ENCAPSULATED PYRETHROIDS WITH IMPROVED EFFICTIVENESS IN SOIL AND LEAF APPLICATIONS

Abstract

The present invention relates to aqueous capsule suspensions based on various pyrethroids, to the production thereof and to the use thereof in the form of an agrochemical formulation, especially for soil application.

Claims

1. A capsule suspension concentrate comprising A) a particulate disperse phase comprising 1) a reaction product of at least one compound having isocyanate-reactive groups a1.1) and an isocyanate or isocyanate mixture a1.2) 2) a pyrethroid a2.1) in an organic, water-insoluble solvent a2.2), 3) one or more additives a3.1) and B) a liquid aqueous phase comprising at least one protective colloid b1.1) and optionally one or more further additives b1.2), wherein the particles of the disperse phase A) optionally have a median particle size of between 1 and 50 μm, and wherein the proportion of a1.2) is between 0.1% and 2% by weight, the proportion of a2.1) is between 1% and 50% by weight, the proportion of organic solvent a2.2) is between 1% and 90% by weight, the proportion of additive a3.1) is between 0.5% and 5% by weight, the proportion of protective colloid b1.1) is between 0.1% and 5% by weight, and the proportion of additive b1.2) is between 0.1% and 15% by weight.

2. The capsule suspension concentrate according to claim 1, wherein the pyrethroid is selected from the group consisting of deltamethrin, beta-cyfluthrin, cypermethrin and lambda-cyhalothrin.

3. The capsule suspension concentrate according to claim 1, wherein component a3.1) comprises at least one compound selected from the group comprising alkyl ethoxylates, alkyl propoxy ethoxylates, fatty acid esters of sorbitan and glycerol, and organomodified trisiloxanes.

4. The capsule suspension concentrate according to claim 1, wherein component a1.1) is water.

5. The capsule suspension concentrate according to claim 1, wherein particles of the disperse phase A) have a median particle size of between 2 and 15 μm.

6. The capsule suspension concentrate according to claim 1, wherein the proportion of a1.2) is between 0.5% and 2.0% by weight, the proportion of a2.1) is between 5% and 15% by weight, the proportion of organic solvent a.2.2) is between 25% and 40% by weight, the proportion of additive a3.1) is between 2% and 5% by weight, the proportion of protective colloid b1.1) is between 0.2% and 1% by weight and the proportion of additive b1.2) is between 0.3% and 3% by weight.

7. The capsule suspension concentrate according to claim 1, wherein the ratio of a2.1) to the isocyanate or isocyanate mixture is between 2:1 and 10:1.

8. The capsule suspension concentrate according to claim 1, wherein the ratio of a1.2) to optionally phase A) is 40:1 to 60:1, optionally 45:1 to 60:1, optionally 45:1-55:1.

9. The capsule suspension concentrate according to claim 1, wherein the organic solvent (a2.2) is selected from the group comprising dialkyl naphthalenes and also a mixture of 1-methyl- and 2-methylnaphthalene and naphthalene.

10. The capsule suspension concentrate according to claim 1, wherein the proportion of phase A) based on the overall formulation is between 30% and 70% by weight.

11. The capsule suspension concentrate according to claim 1, wherein the proportion of a2.1) based on the overall formulation is between 5% and 15% by weight.

12. A process for preparing the capsule suspension concentrate according to claim 1, comprising: 1. producing the phase A) 2. producing the aqueous phase B) 3. producing an emulsion of A) in B) 4. optionally adding component a1.1) (when a1.1. is not water) 5. heating 6. finalizing.

13. A product comprisinq the capsule suspension concentrate according to claim 1 for foliar application.

14. A product comprisinq the capsule suspension concentrate according to claim 1 for soil application.

15. The product according to claim 14, wherein release takes place over a relatively long period of time.

16. The capsule suspension concentrate according to claim 1 for soil application of pyrethroid, optionally of deltamethrin.

Description

DESCRIPTION OF THE METHOD

[0143] Activity tests were carried out in long plastic containers filled with 5.9 kg of pH 7.1 sandy loam soil containing 1.8% humus. A furrow 5 cm deep was formed and four maize seeds (Ronaldino variety) were placed therein 7 cm apart. The test formulations were diluted in 4 ml of tap water and mixed homogeneously with 700 g of sandy loam soil. The treated soil was used to fill the open furrow and to cover the seeds, which resulted in a total soil weight of 6.6 kg per container. Infestation with 450 Diabrotica balteata eggs per container was carried out by pipette one day after sowing. The soil moisture content was adjusted to 50% of the specific field capacity and increased to 80% once the first hatched Diabrotica balteata larvae had appeared. The growth conditions were at a constant temperature of 25° C., 60-70% relative humidity and 14 h illumination with sodium vapour lamps. The test setup comprised three replicates per treatment. The tests were assessed 21 days after infestation by counting the number of damaged plants and measuring the fresh shoot weights per container.

[0144] Because the absolute numbers can vary greatly from one test series to the next, the tables in all cases show only results that were also carried out in a parallel test. Where appropriate, as two or more tables with the respective reference results are indicated.

[0145] Comparison of different formulation types:

TABLE-US-00003 # 1 N1 N2 N3 N4 Name K-Othrine Decis Forte GR0.4 GR0.4 SC025 EC100 (commercial (commercial product) product) Deltamethrin 0.4 0.4 Propylene glycol 0.27 Biodac 30/60 99.2 96 Citric acid 0.003 Lucramul PS 29 0.13 Lucramul Hot 5902 0.12 Ruetasolv Di 3.48 Antifoam 0.003

TABLE-US-00004 # Healthy plants/% 1 83.3 N1 25.0 N2 44.4 N3 0.0 N4 0.0 UTC not infested 100 UTC infested 0.0

[0146] Formulation #1 according to the invention shows markedly better activity than all comparative examples.

[0147] 3. Comparison of Different CS Recipes

[0148] (Unless otherwise stated, the following test conditions applied: DLT application conditions always 60 g/ha, observation period 21 days after infestation) [0149] a. Concentration of AI

TABLE-US-00005 # Healthy plants/% Shoot weight/g 2 100 89.7 3 100 91 4 100 84.7 UTC not infested 100 79.7 UTC infested 0 29.3 [0150] The AI concentration in the formulation can be varied at the same active ingredient application rate with equally good activity. [0151] b. Different Active Ingredients [0152] Comparison of the formulation according to the invention vs. commercial products (capsule suspension or granules) of lambda-cyhalothrin, beta-cyfluthrin, cypermethrin

TABLE-US-00006 Shoot weight/g # 5 g ai/ha 10 g ai/ha 30 g ai/ha 60 g ai/ha 5 10.2 13.6 15.0 12.7 Lambda-cyhalothrin CS100 7.0 4.4 6.5 9.6 (Karate Zeon) Lambda-cyhalothrin GR0.4 8.2 10.0 11.7 14.9 6 9.7 14.2 14.2 Beta-cyfluthrin GR0.4 7.2 7.5 11.3 7 7.9 14.7 15.4 Cypermethrin MG0.8 (Belem) 6.3 7.0 6.8 UTC not infested 9.9 UTC infested 1.7 [0153] All formulations according to the invention show at least comparable, mostly markedly better, effectiveness at the same AI application rate as the commercial products of the same active ingredient. [0154] c. Composition of Capsule Shell [0155] Formulations according to the invention having varying capsule thicknesses, isocyanate types, crosslinking and protective colloids are tested hereinbelow.

TABLE-US-00007 # Healthy plants/% Shoot weight/g 8 33.3 38.8 UTC not infested 100 36.4 UTC infested 0 13.6

TABLE-US-00008 # Healthy plants/% Shoot weight/g  3 66.7 41.2  9 16.7 42.2 10 1.0 28.0 11 1.0 14.86 12 0.0 31.6 13 25.0 39.2 UTC not infested 100 34 UTC infested 0 21.6

TABLE-US-00009 # Healthy plants/% Shoot weight/g  9 83.3 72.8  3 83.3 71.8 14 66.7 67.0 UTC not infested 100 72.2 UTC infested 8 26.2

TABLE-US-00010 # Healthy plants/% Shoot weight/g  3 100 26.4 15 100 37 16 100 39.3 UTC not infested 100 27.4 UTC infested 8 15.7 [0156] All formulations according to the invention show activity. The activity after 21 days is strongly dependent on the nature of the capsule shell. The required release profile can accordingly be adjusted through appropriate selection of the shell composition or by mixing different formulations. [0157] d. Type and amount of adjuvant

TABLE-US-00011 # Healthy plants/% Shoot weight/g 17 66.7 63.3 18 91.7 81.7  1 100 91.0 19 100 88.7 UTC not infested 100 79.7 UTC infested 0 29.3

TABLE-US-00012 # Healthy plants/% Shoot weight/g 20 100 28.7 21 100 36.3 22 100 38.0 23 100 36.7 10 + BT V tankmix 16.7 21.3 UTC not infested 100 40.7 UTC infested 8.3 17.0

TABLE-US-00013 # Healthy plants/% Shoot weight/g 20 100 30.6 24 100 41.1 25 25 36.7 26 100 45.2 UTC not infested 100 27.4 UTC infested 8 15.7 [0158] It was surprisingly found that the adjuvant needs to be present for optimal activity in the capsule, while tankmix additives do not show adequate activity. Moreover, adjuvants having terminal hydroxyl functionality show even better activity than those with methoxy functionality. [0159] Optical assessment of the capsule suspensions under the microscope after drying of the formulation:

TABLE-US-00014 0% BreakThru 0.5% 1% 2% 3% Protective colloid Vibrant BT V BT V BT V BT V Kuraray Poval 26-88 #27: − #28: − #29: o #30: + Borresperse NA #31: − #18 − #20: o  #3: + Assessment scheme: − = poor, o = borderline, + = good [0160] e. Influence of soil conditions [0161] 1. Standard soil, 2. Standard soil+20% peat;

TABLE-US-00015 Healthy plants/% Shoot weight/g # 1. Standard soil 2. +20% peat 1. Standard soil 2. +20% peat 3 100 91.7 36.3 30.7 8 100 100 35.3 39.0 UTC not 100 100 40.7 42.7 infested UTC 8.3 16.7 17.0 17.7 infested [0162] It was surprisingly found that the activity is independent of the soil composition. [0163] Soil Moisture Content [0164] Application scenarios: [0165] A) Formulation according to the invention is introduced into uppermost soil layer (approx. 40-50% water-retention capacity)=standard [0166] B) Formulation according to the invention is introduced into uppermost soil layer (approx. 40-50% water-retention capacity) and stored for 7 days under damp conditions. [0167] C) Formulation according to the invention is introduced into uppermost soil layer (approx. 40-50% water-retention capacity) and the treated soil was dried for 7 days (<20% water-absorption capacity). [0168] D) Soil was dried for 7 days (<20% water-absorption capacity), the formulation according to the invention applied into the dried soil and then renewed watering carried out after sowing.

TABLE-US-00016 Healthy plants/% Shoot weight/g # A) B) C) D) A) B) C) D) 3 91.7 100 100 83.3 24.0 25.3 21.3 20.0 8 100 100 100 100 21.3 21.7 22.3 19.0 UTC not 19.0 infested UTC infested 0 5.7 [0169] It was surprisingly found that the activity is independent of the soil moisture conditions. [0170] f. Comparison with Commercial Product

TABLE-US-00017 # Healthy plants/% Shoot weight/g 9 83.3 72.8 DelCaps CS050 4.2 32.5 UTC not infested 100 72.2 UTC infested 8 26.2 [0171] With soil application, the commercial product shows markedly poorer activity than the formulation according to the invention. [0172] g. Influence of Particle Size in Different Batches of the Same Recipe

TABLE-US-00018 # Healthy plants/% Shoot weight/g 3a 100 61.2 3b 100 67.1 8a 100 63.7 8b 100 67.6 UTC not infested 100 69.7 UTC infested 0 34.1 [0173] Relatively small variations in particle size have no influence on the activity.

[0174] 4. Outdoor Trials [0175] The formulations according to the invention were tested in outdoor trials versus Belem GR (active ingredient: cypermethrin) as standard against wireworm in maize. The capsule formulations were sprayed (in furrow spray application) at an application rate of 60 g a.i./ha. (comparison Belem MG 0.8 is applied at 96 g a.i./ha) into the seed furrow. [0176] The reported activity is the mean of 4 individual results.

TABLE-US-00019 # Activity/% Untreated 46.9  8 73.8  3 75.7  9 70.7 10 62.0 11 45.9 8 + 11 65.0 Belem 61.3 MG 0.8 [0177] The formulations according to the invention show better activity compared with the standard. In addition, the release rate can be adjusted by mixing two formulations having different release (#8+#11). This results in an average activity.

[0178] 5. Foliar Application [0179] The formulations according to the invention were tested pre-infested in the greenhouse on [0180] Myzus persicae (MYZUPE) on cabbage (Melissa) and bell peppers (Feher); [0181] Aphis gossypii (APHIGO) on cotton (Viky); [0182] with mixed populations. [0183] The application concentration was 400 1/ha with a track sprayer. Three replicates were in each case carried out. The tests with MYZUPE were carried out at 20° C. and with APHIGO at 23° C. [0184] Evaluation was after 1, 4 and 7 days (1, 4, 7 d) after application. [0185] Application rate: track sprayer with 400 1/ha, contact, in each case three replicates

TABLE-US-00020 Application % mortality of Myzus persicae % mortality of Myzus persicae % mortality of Aphis gosypii on concentration on bell pepper on cabbage cotton g a.i./ha 1 d 4 d 7 d 1 d 4 d 7 d 1 d 4 d 7 d N1 4.8 23 27 37 37 40 37 23 50 40 0.96 10 10 3 10 10 0 7 7 3 0.19 0 0 0 0 0 0 0 0 0 0.038 0 0 0 0 0 0 0 0 0 32 4.8 87 99 100 77 97 97 70 89 89 0.96 60 73 83 63 67 40 47 83 83 0.19 20 20 23 20 13 3 13 23 10 0.038 0 0 0 0 0 0 3 3 0 [0186] The formulation according to the invention shows better activity than SC025 (N1)

[0187] Materials Used

[0188] Deltamethrin is an active substance from Bayer AG, Leverkusen.

[0189] Beta-cyfluthrin is an active substance from Bayer AG, Leverkusen.

[0190] Cypermethrin was obtained from Agros Organics BVBA, Geel, Belgium.

[0191] Break-Thru® Vibrant is a nonionic organic surfactant from Evonik Industries AG, Essen.

[0192] Breakthru® S240 is a polyether-modified trisiloxane from Evonik Industries AG, Essen.

[0193] Synergen W 06 is a fatty alcohol alkoxylate from Clariant Produkte (Deutschland) GmbH, Frankfurt.

[0194] Genapol EP 2584 is a fatty alcohol alkoxylate from Clariant Produkte (Deutschland) GmbH, Frankfurt.

[0195] Genapol X-060 is a fatty alcohol polyglycol ether from Clariant Produkte (Deutschland) GmbH, Frankfurt.

[0196] Genapol XM 060 is a fatty alcohol polyglycol ether having terminal methyl group based on Genapol X-060 from Clariant Produkte (Deutschland) GmbH, Frankfurt.

[0197] Desmodur® 44V 20 L is a mixture of polymeric isocyanates based on diphenylmethane 4,4′-diisocyanate from Covestro AG, Leverkusen.

[0198] Desmodur® T80 is a TDI (toluene diisocyanate) mixture from Covestro AG, Leverkusen.

[0199] Silcolapse® 426 R is a defoamer from Elkem Silicones Germany GmbH, Libeck.

[0200] Silfoam® SRE is a defoamer from Wacker Chemie AG, Munich.

[0201] Kuraray Poval® 26-88 is a partially saponified polyvinyl alcohol from Kuraray Europe GmbH, Hattersheim.

[0202] Borresperse® NA is a lignosulfonate from Borregaard, Sarpsborg, Norway.

[0203] Standard Chemicals:

[0204] Xanthan gum is a thickener for aqueous systems (various suppliers).

[0205] The biocides which can be used are all commercial available and licensed biocides, examples include Proxel® GXL from Lonza and Kathon™ CG/ICP from Dupont.

[0206] Solvesso 200 ND is an aromatic hydrocarbon (various suppliers).

[0207] Diethylenetriamine and ammonia are standard chemicals and may be obtained from various suppliers.

[0208] Comparison Products:

[0209] DelCaps 050 CS is a product containing encapsulated deltamethrin from INNVIGO, Warsaw, Poland.

[0210] BELEM® 0.8 MG is a commercial product containing cypermethrin as active ingredient.