Agrochemical formulation

Abstract

The present invention relates to a composition comprising an aqueous continuous phase; a first dispersed phase which comprises styrene-maleimide copolymer particles; and a second dispersed phase which is either oil droplets, suspended particles or a capsule suspension; and to use of those compositions to control agricultural pests or diseases. It also relates to use of such compositions where rainfastness is important.

Claims

1. A composition comprising: (i) an aqueous continuous phase; (ii) a first dispersed phase dispersed in (i) which is particles with themselves comprise a styrene-maleimide co-polymer; and (iii) a second dispersed phase dispersed in (i) which is either droplets comprising an oil, is suspended solid particles, or is suspended capsules and wherein the second dispersed phase further comprises an agrochemical wherein the agrochemical is either an oil or is dissolved in oil, or is the suspended solid particles, or is present within the suspended capsules.

2. A composition as claimed in claim 1, where the agrochemical is an herbicide, a fungicide, or an insecticide.

3. A composition as claimed in claim 2, where the agrochemical is a fungicide or an insecticide.

4. A composition as claimed in claim 3, wherein the agrochemical is a strobilurin.

5. A composition as claimed in claim 1, where the concentration of the agrochemical is from 5% to 40% by weight.

6. A composition as claimed in claim 4, which further comprises a triazole fungicide.

7. A Composition as claimed in claim 6, where the total agrochemical concentration is from 55 to 40% by weight.

8. A composition as claimed in claim 1, where the second dispersed phase is droplets of an oil adjuvant.

9. A composition as claimed in claim 1, where the co-polymer has an anhydride monomer content which is from 15 to 50 mol %.

10. A composition as claimed in claim 1, where the weight averaged molecular weight of the styrene-maleimide co-polymer is form 4,000 to 500,000 g/mole.

11. A composition as claimed in claim 1, where the styrene-maleimide copolymer is of formula (I) ##STR00002## where m is from 250 to 800; and n is from 100 to 400.

12. A composition as claimed in claim 11, where m is from 559 to 575; and n is from 200 to 225.

13. A composition as claimed in claim 11 where the concentration of the co-polymer is from 2 to 50% by weight.

Description

EXAMPLE 1

(1) Improved rainfastness of azoxystrobin with styrene maleimide copolymer on corn.

(2) This study demonstrates that the addition of styrene malemide copolymer can reduce the loss of an active ingredient from a leaf surface during rainfall.

(3) A range of substrates can be used in this test with the chosen material in this example being a maize leaf. Herein the maize plants, avenir variety, were grown for 3 weeks to the 5 leaf stage. These leaves were mounted using double sided tape to flat tiles (30 cm by 30 cm at an even spacing of 3 leaves per tile.

(4) A deposition solution was then prepared at the concentration which would be used under commercial application conditions. In this case 0.67 g of an azoxystrobin 200 g/1 SC formulation and 0.25 g Activator 90 (non-ionic surfactant) were added to 98.58 g water for the control and the effect of the styrene malemide polymer determined by creating a similar sample with 0.3% w/w of the water replaced by styrene malemide copolymer.

(5) Twenty 0.2 l droplets were applied to each substrate using a micro applicator. The substrate was allowed to dry for 2 hours. After the drying period one board containing 6 leaves per treatment were rained on, at 10 mm/hour for one hour while the other board was sampled by washing each leaf with 20 mls of acetonitrile (Sigma Aldrich) and gentle agitation for 20 seconds. The rainfall was simulated using a rain tower which combines the rate of water flow and shutter opening to achieve the target intensity of rainfall. The rain tower was positioned such that the droplets reached their terminal velocity before hitting the target surface. After the raining period, the rained on leaves were washed using the same protocol (gentle agitation in 20 ml acetonitrile for 20 seconds).

(6) The quantities of azoxystrobin in the acetonitrile solutions were determined via LCMS (Thermo TSQ Quantum LC/MS/MS, Column 845) and the % active ingredient remaining after rainfall was determined by dividing the quantity of azoxystrobin on each leaf after rainfall by that before rainfall. Azoxystrobin SC+Activator 90: 3.5% azoxystrobin remained on the leaves. Azoxystrobin SC+Activator 90+styrene malemide copolymer: 29% azoxystrobin remained on the leaves.

EXAMPLE 2

(7) Improved rainfastness of azoxystrobin with styrene maleimide copolymer on soya.

(8) This study demonstrates that the addition of styrene malemide copolymer can reduce the loss of an active ingredient from a leaf surface during rainfall.

(9) A range of substrates can be used in this test with the chosen material in this example being a soya leaf. Herein the soya, Glycine Max (Williams variety), was grown for 4 weeks in 4 inch pots with the top 2 tri-foliates used in the study. The leaves were mounted using double sided tape to flat tiles (30 cm by 30 cm) at an even spacing of 6 leaves per tile.

(10) A deposition solution was then prepared at the concentration which would be used under commercial application conditions. In this case 0.375 g of an azoxystrobin SC formulation (containing 200 g/l azoxystrobin) and 7.5 g Nimbus were added to 98.6 g water for the control and the effect of the styrene malemide co-polymer determined by creating a similar sample with 0.3% w/w of the water replaced by styrene malemide co-polymer.

(11) Twenty 0.2 l droplets were applied to each substrate using a micro applicator. The substrate was allowed to dry for 2 hours. After the drying period one board containing 6 leaves per treatment were rained on, at 10 mm/hour for one hour while the other board was sampled by washing each leaf with 20 mls of acetonitrile (Sigma Aldrich) and gentle agitation for 20 seconds. The rainfall was simulated using a rain tower which combines the rate of water flow and shutter opening to achieve the target intensity of rainfall. The rain tower was positioned such that the droplets reached their terminal velocity before hitting the target surface. After the raining period, the rained on leaves were washed using the same protocol (gentle agitation in 20 ml acetonitrile for 20 seconds).

(12) The quantities of azoxystrobin in the acetonitrile solutions determined via LCMS (Thermo TSQ Quantum LC/MS/MS, Column 845) and the % active ingredient remaining after rainfall determined by dividing the quantity of AZ on each leaf after rainfall by that before rainfall. Azoxystrobin SC+Nimbus: 15% azoxystrobin remained on the leaves. Azoxystrobin SC+Nimbus: styrene malemide copolymer 55% remained on the leaves.

EXAMPLE 3

(13) This example demonstrates that while acrylic polymers known for their water barrier properties can improve the rainfastness of the active ingredient they can also, disadvantageously, reduce the bioavailability.

(14) The method described in Example 2 was used to assess the rainfastness of azoxystrobin in the presence of Nimbus on Soya leaves with the addition of various polymers. The acrylic emulsion used was Neocryl XK-230 (DSM) and the acrylic latex (Neocryl XK-90).

(15) The bioavailability of the azoxystrobin was assessed by spraying three week old soya plant (William's variety) using a track sprayer and a standard flat fan nozzle at an equivalent water volume of 50 l/ha containing 9 g/ha of azoxystrobin, 30 g/ha Nimbus and 0.3% w/w of the tested copolymers. The plants were inoculated with 10.sup.5 spores per ml of water one day after spray application and the first tri-foliates were assessed for fungal control after a further 14 days.

(16) TABLE-US-00001 TABLE 1 % of azoxystrobin % control of remaining on the Phakapsora Compound leaf surface pachyrhizia none 15 100 Styrene Maleimide 55 100 copolymer Acrylic emulsion 66 11 Acrylic latex 20 43

(17) The data within the table show that while polymers improve the rainfastness of azoxystrobin surprisingly only the styrene maleimide allows the active ingredient to deliver acceptable biological performance.

EXAMPLE 4

(18) This example demonstrates the lack of impact on uptake of cyproconazole by the styrene maleimide copolymer.

(19) 4 pots of soya, Williams's variety, were grown in the glasshouse for four weeks until the plants reached the 3-4 trifoliate stage. These plants were tracksprayed with the treatment list below at a rate of 24 g a.i./ha in a water volume of 80 l/ha. All treatments included Nimbus at a rate of 600 ml/ha.

(20) At time zero, 5 hours after application and 1, day after fully expanded leaves were cut off, weighed and shaken in 10 ml of acetonitrile to remove the unabsorbed foliar deposits. Ten replicate leaves were sampled per treatment and the samples analysed by LCMS (Thermo TSQ Quantum LC/MS/MS, Column 845).

(21) TABLE-US-00002 TABLE 2 % of cyproconazole % of cyproconazole within the plant within the plan (5 hours after (1 day after Compound application) application) Cyproconazole 80g/l SC + 67 92 NIMBUS Cyproconazole 80g/l SC + 73 87 Styrene Maleimide copolymer + NIMBUS Cyproconazole 80g/l SC + 45 78 Acrylic latex + NIMBUS

(22) The treatment containing the acrylic latex is has a statistically significant lower uptake of cyproconazole than the treatments containing no additional polymer and the styrene maleimide copolymer, which are statistically equivalent.

EXAMPLE 5

(23) Effect of styrene maleimide rate on the rainfastness of an azoxystrobin 200 g/l SC.

(24) This study demonstrates that the amount of styrene malemide copolymer used positively correlates with the rainfastness of the resulting azoxystrobin-containing formulation.

(25) A range of substrates can be used in this test with the chosen material in this example being a soya leaf. Herein the soya, Glycine Max, was grown for 4 weeks in 4 inch pots with the top 2 tri-foliates used in the study. The leaves were mounted using double sided tape to flat tiles (30 cm by 30 cm) at an even spacing of 6 leaves per tile.

(26) A deposition solution was then prepared at the concentration which would be used under commercial application conditions. In this case 0.2 g of an azoxystrobin SC formulation (containing 200 g/l azoxystrobin) and 0.4 g Nimbus were added to 99.4 g water for the control and the effect of the styrene maleimide co-polymer determined by creating similar samples with 0.003, 0.006, 0.06, 0.12, 0.30% w/w of the water replaced by styrene malemide co-polymer.

(27) Twenty 0.2 l droplets were applied to each substrate using a micro applicator. The substrate was allowed to dry for 2 hours. After the drying period one board containing 6 leaves per treatment were rained on, at 10 mm/hour for one hour while the other board was sampled by washing each leaf with 20 mls of acetonitrile (Sigma Aldrich) and gentle agitation for 20 seconds. The rainfall was simulated using a rain tower which combines the rate of water flow and shutter opening to achieve the target intensity of rainfall. The rain tower was positioned such that the droplets reached their terminal velocity before hitting the target surface. After the raining period, the rained on leaves were washed using the same protocol (gentle agitation in 20 ml acetonitrile for 20 seconds).

(28) The quantities of azoxystrobin in the acetonitrile solutions determined via LCMS (LC/MS/MS comprising of Acquity LC and Thermo TSQ-Ultra) and the % active ingredient remaining after rainfall determined by dividing the quantity of AZ on each leaf after rainfall by that before rainfall.

(29) TABLE-US-00003 TABLE 3 % azoxystrobin remaining Treatment on Leaves after rainfall Azoxystrobin SC 3.1 Azoxystrobin SC + 0.003% 11.0 styrene maleimide co-polymer Azoxystrobin SC + 0.006% 5.6 styrene maleimide co-polymer Azoxystrobin SC + 0.06% 15.9 styrene maleimide co-polymer Azoxystrobin SC + 0.12% 17.3 styrene maleimide co-polymer Azoxystrobin SC + 0.30% 32.2 styrene maleimide co-polymer

EXAMPLE 6

(30) Preparation of a Built-In Formulation

(31) Formulations containing the styrene maleimide copolymer were prepared by the substitution of water from a typical SC [example compositions of which are given below]. These were prepared using standard preparation methods. As is common in suspension concentrate formulations the active ingredients were bead milled to improve colloidal stability to a size of around 1-2 microns and added as a millbase, those skilled in the art will appreciate the addition of dispersants will increase the efficiency of the milling step. During addition of these components the form the polymer containing SC the formulation was mixed under high shear in a jacketed vessel at 10 C. for 10 minutes. The output was free flowing suspension concentrates.

(32) TABLE-US-00004 TABLE 4 Order of Quantity in Quantity in Component addition (g/L) (g/L) Azoxystrobin 3 83 83 Cyproconazole 4 33 33 Styrene malemide 2 340 120 copolymer Kelzan 5 2 2 Water make-up 1 make-up to make-up to 1 litre 1 litre

EXAMPLE 7

(33) Rainfastness of an azoxystrobin 200 g/l SC when mixed with a styrene maleimide-containing tank-mix adjuvant.

(34) The example demonstrates that the styrene malemide copolymer can be combined with commercial tank-mix adjuvants to form emulsions which retains their rainfastness properties on spray tank dilution. Those skilled in the art will recognise such a composition would make a powerful tank mix adjuvant.

(35) Preparation of Mix 1

(36) Nimbus oil (6.0 ml) was added to a dispersion of Nanotope 26 SO50 WA50-30 (4.5 ml) in water (5.5 ml). The resulting mixture was rolled overnight.

(37) Preparation of Mix 2

(38) Nimbus oil (3.0 ml) was added to a dispersion of Nanotope 26 SO50 WA50-30 (4.5 ml) in water (2.0 ml). The resulting mixture was rolled overnight.

(39) Preparation of Mix 3

(40) Nimbus oil (5.0 ml) was added to a dispersion of Nanotope 26 SO50 WA50-30 (2.0 ml) in water (3.0 ml). The resulting mixture was rolled overnight.

(41) The rainfastness study was conducted in the same manner as Example 2. Spray dilutions of 80 l/ha were prepared, comprising azoxystrobin SC at 300 ml/ha and the other components at the rate stated in the table below.

(42) TABLE-US-00005 TABLE 5 % AI Remaining on Leaves Standard Treatment after Rainfall Deviation Azoxystrobin SC + 0.6 l/ha Nimbus 7 6.1 Azoxystrobin SC + 0.6 L/ha Nimbus + 44 11.0 450 ml/ha Nanotope 26 SO50 WA50-30 Azoxystrobin SC + 1.6 l/ha Tankmix 1 40 24.7 Azoxystrobin SC + 0.7 l/ha Tankmix 1 47 19.4 Azoxystrobin SC + 0.95 l/ha Tankmix 2 72 8.2 Azoxystrobin SC + 0.7 l/ha Tankmix 2 51 6.5

EXAMPLE 8

(43) Improved rainfastness of izopyrazam with styrene maleimide copolymer on soya.

(44) This study demonstrates that the addition of styrene malemide copolymer can reduce the loss of an active ingredient from a leaf surface during rainfall.

(45) A range of substrates could have been used in this test but the chosen material in this example was soya leaf; soya, Glycine Max (Williams variety), was grown for 4 weeks in 4 inch pots with the top 2 tri-foliates used in the study. The leaves were mounted, using double sided tape, to flat tiles (30 cm by 30 cm) at an even spacing of 6 leaves per tile.

(46) A deposition solution was then prepared at a concentration which could be used under commercial application conditions. In this case 0.25 g of an isopyrazam SC formulation (containing 250 g/l isopyrazam) was added to 99.58 g water as the control sample whilst the effect of the styrene malemide co-polymer was determined by creating a similar sample in which 0.5 g of the water was replaced by styrene malemide co-polymer.

(47) Twenty 0.2 l droplets were applied to each substrate using a micro applicator. The substrate was allowed to dry for 2 hours. After the drying period, one board containing 6 leaves per treatment was rained on, at 10 mm/hour for one hour while the other board was sampled by washing each leaf with 30 ml of acetonitrile (Sigma Aldrich) with gentle agitation for 20 seconds. The rainfall was simulated using a rain tower which combines the rate of water flow and shutter opening to achieve the target intensity of rainfall. The rain tower was positioned such that the droplets reached their terminal velocity before hitting the target surface. After the raining period, the rained on leaves were washed using the same protocol (gentle agitation in 30 ml acetonitrile for 20 seconds).

(48) The quantities of izopyrazam in the acetonitrile solutions were determined by mass spectrometry using a Waters Acquity UPLC and Thermo TSQ Quantum Ultra Triple Quadrupole MS Instrument or just LC/MS/MS. Column: Phase Kinetex C18 Length (mm) 50 Internal diameter (mm) 3.0 Particle Size (m) 2.6

(49) For all tests, the % active ingredient remaining after rainfall determined by dividing the quantity of izopyrazam on each leaf after rainfall by that before rainfall, leading to the following results: Izopyrazam SC alone: after rainfall, 47% isopyrazam remained on the leaves. Whereas: Izopyrazam SC+styrene malemide copolymer: after rainfall 84% isopyrazam remained on the leaves. Clearly the styrene malemide co-polymer has dramatically improved the rainfastness of the isopyrazam.

EXAMPLE 9

(50) Improved rainfastness of Helios SC with styrene maleimide copolymer on soya.

(51) This study demonstrates that the addition of styrene malemide copolymer can reduce the loss of a model active ingredient (AI) from a leaf surface during rainfall. Helios SC is a UV tracer commonly used as a model for an AI, containing particles of 2,2-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole).

(52) A range of substrates could be used in this test but the chosen material in this example was soya leaf; soya, Glycine Max (Williams variety), was grown for 4 weeks in 4 inch pots with the top 2 tri-foliates used in the study. The leaves were mounted, using double sided tape, to flat tiles (30 cm by 30 cm) at an even spacing of 6 leaves per tile.

(53) A deposition solution was then prepared at a concentration which could be used under commercial application conditions. In this case 0.181 g of a Helios SC formulation (containing 500 g/l 2,2-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole)) was added to 99.684 g water as the control sample whilst the effect of the styrene malemide co-polymer was determined by creating a similar sample with 0.5 g of the water replaced by styrene malemide co-polymer.

(54) Twenty 0.2 l droplets were applied to each substrate using a micro applicator. The substrate was allowed to dry for 2 hours. After the drying period, one board containing 6 leaves per treatment was rained on, at 10 mm/hour for one hour while the other board was sampled by washing each leaf with 30 ml of acetonitrile (Sigma Aldrich) with gentle agitation for 20 seconds. The rainfall was simulated using a rain tower which combines the rate of water flow and shutter opening to achieve the target intensity of rainfall. The rain tower was positioned such that the droplets reached their terminal velocity before hitting the target surface. After the raining period, the rained on leaves were washed using the same protocol (gentle agitation in 30 ml acetonitrile for 20 seconds).

(55) The quantities of 2,2-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole) in the acetonitrile solutions were determined via fluorimetry (Tecan M200 Pro, emission wavelength 429 mm) and the % active ingredient remaining after rainfall was determined by dividing the quantity of 2,2-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole) on each leaf after rainfall by that before rainfall, leading to the following results: Helios SC alone: after rainfall 41% 2,2-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole) remained on the leaves. Whereas Hellos SC+styrene malemide copolymer: after rainfall 78% 2,2-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole) remained on the leaves. Clearly the styrene malemide co-polymer has dramatically improved the rainfastness of the model AI.

EXAMPLE 10

(56) Improved Rainfastness of cyantraniliprole with styrene maleimide copolymer on soya.

(57) This study demonstrates that the addition of styrene malemide copolymer can reduce the loss of an active ingredient from a leaf surface during rainfall.

(58) A range of substrates can be used in this test with the chosen material in this example being a soya leaf. Herein the soya, Glycine Max (Williams variety), was grown for 4 weeks in 4 inch pots with the top 2 tri-foliates used in the study. The leaves were mounted using double sided tape to flat tiles (30 cm by 30 cm) at an even spacing of 6 leaves per tile.

(59) A deposition solution was then prepared at the concentration which would be used under commercial application conditions. In this case 0.12 g of cyantraniliprole technical was added to 99.82 g water for the control and the effect of the styrene malemide co-polymer determined by creating a similar sample with 0.5 g of the water replaced by styrene malemide co-polymer.

(60) Twenty 0.2 l droplets were applied to each substrate using a micro applicator. The substrate was allowed to dry for 2 hours. After the drying period one board containing 6 leaves per treatment were rained on, at 10 mm/hour for one hour while the other board was sampled by washing each leaf with 30 mls of acetonitrile (Sigma Aldrich) and gentle agitation for 20 seconds. The rainfall was simulated using a rain tower which combines the rate of water flow and shutter opening to achieve the target intensity of rainfall. The rain tower was positioned such that the droplets reached their terminal velocity before hitting the target surface. After the raining period, the rained on leaves were washed using the same protocol (gentle agitation in 20 ml acetonitrile for 20 seconds).

(61) The quantities of cyantraniliprole in the acetonitrile solutions determined by mass spectrometry using a Waters Acquity UPLC and Thermo TSQ Quantum Ultra Triple Quadrupole MS Instrument or just LC/MS/MS. Column: Phase Ace C18 Length (mm) 50 Internal diameter (mm) 3.0 Particle Size (m) 3 and the % active ingredient remaining after rainfall determined by dividing the quantity of cyantraniliprole on each leaf after rainfall by that before rainfall. Cyantraniliprole: 2% cyantraniliprole remained on the leaves. Cyantraniliprole+styrene malemide copolymer: 45% cyantraniliprole remained on the leaves.

EXAMPLE 11

(62) Improved rainfastness of chlorothalonil with styrene maleimide copolymer on soya.

(63) This study demonstrates that the addition of styrene malemide copolymer can reduce the loss of an active ingredient from a leaf surface during rainfall.

(64) A range of substrates can be used in this test with the chosen material in this example being a soya leaf. Herein the soya, Glycine Max (Williams variety), was grown for 4 weeks in 4 inch pots with the top 2 tri-foliates used in the study. The leaves were mounted using double sided tape to flat tiles (30 cm by 30 cm) at an even spacing of 6 leaves per tile.

(65) A deposition solution was then prepared. In this case 3.6 g of a chlorothalonil SC formulation (containing 720 g/l chlorothalonil) was added to 97.3 g water for the control and the effect of the styrene malemide co-polymer determined by creating a similar sample with 0.5% w/w of the water replaced by styrene malemide co-polymer.

(66) Twenty 0.2 l droplets were applied to each substrate using a micro applicator. The substrate was allowed to dry for 2 hours. After the drying period one board containing 6 leaves per treatment were rained on, at 15 mm/hour for one hour while the other board was sampled by washing each leaf with 15 ml of acetonitrile (Sigma Aldrich) and gentle agitation for 20 seconds. The rainfall was simulated using a rain tower which combines the rate of water flow and shutter opening to achieve the target intensity of rainfall. The rain tower was positioned such that the droplets reached their terminal velocity before hitting the target surface. After the raining period, the rained on leaves were washed using the same protocol (gentle agitation in 15 ml acetonitrile for 20 seconds).

(67) The quantities of chlorothalonil in the acetonitrile solutions determined via LCMS (Thermo TSQ Quantum LC/MS/MS, Column 845) and the percent active ingredient remaining after rainfall was determined by dividing the quantity of chlorathalonil on each leaf after rainfall by that before rainfall. Chlorothalonil SC: 19% chlorathalonil remained on the leaves. Chlorothalonil SC+styrene malemide copolymer: 93% chlorathalonil remained on the leaves.