AQUEOUS COMPOSITION OF DITHIOCARBAMATE FUNGICIDE

Abstract

The invention relates to an aqueous composition comprising polyelectrolyte complex, dithiocarbamate fungicide, an aqueous carrier and an agriculturally acceptable additive. The invention further relates to a method for producing the aqueous composition according to the invention and to the use of said composition. The invention additionally relates to a method of protecting a plant, and to a method of preventing, reducing and/or eliminating the presence of a pathogen on a plant, by contacting said plant with a composition of the invention.

Claims

1. An aqueous concentrate composition comprising a polyelectrolyte complex, a dithiocarbamate fungicide, an aqueous carrier, and an agriculturally acceptable additive.

2. The aqueous composition of claim 1, wherein: a) the polyelectrolyte complex is an insoluble solid in the aqueous carrier, b) the concentration of the polyelectrolyte complex in the composition is between 1 and 50 g/kg, c) the polyelectrolyte complex is a complex of at least one polycation and at least one polyanion, d) the concentration of the dithiocarbamate fungicide in the composition is between 350 and 450 g/L, e) the concentration of the dithiocarbamate fungicide in the composition is 30-40% by weight or 28-37% by weight based on the total weight of the composition, and/or f) the agriculturally acceptable additive is a dispersant.

3. (canceled)

4. (canceled)

5. The aqueous composition of claim 1, wherein the polyelectrolyte complex is a complex of at least one polycation and at least one polyanion, and wherein: a) the polycation is selected from the group consisting of cationic starch, poly(allylamine) (PAA), chitosan, epsilon-poly (L-lysine), chitosan derivatives such as thiolated chitosan, 5-methyl-pyrrolidinone-chitosan and chitosan oligosaccharide, DEAE-dextran and any combination thereof, b) the polyanion is selected from the group consisting of alginate, a lignin compound, pectin, carrageenan, humic acid, fulvic acid, sodium alkyl naphtalene sulfonate, poly-γ-glutamic acid, maleic starch half-ester, carboxymethyl cellulose, chondroitin sulphate, dextran sulphate, hyaluronic acid, poly(acrylic acid), polyphosphoric acid, poly(L-lactide) and any combination thereof, c) the concentration of the polycation in the composition is 0.01-10% by weight based on the total weight of the composition, and/or d) the concentration of the polyanion in the composition is 0.01-10% by weight based on the total weight of the composition.

6. The aqueous composition of claim 1, wherein the polyelectrolyte complex is a complex of at least one polycation and at least one polyanion, and wherein: a) the polycation is poly(allylamine) (PAA), chitosan, epsilon-poly (L-lysine) or any combination thereof, and/or b) the polyanion is lignosulfonate.

7. (canceled)

8. (canceled)

9. (canceled)

10. (canceled)

11. (canceled)

12. (canceled)

13. (canceled)

14. (canceled)

15. (canceled)

16. The aqueous composition of claim 1, wherein the composition comprises a dispersant and wherein: a) the dispersant is anionic, b) the dispersant is selected from the group consisting of lignosulfonate, modified acrylic polymer or any combination thereof, and/or c) the concentration of the dispersant in the composition is 1-12% by weight based on the total weight of the composition.

17. (canceled)

18. The aqueous composition of claim 16, wherein the modified acrylic polymer is modified styrene acrylic polymer, polymethyl methacrylate-polyethylene glycol graft copolymer or any combination thereof.

19. (canceled)

20. (canceled)

21. The aqueous composition of claim 1, wherein the composition comprises a wetting agent, an anti-foam agent, an antifreezing agent, a non-ionic hydrocarbon-based surfactant that is not tristyrylphenyl ether phosphate, a preservative, a rheology modifier, and/or an additional bioactive ingredient.

22. The aqueous composition of claim 21, wherein: a) the wetting agent is nonionic and/or a polyalkylene oxide block copolymer, b) the anti-foam forming agent is silicone-based, c) the antifreezing agent is propylene glycol, and/or d) the preservative is a biocide.

23. (canceled)

24. The aqueous composition of claim 21, wherein: a) the concentration of the wetting agent in the composition is 1-10% by weight based on the total weight of the composition, b) the concentration of the anti-foam forming agent is 0.1-1% by weight based on the total weight of the composition, c) the concentration of the antifreezing agent in the composition is 1-10% by weight based on the total weight of the composition, d) the concentration of the non-ionic hydrocarbon-based surfactant in the composition is 0.001-0.1% by weight based on the total weight of the composition, e) the concentration of the preservative in the composition is 0.01-5% by weight based on the total weight of the composition, and/or f) the concentration of the rheology modifier in the composition is 1-10% by weight based on the total weight of the composition.

25. (canceled)

26. The aqueous composition of claim 1, wherein the composition comprises a dispersant and a wetting agent, and wherein: a. the dispersant is anionic and the wetting agent is non-ionic, b) the dispersant is a modified styrene acrylic polymer and the wetting agent is a polyalkylene oxide block copolymer, and/or c. the weight ratio between the dispersant and the wetting agent in the composition is between 2:1 to 1:2.

27-42. (canceled)

43. The aqueous composition of claim 1, wherein the composition comprises: a. 28-37% w/w of mancozeb, b. 0.3-0.1.2% w/w of polycation, c. 2-2.5% w/w of polyanion, d. 4-4.5% w/w of anti-freeze agent, e. 0.2-0.7% w/w of silicone-based anti-foam agent, f. 1.5-3.5% w/w of dispersant, g. 1.5-3.5% w/w of wetting agent, h. 0.05-0.1% w/w of biocide, i. 4.5-5.5% w/w of rheology modifier, and j. 45-55% w/w of water.

44. The aqueous composition of claim 1, wherein: a) the composition is in the form of a suspension concentrate, b) the composition comprises solid particles having d50 of 2 microns or less, c) the composition comprises solid particles having d90 of 10 microns or less, and/or d) the composition has a viscosity of 1000 mPas or less (Brockfield SP63—60 rpm).

45. (canceled)

46. (canceled)

47. (canceled)

48. A process for producing the aqueous composition of claim 1 comprising the following steps: (a) obtaining the polyelectrolyte complex, (b) mixing the polyelectrolyte complex obtained in step (a) with the dithiocarbamate fungicide and the agriculturally acceptable additive.

49. The process of claim 48, wherein: a) the polyelectrolyte complex is obtained by mixing polycation with polyanion in the presence of aqueous carrier, b) the dithiocarbamate fungicide is mancozeb, and/or c) the agriculturally acceptable additive is a dispersant and the dispersant is lignosulfonate, modified acrylic polymer or combination hereof.

50. (canceled)

51. (canceled)

52. (canceled)

53. (canceled)

54. (canceled)

55. The process of claim 48, wherein the composition comprises a stabilizer, anti-foam forming agent, antifreezing agent, surfactant, wetting agent, biocide and/or rheology modifier, and step (b) comprises mixing the stabilizer, anti-foam forming agent, antifreezing agent, surfactant, wetting agent, biocide and/or rheology modifier with the composition obtained in step (a) and (b) and the agriculturally acceptable carrier.

56. (canceled)

57. A delivery system comprising a polyelectrolyte complex, a dithiocarbamate fungicide, an aqueous carrier and an agriculturally acceptable additive.

58. A method of treating a plant, or a part of a plant, against a pathogen, comprising contacting the plant, or part of the plant, with the aqueous composition of claim 1.

59. The method of claim 58, wherein the aqueous composition is applied at an amount of 0.01-2 g/ha of the dithiocarbamate fungicide and/or the dithiocarbamate fungicide is mancozeb.

60. (canceled)

61. The method of claim 58, wherein treating the plant, or a part of the plant, against a pathogen comprises: a) protecting a plant, or a part of a plant, against a pathogen, comprising contacting said plant, or part of said plant, with the aqueous composition of claim 1, b) preventing, reducing and/or eliminating the presence of a pathogen on a plant, or a part of a plant, comprising contacting said plant, or part of said plant, with the aqueous composition of claim 1, or c) controlling diseases caused by phytopathogenic fungi in plants or on propagation material thereof which comprises contacting the plants, or propagation material thereof, with the aqueous composition of claim 1.

62. (canceled)

63. (canceled)

64. (canceled)

65. A method for (i) increasing biological activity of a dithiocarbamate fungicide on a target, (ii) increasing uptake of a dithiocarbamate fungicide into a target, (iii) increasing penetration of a dithiocarbamate fungicide into a target, (iv) increasing retention of a dithiocarbamate fungicide by a target, (v) increasing absorbance of a dithiocarbamate fungicide by a target, and/or (vi) increasing or enhancing bioavailability of a dithiocarbamate fungicide to a target comprising applying the composition of claim 1 to the plant, part of a plant and/or soil.

Description

4. EXPERIMENTAL SECTION

[0433] Several compositions with varying polyelectrolyte complex and mancozeb were tested in the experiments described herein below:

[0434] Polyelectrolyte complex of chitosan, polyallylamine (PAA) or poly-L-lysine (PLL) as polycations, in combination with lignosulfonate as polyanion.

[0435] Materials and Methods

[0436] The compositions are as follows: [0437] DT-CE-M2-300-01T: a composition comprising mancozeb and lignosulfonate-chitosan polyelectrolyte complex [0438] DT-CE-M2-300-02T: a composition comprising mancozeb and lignosulfonate-PAA polyelectrolyte complex

[0439] The following is a lab scale procedure for the preparation of invention composition: [0440] 1) Dissolve Polycation (Chitosan or Poly-allyamine) in water and 1,2 propanediol while stirring in acidic conditions, using, for example 0.4% w/v of acetic acid. [0441] 2) Add polyanion (Borresperse CA) into the polycation solution and mix for an additional 15-30 minutes. [0442] 3) Add the mancozeb portion-wise and mix for an additional 15-30 minutes. [0443] 4) Add antifoaming, Silcolapse 426R. [0444] 5) Add Metasperse 500L and Atlas G5002L and mix for 15-30 minutes. [0445] 6) Milling for 5 min with dispermat. [0446] 7) Add the 2% in water Rhodopol 23 pregel and the biocide (Acticide MBS) to the post milled suspension and mix until a homogeneous formulation is obtained, 30-60 minutes

[0447] Note: [0448] All the addition and mixing time were performed using a mechanical stirrer. [0449] The milling was performed using a Dispermat SL Nano with a 50 mL milling chamber full for ≈80% of ZrO.sub.2 beads 0.75-1.0 mm in size.

[0450] Typical in-process parameters are summarized in Table 1 below.

TABLE-US-00001 TABLE 1 Typical in-process parameters Viscosity Particles size mPas Steps d.sub.50 d.sub.90 (Brookfield SP-63) End of step 2 - PEM suspension 7 67 50 End of step 3 - After addition of AI 1.2 2.5 500 End of step 5 - After addition of 1.6 3.8 50 surfactants End of step 6 - After milling 1.1 2.6 150 End of step 7 - After Xanthan gum 1.1 2.6 300 dispersion

Example 1. Composition of Mancozeb and Lignosulfonate-Chitosan Polyelectrolyte Complex

[0451] A composition of mancozeb and lignosulfonate-chitosan polyelectrolyte complex (DT-CE-M2-300-01T, shown in Table 2) was prepared and its physicochemical properties are summarized in Tables 3.

Preparation Method for DT-CE-M2-300-01T

[0452] 1) Dissolution of chitosan in water and 1,2 propanediol cosolvent while stirring in acidic conditions using, for example, 0.4% w/v of acetic acid. [0453] 2) Add lignosulfonate into the chitosan solution and mix for an additional 15-30 minutes. [0454] 3) Addition of mancozeb portion-wise and mixing for an additional 15-30 minutes period. [0455] 4) Addition of antifoaming, Rhodorsil 426R. [0456] 5) Addition of dispersant Metasperse 500L and Atlas G5002L and mixing for 15-30 minutes. [0457] 6) Milling for 5 min with Dispermat SL Nano milling machine in a 50 ml milling chamber with ZrO2 beads of 0.75-1.0 mm in size. [0458] 7) Addition of 2% in water Rhodopol 23 pregel and the biocide (Acticide MBS) to the post milled suspension and mixing until a homogeneous formulation is obtained, 30-60 minutes.

TABLE-US-00002 TABLE 2 Composition comprising mancozeb and lignosulfonate- chitosan polyelectrolyte complex (DT-CE-M2-300-01T) Ingredients g/L % w/w Distilled Water 642.4 53.2% Mancozeb 91% 360.0 30.1% Chitosan (WSC-2 GTC) 5.6 0.5% CaLS (Borresperse-Ca) 28.0 2.3% Metasphere 500L 24.0 2.1% Atlas G5002L 24.0 2.1% Rhodorsil 426R 5.0 0.5% propan 1,2 diol 50.0 4.1% acticide MBS 1.000 0.084% Rhodopol 23 60.0 5.2% Total 1200.0 100.00%

TABLE-US-00003 TABLE 3 Physicochemical properties of DT-CE-M2-300-01T Viscosity (cP) Particle size (pm) S63 R12 rpm S63 R60 rpm d0.5 d0.9 pH density (g/mL) 915 392 1.7 9.3 6.35 1.214

Example 2. Composition of Mancozeb and Lignosulfonate-PAA Polyelectrolyte Complex

[0459] A composition of mancozeb and lignosulfonate-PAA polyelectrolyte complex (DT-CE-M2-300-02T, shown in Table 4) was prepared and its physicochemical properties are summarized in Table 5.

Preparation Method for DT-CE-M2-300-02T

[0460] 1) Dilution of PAA Hydrochloride in water and 1,2 propanediol cosolvent while stirring. [0461] 2) Add lignosulfonate into the chitosan solution and mix for an additional 15-30 minutes. [0462] 3) Addition of mancozeb portion-wise and mixing for an additional 15-30 minutes period. [0463] 4) Addition of antifoaming, Rhodorsil 426R. [0464] 5) Addition of dispersant Metasperse 500L and Atlas G5002L and mixing for 15-30 minutes. [0465] 6) Milling for 5 min with Dispermat SL Nano milling machine in a 50 ml milling chamber with ZrO2 beads of 0.75-1.0 mm in size. [0466] 7) Addition of 2% in water Rhodopol 23 pregel and the biocide (Acticide MBS) to the post milled suspension and mixing until a homogeneous formulation is obtained, 30-60 minutes.

TABLE-US-00004 TABLE 4 Composition comprising mancozeb and lignosulfonate- PAA polyelectrolyte complex (DT-CE-M2-300-02T) Ingredients g/L % w/w Distilled Water 636.9 53.1% Mancozeb 91% 360.0 29.9% PAA 50% 11.2 1.0% CaLS (Borresperse-Ca) 27.9 2.3% Atlas G5002L 24.0 2.1% metasperse 500L 24.0 2.1% Rhodorsil 426R 5.0 0.5% propan 1,2 diol 50.0 4.1% acticide MBS 1.000 0.081% Rhodopol 23 60.0 5.0% Total 1200.0 100.00%

TABLE-US-00005 TABLE 5 Physicochemical properties of DT-CE-M2-300-02T Viscosity (cP) Particle size (pm) S63 R12 rpm S63 R60 rpm d0.5 d0.9 pH density (DMA) 1070 344 1.7 9.9 6.34 1.216

TABLE-US-00006 TABLE 6 CF1700-21 = DT-CE-M2-300-02T Ingredient g/L % w/w Function Physical state Distilled Water 577.8 48.2% Continues phase Liquid Propan 1,2 diol 50.0 4.2% Antifreeze-cosolvent Low viscosity liquid Poly-allylamine HCl (50% in water) 11.2 0.9% Polycation Medium viscosity liquid Borresperse CA 28.0 2.3% Polyanion Powder Mancozeb 86% (360 g/L PURE) 419.0 34.9% AI Powder Silcolapse 426R 5.0 0.4% Antifoaming Low viscosity liquid Metasperse 500L 24.0 2.0% Dispersing agent Medium viscosity liquid Atlas G5002L 24.0 2.0% Wetting agent High visoctiy liquid Acticide MBS 1.000 0.08% Biocide Liquid Rhodopol 23 (2% gel in water) 60.0 5.0% Rheology modifier Gel Total 1200.0 100.00%

[0467] In compositions formulated with Metasperse 500+Atlas G5002L, there were no phase separation and/or agglomeration after 1 week at room temperature.

Example 3. Composition of Mancozeb and Lignosulfonate-PAA Polyelectrolyte Complex

[0468] The composition described below is made with an increased amount of mancozeb to provide a minimum mancozeb concentration of 350 g/L. The mancozeb loading was adjusted to meet a concentration of 360 g/L using the last available batch that has a purity of 920%.

TABLE-US-00007 TABLE 7 Composition of mancozeb and lignosulfonate- PAA polyelectrolyte complex (CF1700-21-08) Ingredient g/L % w/w Distilled Water 605.8 50.5% Mancozeb 92% 391.0 32.6% PAA 50% 11.2 0.9% CaLS (Borresperse CA) 28.0 2.3% Atlas G5002L 24.0 2.0% Metasperse 500L 24.0 2.0% Silcolapse 426R 5.0 0.4% Propan 1,2 diol 50.0 4.2% Acticide MBS 1.000 0.08% Rhodopol 23 (2% gel in water) 60.0 5.0% Total 1200.0 100.00%

TABLE-US-00008 TABLE 8 Physicochemical properties of CF1700 (CF1700-21-08) pH 6.26 density (g/mL) 1.222 Viscosity (SP63 - 12 rpm - mPas) 1500 Viscosity (SP63 - 60 rpm - mPas) 460 Particle size (d.sub.50 - pm) 1.0 Particle size (d.sub.90 - pm) 1.7

Example 4. Composition of Mancozeb and Lignosulfonate-PAA Polyelectrolyte Complex

[0469] A composition of mancozeb and lignosulfonate-PAA polyelectrolyte complex was prepared.

[0470] The composition of mancozeb and lignosulfonate-PAA complex was produced with 3% instead of 2% of both dispersant and wetting agent, and with 4% instead of 5% of xanthan gum pre-gel to improve the viscosity increase issue observed in the previous prototypes.

[0471] The composition of mancozeb and lignosulfonate-PAA polyelectrolyte complex of the present invention (CF 1705) is provided in Table 9. The physicochemical properties of CF1705 is summarized in Table 10.

TABLE-US-00009 TABLE 9 Composition of mancozeb and lignosulfonate- PAA polyelectrolyte complex (CF1705) Ingredient g/L w/w % Function Distilled Water 566.8 47.2% Continuous phase Mancozeb 86.1% (Batch 418.0 34.8% AI 242288) PAA 50% 11.2 0.9% Polycation CaLS (Borresperse-Ca) 28.0 2.3% Polyanion Atlas G5002L 36.0 3.0% Wetting agent Metasperse 500L 36.0 3.0% Dispersant Silcolapse 426R 5.0 0.4% Antifoaming propan 1,2 diol 50.0 4.2% Antifreeze- cosolvent acticide MBS 1.000 0.08% Biocide Rhodopol 23 (2% gel 48.0 4.0% Rheology modifier in water) Total 1200.0 100.00%

TABLE-US-00010 TABLE 10 Physicochemical properties of CF1705 Batches 26-01 26-02 26-03 pH pure 6.6 6.6 6.6 Density (g/mL) 1.23 1.24 1.24 Viscosity (SP63 - 12 rpm) 610 840 880 Viscosity (SP63 - 60 rpm) 260 350 360 DIN 4 CUP (s) 24 27 29 Particle size d.sub.50 (μm) 1.1 1.1 1.1 Particle size d.sub.90 (μm) 2.9 2.7 2.6

[0472] Comparative Data

[0473] Four composition with other dispersants were tested, and the results are summarized in Tables 11a-d.

TABLE-US-00011 TABLE 11a g/L % w/w Distilled Water 528.6 44.0%  Mancozeb (85% w/w - Mz 450 37.5%  pure 382 g/L - 31.8% w/w) Chitosan 5.6 0.45%  HCl 36% 2.8 0.23%  Borresperse CA 28 2.3% Soprophor FL 30 2.5% Atlox 4913 40 3.3% Rhpdprsil 426R 5 0.4% propan 1,2 diol 50 4.2% Rhodoppl 23 pregel 60 5.0% Total 1200 100% 

TABLE-US-00012 TABLE 11b g/L % w/w Distilled Water 528.6 44.0%  Mancozeb (85% w/w - Mz 450 37.5%  pure 382 g/L - 31.8% w/w) Chitosan 5.6 0.45%  HCl 36% 2.8 0.23%  Borresperse CA 28 2.3% Soprophor FL 30 2.5% Atlas G5002L 40 3.3% Rhpdprsil 426R 5 0.4% prppan 1,2 diol 50 4.2% Rhodoppl 23 pregel 60 5.0% Total 1200 100% 

TABLE-US-00013 TABLE 11c g/L % w/w Distilled Water 520.6 43.4%  Mancozeb (85% w/w - Mz 480 40.0%  pure 408 g/L - 34% w/w) Chitosan 5.6 0.45%  HCl 36% 2.8 0.23%  Borresperse CA 28 2.3% Atlox ™ PN-100 48 4.0% Rhodorsil 426R 5 0.4% propan 1,2 diol 50 4.2% Rhodoppl 23 60 5.0% Total 1200 100% 

TABLE-US-00014 TABLE 11d g/L % w/w Distilled Water 544.6 45.4%  Mancozeb (85% w/w - Mz 480 40.0%  pure 408 g/L - 34% w/w) Chitosan 5.6 0.45%  HCl 36% 2.8 0.23%  Borresperse CA 28 2.3% Atlox ™ PN-100 24 2.0% Rhodorsil 426R 5 0.4% propan 1,2 diol 50 4.2% Rhodoppl 23 60 5.0% Total 1200 100% 

[0474] General Procedure [0475] 1. Dissolve Chitosan in water and 1,2 propanediol while stirring. In acidic conditions using 0.4% w/v of acetic acid [0476] 2. Add Calcium lignosulfonate into the chitosan solution and mix for an additional 15-30 minutes. [0477] 3. Add the Mancozeb portion-wise and mix for an additional 15-30 minutes. [0478] 4. Add antifoaming, Silcolapse 426R. [0479] 5. Add dispersant and wetting agent (in the sequence as written in Table 12) and mix for 15-30 minutes. [0480] 6. Milling for 5 min with dispermat. [0481] 7. Add the 2% in water Rhodopol 23 pre-gel and the biocide (Acticide MBS) to the post milled suspension and mix until a homogeneous formulation is obtained, 30-60 minutes.

[0482] Physicochemical properties such as viscosity, aggregation, and phase separation for the different compositions were measured and summarized in Table 12.

TABLE-US-00015 TABLE 12 Comparative data of compositions with different dispersants Viscosity Aggregation (SP63 - after 1 Phase separation 60 rpm) week at room (More than 10% Surfactants T zero temperature 1 week at RT) Soprophor FL 2.5% + >2000 yes yes Atlox4913 3.3% Soprohor FL 2.5% + >2000 yes yes Atlas G5002L 3.3% Atlox TM PN-100 4.0% 1610 yes yes Atlox TM PN-100 2.0% 1078 yes yes