d) 2.2 Biocides (e) 2.6 Antifreeze (e) 100 Antifoam (e) 2 Additive from table 12 (b) 50 Water To volume (~704)

[0222] The method of preparation used was according to Method 2 with the wash-off determined according to Method 1 with six replicates and the stability determined according to Method 4 described previously.

TABLE-US-00022 TABLE 12 List of additives used in Example 10 and corresponding wash-off and stability results. Stability Stability 15/ Additive % wash-off 1W45 30 (x5) (20) 56 Stable: fluid Stable: fluid suspension, suspension, particles particles dispersed dispersed No rainfast-additive 63 Stable: fluid Stable: fluid suspension, suspension, particles particles dispersed dispersed

[0223] This example shows that the resin stabilised emulsion polymer additive (20) when included in the formulation resulted in a decrease in the amount of active ingredient washed off. Furthermore, the resin stabilised emulsion polymer did not cause the formulation to become unstable.

Example 11

[0224] Formulations were prepared with the following recipes:

TABLE-US-00023 Component (g/l) Example 11 Diflufenican (a) 90 Flufenacet (a) 240 Flurtamone (a) 120 Non-ionic dispersants (c) 58.5 Anionic dispersants (c) 5.9 Rheological modifier (d) 3.5 Biocides (e) 2.3 Antifreeze (e) 93.6 Antifoam (e) 11.7 pH adjuster (e) 5.9 Additive from table 13 (b) 50 Water To volume (~724)

[0225] The method of preparation used was according to Method 2 with the wash-off determined according to Method 1 and the stability determined according to Method 4 described previously.

TABLE-US-00024 TABLE 13 List of additives used in Example 11 and corresponding wash-off and stability results. Stability Stability 15/ Additive (from table 2) % wash-off 1W45 30 (x5) (20) 25 Stable: fluid Stable: fluid suspension, suspension, particles particles dispersed dispersed No rainfast-additive 75 Stable: fluid Stable: fluid suspension, suspension, particles particles dispersed dispersed

[0226] This example shows that the resin stabilised emulsion polymer additive (20) when included in the formulation resulted in a substantial decrease in the amount of active ingredient washed off. Furthermore, the resin stabilised emulsion polymer did not cause the formulation to become unstable.

Example 12

[0227] Formulations were prepared with the following recipes:

TABLE-US-00025 Component (g/l) Example 12 Clomeprop (a) 90 Fentrazamide (a) 60 Tefuryltrione (a) 60 Anionic dispersants (c) 10.6 Rheological modifier (d) 2.4 Biocides (e) 0.5 Antifreeze (e) 53 Antifoam (e) 2.1 pH adjuster (e) 10.6 Additive from table 14 (b) 40 Water To volume (~769)

[0228] The method of preparation used was according to Method 2 with the wash-off determined according to Method 1 and the stability determined according to Method 4 described previously.

TABLE-US-00026 TABLE 14 List of additives used in Example 12 and corresponding wash-off and stability results. Stability Stability 15/ Additive (from table 2) % wash-off 1W45 30 (x5) (20) 10 Stable: fluid Stable: fluid suspension, suspension, particles particles dispersed dispersed No rainfast-additive 17.5 Stable: fluid Stable: fluid suspension, suspension, particles particles dispersed dispersed

[0229] This example shows that the resin stabilised emulsion polymer additive (20) when included in the formulation resulted in a decrease in the amount of active ingredient washed off. Furthermore, the resin stabilised emulsion polymer did not cause the formulation to become unstable.

Example 13

[0230] Formulations were prepared with the following recipes:

TABLE-US-00027 Recipe 1 Recipe 2 Recipe 3 Not according to According to According to Component (g/l) the invention the invention the invention Trifloxystrobin (a) 120 120 120 Tebuconazole (a) 240 240 240 Non-ionic dispersants (c) 25 25 25 Anionic dispersants (c) 20 20 20 Rheological modifier (d) 1.0 1.0 1.0 Biocides (e) 2.6 2.6 2.6 Antifreeze (e) 100 100 100 Antifoam (e) 5 5 5 Wetting agents (f) 100 100 90 Additive (13) from table 0 40 40 2 (b) Water To volume To volume To volume (~504) (~464) (~474)

[0231] The method of preparation used was according to Method 1 described previously. Recipe 1 and recipe 2 along with the references Nativo WG and Nativo SC were applied by spray application to rice plants at a trifloxystrobin dose of 50 g/ha and tebuconazole dose of 100 g/ha with a water volume of 100 L/ha. 1 hour after application the plants were placed in a purposely designed rain tower and artificial rain at an intensity of 30 mm/h was applied for 20 minutes. The plants were left to dry and analysed for active ingredients remaining both on and in the plants 15 hours after fungicide application.

TABLE-US-00028 TABLE 15 Amount of active ingredient remaining on and in the plants after artificial rainfall (applied 1 hour after application) measured 15 hours after fungicide application. % active ingredient Recipe Recipe Native Nativo remaining after rain 1 2 WG SC Trifloxystrobin 61.5 88.4 37.7 74.1 (cv. Japonica bailla) Tebuconazole 38.4 47.6 26.7 44.1 (cv. Japonica bailla) Trifloxystrobin 94.3 100 38.2 45.3 (cv. Indica) Tebuconazole 50.7 58.4 24.7 25.2 (cv. Indica)

[0232] This example shows that recipe 2 according to the invention containing the resin stabilised emulsion polymer additive consistently showed the highest rainfastness and lowest wash-off with the highest amount of active ingredient remaining after the application of artificial rain and reduced unwanted off-target losses to the environment.

[0233] Furthermore, after 6 months storage at RT and at 40 C. recipe 3 remained as a stable fluid suspension which readily formed sprayable dispersions on dilution without aggregation of the active ingredient particles demonstrating good stability of recipes according to the invention.

Example 14

[0234] In another example the biological performance of recipe 3 (according to the invention) and Nativo WG was compared outdoors in paddy rice. The biological efficacy for leaf and neck rice blast disease was assessed 13-15 days after the second foliar spray application (assessment 1) and 21-35 days after the second or third foliar spray application (assessment 2) and the yield measured at harvest.

TABLE-US-00029 TABLE 16 Biological efficacy and yield results from example 14. % yield Rates Rates % disease % disease increase trifloxystrobin tebuconazole control control over Formulation g a.i./ha g a.i./ha assessment 1 assessment 2 untreated Nativo WG 50 25 69 56 189 (reference, not 90 45 77 65 192 according to 120 60 74 72 203 the invention) 150 75 74 78 212 Recipe 3 50 25 70 65 197 (according to 90 45 78 74 208 the invention) 120 60 81 80 222 150 75 87 84 218

[0235] Recipe 3 containing the resin stabilised emulsion polymer additive according to the invention showed both improved efficacy and improved yield compared to the reference, Nativo WG.