RU2738360C2 - Synergetic fungicidal mixture - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: synergetic fungicidal mixture contains a combination of metalaxyl-M, cymoxanil and azoxystrobin in weight ratio of 1:1:0.5 to 1:3:30, respectively, and an auxiliary substance, selected from a group consisting of a dispersing component, a foaming inhibitor, a moistening reagent, a disintegrant, an anticaking agent, a carrier and a binding substance.

EFFECT: invention increases efficiency of controlling phytopathogenic fungi.

10 cl, 7 tbl, 4 ex

Description

FIELD OF TECHNOLOGY

This invention relates to a synergistic fungicidal mixture.

GENERAL INFORMATION

Plants, fruits and vegetables are susceptible to fungal attack. In agriculture and horticulture, fungicides are most commonly used to protect against fungi. The most common and widely used method of protecting against fungi is the use of synthetic fungicides. Many types of synthetic fungicides are known, and a significant variety of synthetic fungicide-based formulations are available from different manufacturers to protect against fungi. As fungicides, various compounds such as azoxystrobin, anilazine, cymoxanil and the like are commonly used.

It is always recommended to minimize the use of fungicides to reduce risks to people and the environment. Accordingly, there is a continuing need to improve the fungicidal properties of fungicides without increasing their toxicity to humans and the environment, so that the desired bioeffectiveness is achieved at low doses of application.

Therefore, the present invention provides a synergistic fungicidal mixture that has increased efficacy.

SUMMARY OF THE INVENTION

Some objects of the present invention, which is represented herein by at least one of the embodiments, are indicated below.

An object of the present invention is to obviate one or more of the problems of the art, or at least provide useful analogs.

It is an object of the present invention to provide a synergistic fungicidal mixture.

The object of the present invention is to provide a synergistic fungicidal mixture with increased fungicidal activity.

Other objects and advantages of the present invention will be more apparent from the following description, but are not intended to limit the scope of the present invention.

Summary

This invention relates to a synergistic fungicidal mixture that contains active ingredients, including a combination of metalaxyl-M, cymoxanil and azoxystrobin in a weight ratio of 1: 1: 0.5 to 1: 3: 30, respectively, and at least one excipient, selected from the group consisting of a dispersing component, a foam inhibitor, a wetting agent, a disintegrant, an anti-caking agent, a carrier and a binder.

This invention also relates to a method for preparing a synergistic fungicidal mixture, which includes the step of mixing a predetermined amount of anticaking agent, carrier and commercial metalaxyl-M to obtain a substantially homogenized mixture A; mixing a predetermined amount of industrial azoxystrobin, industrial cymoxanil, a wetting agent and a dispersing additive to obtain a substantially homogenized mixture B; mixing substantially homogenized mixtures A and B to obtain a substantially homogenized mixture C, followed by grinding to a state of substantially homogenized powder with a particle size of 3 μm to 10 μm. You can mix a predetermined amount of substantially homogenized powder, water and foam inhibitor before kneading to a paste; then the pasty mass is formed to obtain wet compressed granules. The wet compressed granules are then dried under controlled conditions and sieved to obtain dried compressed granules with sizes ranging from 0.5 mm to 2 mm.

Detailed description

It has been noted that azoxystrobin, cymoxanil and metalaxyl-M exhibit good fungicidal activity. However, they are prone to resistance through a single mechanism of action.

The present invention therefore provides a synergistic fungicidal mixture that has increased fungicidal activity and is prone to fungal resistance.

That a synergistic fungicidal mixture containing a specific combination of metalaxyl-M, cymoxanil and azoxystrobin as an active ingredient has synergistic fungicidal activity is an accidental finding. A synergistic fungicide requires the right combination to prevent the development of fungal resistance. The fungicidal mixture of the present invention successfully achieves increased fungicidal activity and prevents the development of resistance in fungi. The fungicidal mixture of the present invention exhibits surprising fungicidal activity that exceeds the sum of the activities of the individual components when used alone.

On the one hand, this invention provides a synergistic fungicidal mixture that contains an active ingredient in which a combination of metalaxyl-M, cymoxanil and azoxystrobin in a weight ratio of 1: 1: 0.5 to 1: 3: 30, and at least one auxiliary a substance selected from the group consisting of a dispersing agent, a foam inhibitor, a wetting agent, disintegrants, an anti-caking agent, a carrier and a binder.

The dispersing component is used to uniformly disperse the ingredients of the fungicidal mixture, primarily the active ingredient, throughout the product, in accordance with the release form. In one embodiment, the dispersant component can be at least one selected from the group consisting of sodium lignosulfonate, calcium lignosulfonate, sodium alkyl naphthalene sulfonate, sulfonated aromatic polymeric sodium salt, polycarboxylic acid homopolymer, sodium salt polycarboxylic acid homopolymer, copolymer polycarboxylic acid - copolymers of ethylene oxide / propylene oxide (EO / PO) and the sodium salt of a copolymer of polycarboxylic acid. Typically, the alkyl group may be a C1-C20 alkyl group, and the aromatic group in the sulfonated aromatic polymer is a C1-C20 aromatic group.

A foam inhibitor can be used to prevent the formulation from foaming. In one embodiment, the foam inhibitor can be at least one selected from the group consisting of polydimethylsiloxane powder and polydimethylsiloxane fluid.

The dispersing component is used to wet the ingredients of the composition with water, reducing their surface resistance. In one embodiment, the dispersant component used in the mixture of this invention may be at least one selected from the group consisting of a nonionic surfactant, anionic surfactant, or combinations thereof. Non-limiting examples of a nonionic surfactant include alcohol alkoxylates containing 9 to 15 moles of ethylene oxide. Non-limiting examples of anionic surfactants are alkyl naphthalene sulfonate, dialkyl naphthalene sulfonate, alkyl naphthalene sulfonate condensate, sodium lauryl sulfate, and sodium dodecyl benzenesulfonate. Of the other wetting reagents that may be used, at least one should be selected from the group consisting of alkyl propylene oxide condensates, aryl ethylene oxide condensates, alkyl propylene oxide condensates, aryl propylene oxide condensates, alkyl ethoxylates, and arylethoxylates. Typically, the alkyl group and the aryl group in wetting reagents are a C1-C20 alkyl group.

Disintegrants are compounds that help a substance disintegrate faster in water. In one embodiment, the disintegrant used in the mixture of this invention may be at least one selected from the group consisting of sodium chloride, sodium sulfate, ammonium sulfate, sodium carbonate, sodium bicarbonate, starch and starch derivatives, sodium tripolyphosphate, cross-linked sodium carboxymethylcellulose, cross-linked polyvinylpyrrolidone.

An anti-caking agent is used to prevent the formation of a crust on the fungicide mixture during storage. In one embodiment, the anti-caking agent can be at least one selected from the group consisting of clay, precipitated silica, or metal stearates. In another embodiment, the metal stearate may be selected from the group of materials consisting of zinc stearate, calcium stearate, magnesium stearate, or aluminum stearate.

A carrier is included as a diluent or filler in the formulation. The carrier can be selected from the group consisting of clay, minerals or talc.

A binder is used to bond the ingredients in a mixture to give it the desired strength. In one embodiment, the binder can be at least one of the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamides, dextrose, sucrose, or lactose.

The fungicidal mixture of this invention may be in a form selected from the group consisting of water-dispersible granules, wettable powder, and suspension concentrate.

On the other hand, the present invention provides a method for preparing a fungicidal composition. The method is detailed below.

Specified amounts of anti-caking agent, carrier, and commercial metalaxyl-M are mixed in a mixer to obtain a substantially homogenized mixture A. In one embodiment, metalaxyl-M can be heated to a temperature in the range of 35 ° C to 80 ° C and sprayed onto the anti-caking agent and carrier. followed by stirring until a substantially homogenized mixture A.

Specified amounts of industrial azoxystrobin, industrial cymoxanil, wetting agent, dispersing agent, disintegrant and binder are mixed in a mixer to obtain a substantially homogenized mixture B.

Substantially homogenized blend A and substantially homogenized blend B are blended together in a mixer until substantially homogenized blend C is obtained. Substantially homogenized blend C is then ground to fine particles to form a substantially homogenized powder. In a specific embodiment, the fine particles of the substantially homogenized powder may be from 3 microns to 10 microns in size. In one embodiment, the substantially homogenized mixture B is milled with an air jet mill.

A predetermined amount of substantially homogenized powder, water and foam inhibitor is added to the pasty mass preparation unit and kneaded until a pasty mass is obtained. Then the pasty mass passes through a granulator to obtain wet compressed granules. The wet compressed granules are dried under controlled conditions to obtain dried compressed granules.

In one embodiment, the dried compressed granules can then be sieved to obtain dried compressed granules with a size of 0.5 mm to 2 mm.

In an alternative technique of this invention, industrial azoxystrobin and industrial cymoxanil can first be ground / triturated with a jet mill to a powder, after which the powder is mixed with commercial metalaxyl-M and water, a dispersing agent, a wetting agent, binders, foam inhibitors and carriers to obtain a suspension in which the total solids content is from 40% to 65%. The suspension thus obtained can be subjected to drying in a spray dryer or in a fluidized bed dryer to obtain dried granules. The dried granules are sieved through a sieve to obtain granules ranging in size from 100 microns to 850 microns.

In another alternative method of this invention, commercial azoxystrobin and commercial cymoxanil are mixed with water and a dispersant in a mixer to produce a substantially homogenized mixture D. The substantially homogenized mixture D is ground to fine particles. In an example for one embodiment, grinding occurs using a wet mill. In a specific embodiment, the fine particles of the substantially homogenized mixture D may be from 2 microns to 5 microns in size. The mixture D with fine particles can then be mixed with industrial metalaxyl-M, to which were added water, a dispersing component, a binder, an anticaking agent, a disintegrant, a foam inhibitor and a carrier to obtain a suspension in which the total solids content is from 40% to 65%. The slurry is then dried in a spray dryer or fluid bed dryer to obtain dried granules. The dried granules are sieved through a sieve to obtain granules ranging in size from 100 microns to 850 microns.

In another alternative method of this invention, industrial azoxystrobin, industrial cymoxanil, and industrial metalaxyl-M are mixed with an anticaking agent and a carrier to obtain a substantially homogenized mixture E. The substantially homogenized mixture E is ground in an air-jet mill to obtain a premixed powder with particles ranging in size from 3 μm to 10 μm ... In another container, a predetermined amount of water, a dispersing component, a binder, a wetting agent, a disintegrant and a foam inhibitor are combined to obtain a mixture E. A substantially homogenized mixture E is sprayed onto a substantially homogenized mixture D in a fluidized bed technological unit at a controlled temperature in the range from 30 ° C to 50 ° C to obtain a substantially homogenized mixture of G. The substantially homogenized mixture of G. is then dried at a controlled temperature to obtain dried granules ranging in size from 100 μm to 1000 μm.

Other possible methods are also contemplated by the present invention.

Thus, the present invention provides a stable and ready-to-use synergistic fungicidal mixture containing metalaxyl-M, cymoxanil and azoxystrobin, and a method for its preparation.

The present invention is further described in light of the following experiments, which are provided for illustration only and should not be construed to limit the scope of the present invention. The following experiments can be scaled up to an industrial scale, and the results obtained can be extrapolated to a production scale.

EXPERIMENTAL DATA

A: Synergistic fungicide mixture and its manufacturing process

EXAMPLE 1

35 grams of silicon and 153 grams of kaolin clay were placed in a Z-mixer, where they were mixed for 10 minutes. 110 grams of commercial metalaxyl-M was heated to a temperature in the range of 35 ° C to 80 ° C to obtain molten industrial metalaxyl-M, which was added to the mixer, after which the resulting mixture was mixed for 2 hours to obtain Mix A.

215 g of industrial azoxystrobin, 211 g of industrial cymoxanil, 40 g of sodium alkyl naphthalenesulfonate, 100 g of polycarboxylate, 19 g of sodium lignosulfonate, 5 g of lactose, 110 g of sodium sulfate were placed in a ribbon mixer, where they were mixed for 2 hours to obtain Mix B.

Mix A was added to Mix B in a ribbon blender, after which mixing was continued for an additional 2 hours to obtain Mix C.

Mixture B was placed in a jet mill to obtain a wettable powder with a particle size of 3 to 10 microns.

The wettable powder was placed in a pasty mass preparation unit, to which 2 g of silicon and 40 g of water were also added to obtain a pasty mass.

The pasty mass was compressed using a drum granulator to obtain granules ranging in size from 0.8 mm to 1.2 mm, which were then dried in a fluidized bed dryer at 40 ° C to obtain the final product composition.

EXAMPLE 2

80 grams of silicon and 153 grams of kaolin clay were placed in a Z-mixer, where they were mixed for 10 minutes. The mixer was also filled with 110 grams of molten industrial metalaxyl-M and then the resulting mixture was mixed for 2 hours to obtain Mix A.

215 g of industrial azoxystrobin, 225 g of industrial cymoxanil, 40 g of sodium alkyl naphthalene sulfonate, 60 g of sodium alkyl naphthalene sulfonate, 40 g of sodium lignosulfonate, 75 g of sodium carbonate were placed in a ribbon mixer, where they were mixed for 2 hours to obtain Mix B.

Mix A was added to Mix B in a ribbon blender, after which mixing was continued for an additional 2 hours to obtain Mix C.

Mixture B was placed in a jet mill to obtain a wettable powder with a particle size of 3 to 10 microns.

The wettable powder was placed in a pasty mass preparation unit, to which 2 g of silicon and 40 g of water were also added to obtain a pasty mass.

The resulting pasty mass was compressed using a drum granulator to obtain granules ranging in size from 0.8 mm to 1.2 mm, which were then dried in a fluidized bed dryer at 40 ° C to obtain the final product composition.

Example 3

80 grams of silicon and 153 grams of kaolin clay were placed in a Z-mixer, where they were mixed for 10 minutes. 110 grams of commercial metalaxyl-M heated to a temperature in the range of 35 ° C to 80 ° C was added to the mixer, after which the resulting mixture was mixed for 2 hours to obtain Mix A.

232 g of industrial azoxystrobin, 211 g of industrial cymoxanil, 40 g of sodium alkyl naphthalenesulfonate, 100 g of polycarboxylate, 24 g of sodium lignosulfonate, 48 g of sodium sulfate were placed in a ribbon mixer, where they were mixed for 2 hours to obtain Mix B.

Mix A was added to Mix B in a ribbon blender, after which mixing was continued for an additional 2 hours to obtain Mix C.

Mixture B was placed in a jet mill to obtain a wettable powder with a particle size of 3 to 10 microns.

The wettable powder was placed in a paste preparation unit, to which 2 g of silicon (as an antifoam agent) and 40 g of water were also added to obtain a paste. The pasty mass was compressed using a drum granulator to obtain granules ranging in size from 0.8 mm to 1.2 mm, which were then dried in a fluidized bed dryer at 40 ° C to obtain the final product composition.

EXAMPLE 4

40 g of silicon and 153 g of kaolin clay were placed in a Z-blender, where they were mixed for 10 minutes. 100 g of molten metalaxyl-M heated to a temperature in the range of 35 ° C to 80 ° C was added to the mixer, after which the resulting mixture was mixed for 2 hours to obtain Mix A.

232 g of industrial azoxystrobin, 211 g of industrial cymoxanil, 25 g of sodium alkyl naphthalenesulfonate, 50 g of polycarboxylate, 21 g of sodium lignosulfonate, 166 g of sodium sulfate were placed in a ribbon mixer, where they were mixed for 2 hours to obtain Mixture B.

Mix A was added to Mix B in a ribbon blender and then they were mixed for 2 hours to obtain Mix B. Mix C was placed in a jet mill to obtain a wettable powder with a particle size of 3 to 10 microns.

The wettable powder was placed in a paste preparation unit, to which 2 g of silicon (as an antifoam agent) and 40 g of water were also added to obtain a paste. The pasty mass was compressed using a drum granulator to obtain granules ranging in size from 0.8 mm to 1.2 mm, which were then dried in a fluidized bed dryer at 40 ° C to obtain the final product composition.

EXAMPLE 5

40 grams of silicon and 250 grams of kaolin clay were placed in a Z-blender and mixed for 10 minutes. 13 grams of commercial metalaxyl-M was heated to a temperature in the range of 35 ° C to 80 ° C to obtain molten industrial metalaxyl-M, which was added to the mixer, after which the resulting mixture was mixed for 2 hours to obtain Mix A.

321 g of industrial azoxystrobin, 33 g of industrial cymoxanil, 25 g of sodium alkyl naphthalenesulfonate, 50 g of polycarboxylate, 21 g of sodium lignosulfonate, 10 g of lactose, 235 g of sodium sulfate were placed in a ribbon mixer, where they were mixed for 2 hours to obtain Mix B.

Mix A was added to Mix B in a ribbon blender, after which mixing was continued for an additional 2 hours to obtain Mix C.

Mixture B was placed in a jet mill to obtain a wettable powder with a particle size of 3 to 10 microns.

The wettable powder was placed in a pasty mass preparation unit, to which 2 g of silicon and 40 g of water were also added to obtain a pasty mass.

The pasty mass was compressed using a drum granulator to obtain granules ranging in size from 0.8 mm to 1.2 mm, which were then dried in a fluidized bed dryer at 40 ° C to obtain the final product composition.

Table 1 shows the storage stability of the synergistic fungicidal mixture.

Table 1

No. Content of active ingredients Surfactants
(weight ratio,%) Suspension
(weight ratio,%) Suspension-IUS
(weight ratio,%) IUS-MSA one Azoxystrobin 20 Cymoxanil 20 Metalaxyl-M 10 Surfactant (4)
Polycarboxylate (10)
Lignosulfonate (1.9) 86 85 0.3 2 Azoxystrobin 20
Cymoxanil 22
metalaxyl-M 10
Surfactant (4)
Surfactant condensate (6)
Lignosulfonate (4) 72 60 0.6 3 Azoxystrobin 22
Cymoxanil 20
metalaxyl-M 10 Surfactant (4)
Polycarboxylate (10)
Lignosulfonate (2,4) 66 60 0.8 4 Azoxystrobin 22
Cymoxanil 22
metalaxyl-M 9 Surfactant (2.5)
Polycarboxylate (5)
Lignosulfonate (2.1) 65 60 0.8 5 Azoxystrobin 30
Cymoxanil 3
metalaxyl-M 1 Surfactant (2.5)
Polycarboxylate (5)
Lignosulfonate (2.1) 74 70 0.3

IUS - accelerated aging research

ISA - Wet Sieve Analysis

From the data shown in Table 1, it follows that Examples 1-5 are stable and the value of the suspension parameter does not show a significant decrease even after the analysis of accelerated aging.

B: Study of bioeffectiveness, study of phytotoxicity of synergistic fungicidal sweep

Bioeffectiveness:

The synergistic fungicidal mixture made in accordance with examples 1-5 of the present invention was tested with predetermined concentration values and possible two-way combination methods for preparing a tank mixture, for example, Cymoxanil 50% SP + Azoxystrobin 25% KS (tank mixture), Metalaxil-M 25 % SP + Azoxystrobin 25% KS (tank mix) and Cymoxanil 50% SP + Metalaxil-M 25% SP (tank mix) together with separate fungicides, for example Azoxystrobin 25% KS, Cymoxanil 50% SP and Metalaxil-M 25% SP as well as unprocessed potatoes. Control was carried out for cases of early and late infection. The fungicides were sprayed onto the leaves with a knapsack sprayer with a solid cone spray tip. The application was carried out at the moment the disease began to spread to the field. Spraying was carried out at intervals of 10 days.

The onset of visible disease symptoms was recorded before the first spray, and follow-up observations were made 10 days after each spray. For reporting purposes, the leaves of ten plants from each site were observed and symptoms of disease were scored on a scale of 0 to 9 for early infestation and late infestation and are summarized in Table 2.

Table 2. Nominal disease parameters

Scale Illness rate Reaction intensity 0 No disease = Immune one 1 - 5% infection = Mild 3 6 - 10% infection = Moderately pronounced 5 11 - 25% infection = Anxious 7 26 - 50% infection = Pronounced nine > 50% infection = Extremely pronounced

The disease rate index was calculated using the following formula:

Sum of all numeric values

PDI = ------------------------------------------------ --------------------- X 100

Number of observed plants X

PDI values were transformed using trigonometric transformation and statistically analyzed. The percentage of disease control (% DC) was calculated using the following formula.

Percentage of illness under control - percentage of illness under treatment

DC (%) = --------------------------------------------- ---------------- X 100

Percentage of disease under control

Harvest

When harvesting, data on the yield was recorded on individual plots, after which the yield was calculated depending on the use of the product, and the result was converted into a yield per hectare (k / ha), after which the data were statistically analyzed.

Phytotoxicity

A study was made for possible damage to plants by applying various agents taking into account phytotoxic symptoms: damage to the tips or surface of the leaves, wilting, lightening of veins, necrosis, hyponastia or epinasty for ten plants from each site. The observation results were recorded before spraying, as well as on the 1st, 3rd, 5th, 7th, 10th and 15th day after the application of the agent. Table 3 below summarizes the phytotoxicity test for damage to the tip or leaf surface, scored on a scale of 0 to 10.

Table 3. Evaluation scale of phytotoxicity (EPF)

Crop Responsiveness / Crop Damage Assessment 0-00 0 1-10% one 11-20% 2 21-30% 3 31-40% 4 41-50% 5 51-60% 6 61-70% 7 71-80% 8 81-90% nine 91-100% ten

Statistical data processing: Analysis of variance was carried out using the OPSTAT software.

Table 4. Bioeffectiveness of various fungicidal agents against potato late blight (Rabi, 2016-17)

Medium No. Description of the tool Dose (gr ai / ha) Dose (ml or g / ha) PDI (%) PDC
10 DAA 3rd spray Preliminary calculation 10 DAA
1st spray 10 DAA
2nd spray 10 DAA
3rd spray C1 Azoxystrobin 20% + Cymoxanil 20% + Metalaxyl-M 10% VG (Example No. 1) 100 + 100 + 50 500 0.00
(0.00) 0.00
(0.00) 1.12
(4.88) 2.97
(9.42) 94.62 C2 Azoxystrobin 20% + Cymoxanil 22% + Metalaxyl-M 10% VG (Example No. 2) 100 + 110 + 50 500 0.00
(0.00) 0.00
(0.00) 1.49
(6.9) 3.71 (11.07) 93.28 C3 Azoxystrobin 22% + Cymoxanil 20% + Metalaxyl-M 10% VG (Example No. 3) 110 + 100 + 50 500 0.00
(0.00) 0.00
(0.00) 1.86
(7.74) 4.08 (11.63) 92.61 C4 Azoxystrobin 22% + Cymoxanil 22% + Metalaxyl-M 9% VG (Example No. 4) 110 + 110 + 45 500 0.00
(0.00) 0.38
(2.02) 1.86
(7.74) 4.45 (11.91) 91.94 C5 Azoxystrobin 30% + Cymoxanil 3% + Metalaxyl-M 1% VG (Example No. 5) 150 + 15 + 5 500 0.00
(0.00) 2.97
(9.78) 4.45 (12.11) 8.15 (16.54) 85.23 C6 Cymoxanil 50% SP 600 1200 0.00
(0.00) 5.93 (13.63) 10.00 (18.37) 16.67 (23.96) 69.80 C7 Metalaxil-M 25% SP one hundred 400 0.00
(0.00) 5.56 (13.45) 11.12 (19.46) 17.78 (24.9) 67.78 C8 Azoxystrobin 25% KS 125 500 0.00
(0.00) 7.78 (15.99) 13.34 (21.41) 24.82 (29.85) 55.03 C9 Cymoxanil 50% SP + Azoxystrobin 25% KS (tank mix) 600 + 125 1200 + 500 0.00
(0.00) 2.60
(8.94) 6.30 (14.49) 12.60 (20.76) 77.17 C10 Cymoxanil 25% SP + Azoxystrobin 25% KS (tank mix) 100 + 125 400 + 500 0.00
(0.00) 2.97
(9.59) 7.04 (15.32) 13.71 (21.67) 75.16 C11 Cymoxanil 50% SP + Azoxystrobin 25% KS (tank mix) 600 + 100 1200 + 400 0.00
(0.00) 1.86
(6.37) 4.08 (11.56) 10.38 (18.77) 81.19 C12 Unprocessed - - 0.00
(0.00) 10.75 (19.07) 25.19 (30.12) 55.19 (47.99) - KP (B = 0.05) NS 3.36 3.24 4.04 -

PDI - Percentage of Disease Rate

PDC- Percentage Incidence Control

DAA- Number of days after application

NS- Minor

g a.i./ha- gram of active ingredient per hectare

The results presented in table 4 show that at the beginning of the test, late blight was not observed on any of the plants, which indicates the same type of tests with all means. 10 days after the first application, the greatest infection with late blight was recorded during treatment with C 12 (10.75%). It was noted that all fungicides were able to significantly reduce the severity of the disease compared to untreated areas. The smallest infection with late blight was observed with the use of C1 to C3 (0.00%), which are equivalent to C4 (0.38%). These funds (C1 to C4) were significantly better than the rest.

The highest infection was recorded 10 days after the second application (25.19%). The smallest infection with late blight was observed when using C1 (1.12%), which is equivalent to C2 (1.49%), C3 (1.86%) and C4 (1.86%). These funds (C1 to C4) were significantly better than the rest.

10 days after the third application, a similar trend was observed as with the second application. The smallest late blight infection was observed with the use of C1 (2.97%), which is equivalent to C2 (3.71%), C3 (4.08%) and C4 (4.45%). The highest infection was recorded in untreated areas (55.19%). These funds (C1 to C4) were significantly better than the rest.

The highest percentage of disease control (PDC) was recorded for C1 (94.62%), followed by C2 (93.28%), C3 (92.61%) and C4 (91.94%). The lowest percentage of disease control was recorded in the use of C8 (55.03%), then C7 (67.78%) and C6 (69.80%).

Table 5. Bioeffectiveness of various fungicidal agents against early potato rot (Rabi, 2016-17)

No. of funds Description of the tool Dose (gr ai / ha) Dose (ml or g / ha) PDI (%) PDC
10 DAA 3rd spray Preliminary calculation 10 DAA
1st spray 10 DAA
2nd spray 10 DAA
3rd spray C1 Azoxystrobin 20% + Cymoxanil 20% + Metalaxyl-M 10% VG (Example No. 1) 100 + 100 + 50 500 0.00
(0.00) 0.00
(0.00) 0.00
(0.00) 0.38
(2.02) 97.82 C2 Azoxystrobin 20% + Cymoxanil 22% + Metalaxyl-M 10% VG (Example No. 2) 100 + 110 + 50 500 0.38
(2.02) 0.38
(2.02) 0.38
(2.02) 0.38
(2.02) 97.82 C3 Azoxystrobin 22% + Cymoxanil 20% + Metalaxyl-M 10% VG (Example No. 3) 110 + 100 + 50 500 0.75
(2.86) 0.75
(2.86) 0.75
(2.86) 1.12
(4.88) 93.57 C4 Azoxystrobin 22% + Cymoxanil 22% + Metalaxyl-M 9% VG (Example No. 4) 110 + 110 + 45 500 0.75
(4.04) 0.75
(4.04) 0.75
(4.04) 0.75
(4.04) 95.69 C5 Azoxystrobin 30% + Cymoxanil 3% + Metalaxyl-M 1% VG (Example No. 5) 150 + 15 + 5 500 0.00
(0.00) 0.00
(0.00) 0.00
(0.00) 0.00
(0.00) 100,00 C6 Cymoxanil 50% SP 600 1200 0.38
(2.02) 1.86
(7.55) 7.04 (15.19) 11.86 (20.12) 31.88 C7 Metalaxil-M 25% SP one hundred 400 0.75
(4.04) 1.86
(7.74) 8.52
(16.8) 12.6 (20.76) 27.63 C8 Azoxystrobin 25% KS 125 500 1.12
(4.88) 1.49
(6.90) 2.23
(8.39) 4.08 (11.46) 76.57 C9 Cymoxanil 50% SP + Azoxystrobin 25% KS (tank mix) 600 + 125 1200 + 500 0.75
(4.04) 1.12
(6.06) 4.82 (12.56) 7.78 (16.17) 55.31 C10 Cymoxanil 25% SP + Azoxystrobin 25% KS (tank mix) 100 + 125 400 + 500 0.38
(2.02) 1.86
(7.74) 5.56 (13.59) 8.89 (17.33) 48.94 C11 Cymoxanil 50% SP + Azoxystrobin 25% KS (tank mix) 600 + 100 1200 + 400 0.75
(4.04) 1.49
(6.90) 8.15 (16.36) 11.86 (20.14) 31.88 C12 Unprocessed - - 0.00
(0.00) 5.19 (13.04) 13.71 (21.71) 17.41 (24.65) - KP (B = 0.05) NS 3.94 3.51 3.87 -

PDI - Percentage of Disease Rate

PDC- Percentage Incidence Control

DAA- Number of days after application

NS- Minor

g a.i./ha- gram of active ingredient per hectare

The results presented in Table 5 show that alternaria was observed at the beginning of the trial, but there was no significant difference between the agents, which would indicate an even spread of the disease. The highest infection was recorded 10 days after the first application (5.19%). The smallest infection was observed with the use of C1 (0.00%) and C5 (0.00%), which are equivalent to C2 (0.38%), C3 (0.75%) and C4 (0.75%). These products (C1 to C5) were significantly better in quality compared to the others.

10 days after the second application, no signs of disease were observed when treated with agents C1 to C5. The highest infection was recorded in the areas under control (13.71%). The smallest infection was observed with the use of C1 (0.00%) and C5 (0.00%), which are equivalent to C2 (0.38%), C3 (0.75%) and C4 (0.75%). These products (C1 to C5) were significantly better in quality compared to the others.

A similar trend was observed 10 days after the third application. The smallest infection was observed with the use of C5 (0.00%), which is equivalent to C1 and C2 (0.38%), as well as C4 (0.75%) and C3 (1.12%). The highest infection was recorded in untreated areas (17.41%). These funds (C1 to C5) were significantly better than the rest.

The highest percentage of disease control (PDC) was recorded in the use of C5 (100%), then in C1 and C2 (97.82%), C4 (95.69%), C3 (93.57%;) ... The lowest percentage of disease control was recorded in the use of C7 (27.63%), then C6 and C11 (31.88%), C10 (48.94%) and C9 (55.31%).

Table 6: Effects of various fungicides on potato yield (Rabi, 2016-17)

From the data in Table 6, it follows that for all cases of application of the agent, a significant increase in yield was noted compared to untreated plots (178.67 kg / ha). The highest yield was recorded in the use of C1 (246 k / ha), which significantly surpasses the other applications of the agent, which were for C2 (240.33 k / ha), C3 (238 k / ha) and C4 (230 k / ha) / ha), and C5 closes this row (226.67 k / ha). The lowest yield was recorded on the untreated area (178.67 kg / ha).

Table 7. The effect of phytotoxicity on potatoes when using different fungicidal agents (Rabi, 2016-17)

No. facilities Description of the tool Dose * Phytotoxicity (On a phytotoxicity rating scale from 0 to 10) gr a.i. / ha ml or g / ha Before spraying Days After Application (DAA) one 3 5 7 ten 15 C1 Azoxystrobin 20% + Cymoxanil 20% + Metalaxyl-M 10% VG
(Example # 1) 100 + 100 + 50 500 0 0 0 0 0 0 0 C2 Azoxystrobin 20% + Cymoxanil 22% + Metalaxyl-M 10%
(Example No. 2) 100 + 110 + 50 500 0 0 0 0 0 0 0 C3 Azoxystrobin 22% + Cymoxanil 20% + Metalaxyl-M 10%
(Example No. 3) 110 + 100 + 50 500 0 0 0 0 0 0 0 C4 Azoxystrobin 22% + Cymoxanil 22% + Metalaxyl-M 9%
(Example No. 4) 110 + 110 + 45 500 0 0 0 0 0 0 0 C5 Azoxystrobin 30% + Cymoxanil 3% + Metalaxyl-M 1%
(Example No. 5) 150 + 15 + 5 500 0 0 0 0 0 0 0 C6 Azoxystrobin 20% + Cymoxanil 20% + Metalaxyl-M 10% VG
(Example # 1) 200 + 200 + 100 1000 0 0 0 0 0 0 0 C7 Azoxystrobin 20% + Cymoxanil 22% + Metalaxyl-M 10%
(Example No. 2) 200 + 220 + 100 1000 0 0 0 0 0 0 0 C8 Azoxystrobin 22% + Cymoxanil 20% + Metalaxyl-M 10%
(Example No. 3) 220 + 200 + 100 1000 0 0 0 0 0 0 0 C9 Azoxystrobin 22% + Cymoxanil 22% + Metalaxyl-M 9%
(Example No. 4) 220 + 220 + 90 1000 0 0 0 0 0 0 0 C10 Azoxystrobin 30% + Cymoxanil 3% + Metalaxyl-M 1%
(Example No. 5) 300 + 30 + 10 1000 0 0 0 0 0 0 0 C11 Unprocessed - - 0 0 0 0 0 0 0

Phytotoxic symptoms: damage to the tips or surface of leaves, wilting, lightening of veins, necrosis, hyponastia, or epinasty

g a.i./ha- gram of active ingredient per hectare

Various combinations of fungicides were sprayed at doses of X (500 g / ha) and 2X (1000 g / ha); phytotoxic effects such as leaf tip / surface damage, vein lightening, wilting, necrosis, hyponastia or epinasty of the potato crop are presented in Table 7. Phytotoxicity parameters were monitored before spraying and 3, 5, 7, 10 and 15 days after application ... No phytotoxicity effect on potatoes after spraying was observed. No negative effect on potato yield in the field treated with a mixture of fungicides at a maximum dose of 1000 g / ha was found.

Therefore, the synergistic fungicidal mixture of the present invention (azoxystrobin, cymoxanil, metalaxyl-M) effectively fights cases of early and late infestation of potatoes. Among them, azoxystrobin 20% + cymoxanil 20% + metalaxyl-M 10% are highly effective.The effectiveness of the synergistic fungicides of this invention is much superior to commercially available fungicides (azoxystrobin 25% KS, cymoxanil 50% SP and metalaxyl-M 25% SP) or their possible two-way methods combination for preparation of tank sweep. The synergistic fungicidal mixture contributes to a higher yield of potatoes. No effect of phytotoxicity on potatoes was found using the synergistic fungicidal mixture of the present invention.

Therefore, the fungicidal mixture of the present invention exhibits a synergistic effect for disease control. In addition, the fungicidal mixture is effective with long-term use and combats resistance in the fungus, thereby limiting yield losses compared to using separately azoxystrobin 25% KS, cymoxanil 50% CP and metalaxyl-M 25% CP, or possible two-way combination methods for preparing tank sweep.

Technical advantages and economic value

The invention described above has a number of technical advantages, including the production of a fungicidal mixture that

- has increased fungicidal activity and

- fights against the manifestations of resistance in the fungus.

The above description of a particular embodiment discloses the general properties of the invention so fully that, using the available data, it is easy to modify and / or adapt this particular embodiment for various purposes without departing from the basic concept; thus, any modifications and changes are intended and should be within the limits of the allowable values and series of equivalents for the illustrated embodiment of the invention. It should be understood that the phraseology and terminology used above are intended to be descriptive and not limiting. Thus, while embodiments of the invention have been described in terms of preferred embodiments, those skilled in the art will understand that embodiments of the present invention may be practiced with variations within the spirit and scope of the embodiments of the present disclosure.

Throughout this specification, the words "contains" or "containing" will mean the inclusion of the claimed element, in whole or in stages, or a group of elements, in whole or in stages, but not the exclusion of any other element, in whole or in stages, or a group of elements, in whole or in stages.

The use of the expression "at least" or "at least one" implies the use of one or more elements or ingredients or amounts, as the use may be in an embodiment of the invention to achieve one or more of the desired objectives or results.

Any consideration of documents, protocols, materials, devices, articles, etc. included in this specification is intended solely to provide the context of the invention. This should not be taken as an admission that any or all of these issues form part of or are general knowledge in the field pertaining to the invention, on the basis that the data existed prior to the priority date of this application.

Numerical values given for various physical indicators, sizes or quantities are approximate; higher / lower values than the numerical values for the specified parameters, sizes or quantities are intended to be within the scope of the invention, unless otherwise indicated in the specification.

While much attention is given here to the components and constituent parts of the preferred embodiments of the invention, it will be appreciated that many embodiments are possible and that many changes can be made within the preferred embodiments without departing from the basic principles of the invention. These and other changes in the preferred embodiment, as well as other embodiments of the invention, will be apparent to those skilled in the art from the foregoing description, and it should be clearly understood that the above description is to be construed simply as an illustrative disclosure and not as limitation.

Claims (15)

1. A synergistic fungicidal composition containing: a. metalaxyl-M, b. cymoxanil, c. azoxystrobin and d. at least one excipient, in which the mass ratio of metalaxyl-M, cymoxanil and azoxystrobin is from 1: 1: 0.5 to 1: 3: 30. 2. A synergistic fungicidal composition according to claim 1, wherein said excipient is selected from the group consisting of a dispersing component, a foam inhibitor, a wetting agent, a disintegrant, an anti-caking agent, a carrier or a binder. 3. A synergistic fungicidal composition according to claim 2, wherein said dispersant component is at least one selected from the group consisting of sodium lignosulfonate, calcium lignosulfonate, sodium alkyl naphthalene sulfonate, sulfonated aromatic polymer sodium salt, polycarboxylic acid homopolymer, sodium salt of homopolymer polycarboxylic acid, polycarboxylic acid copolymer, ethylene oxide / propylene oxide (EO / PO) block copolymers, and polycarboxylic acid copolymer sodium salt. 4. A synergistic fungicidal composition according to claim 2, wherein said foam inhibitor is at least one selected from the group consisting of polydimethylsiloxane powder and polydimethylsiloxane liquid. 5. A synergistic fungicidal composition according to claim 2, wherein said wetting agent is at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, or combinations thereof. 6. A synergistic fungicidal composition according to claim 2, wherein said disintegrant is at least one selected from the group consisting of sodium chloride, sodium sulfate, ammonium sulfate, sodium carbonate, sodium bicarbonate, starch and starch derivatives, sodium tripolyphosphate, transversely cross-linked sodium carboxymethylcellulose, cross-linked polyvinylpyrrolidone. 7. A synergistic fungicidal composition according to claim 2, wherein said anti-caking agent is at least one selected from the group consisting of clay, precipitated silica and metal stearates selected from the group consisting of zinc stearate, calcium stearate, magnesium stearate and aluminum stearate. 8. A synergistic fungicidal composition according to claim 2, wherein said carrier is selected from the group consisting of clay, minerals and talc. 9. A synergistic fungicidal composition according to claim 2, wherein said binder is at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamides, dextrose, sucrose and lactose. 10. The synergistic fungicidal composition of claim 1, wherein said fungicidal composition is in at least one of dosage forms selected from the group consisting of water dispersible granules, wettable powder or suspension concentrate.