UA155364U - Method of preparation of fungicidal composition - Google Patents

Abstract

A method for obtaining a fungicidal composition in the form of a suspension containing propiconazole, pyraclostrobin, boscalid and auxiliary agents includes the following steps: a) combine boscalid and pyraclostrobin in an acidic aqueous solution in the first reactor and disperse the resulting mixture, b) mix oil and propiconazole in the second reactor to obtain an emulsion, c) mix the dispersion of boscalid and pyraclostrobin from the first reactor with the propiconazole emulsion from the second reactor to obtain a suspension.

Description

The utility model belongs to the field of chemical protection of agricultural crops, in particular to fungicidal compositions intended for the protection of cultivated plants, in particular grain crops from diseases of fungal etiology.

Fungicides (from the Latin rypadi - mushroom and saedo - kill, destroy) - substances used to protect plants from pathogens of fungal diseases. Chemical substances used to protect plants from bacterial diseases (bactericides) also belong to this group.

The possibility of curing plants from fungal diseases by treating the leaves or root system with preparations was established in the 19th century, when the origin of fungal diseases was first substantiated and the first inorganic protective fungicides were created - Bordeaux liquid, etc. The steps taken in this direction led to certain successes: potato scab was suppressed with sulema, grape anthracnose with copper vitriol, pear burn with zinc chloride. With the advent of such protective fungicides as dithiocarbamates and captan, a large number of organic compounds were synthesized and tested in the 1940s to find out their medicinal properties. In most cases, they were not effective enough or had a negative impact on plant development when destroying pathogens. In further studies, it was proved that plants are able to show resistance against phytopathogenic fungi and this resistance depends on the presence of natural antifungal compounds in plants or on the release of such compounds (phytoalexins) by plants in response to pathogen invasion. Some of the phytoalexins were isolated, but they were ineffective when applied to leaves because they did not reach the area that needed treatment. Plants secreted phytoalexins only in places of plant damage. But it became clear to scientists: if phytoalexins are formed in plants, then they can be synthesized. Considerable success was achieved by chemists and doctors who obtained bactericidal systemic fungicides that are non-toxic to humans. With the discovery of penicillin in 1940, the selection of a series of chemotherapeutic antibiotics began, the effectiveness of many of which was also studied on plants.

The modern assortment of fungicides is classified on the basis of three main principles: depending on the nature of the effect on pathogens, purpose and chemical nature. According to the nature of action on pathogens, fungicides are divided into two groups: protective (prophylactic) and therapeutic (curative, eradicating, curative, destroying).

Depending on the chemical properties, fungicides are: - inorganic: copper - copper sulfate, copper chloride; sulfur compounds - lime-sulfur decoction, ground and colloidal sulfur; mercury - mercury chloride; - organic (the largest group), for example: carbamic acid derivatives - zineb, cuprocin-1, polymarcin, polycarbacin; phthalimides - captan, phthalan; quinones - figon; ethers of dinitroalkalphenols - karatan; organomercury compounds - granozan, mercurhexane; oxathione compounds - vitavax; drugs based on benzimidazole - benomyl; - biological: preparations of living organisms, products of their vital activity, used by farmers to protect the plant during its growing season from diseases caused by fungal and bacterial pathogens.

The nature of the use of fungicides is also different. They are used to treat seeds "- used to fight diseases whose pathogens are spread with seeds or are in the soil. There are preparations for soil treatment - they destroy soil pathogens of plant diseases, they are especially effective in greenhouses and greenhouses. There are fungicides for treating plants during the dormant period - they destroy the wintering stages of the pathogen are used in early spring before budding, in late autumn and in winter. Fungicides for processing during the growing season are mainly preventive drugs used in summer for spraying and fumigation of storage facilities, in particular grain storages and vegetable storages.

When choosing fungicides, first of all, information about the sources of primary and secondary infection, as well as the time of damage and the rate of infection growth are taken into account. Against pathogens on the surface of the seeds and in the soil, you can use a fungicide of contact protective action, which is characterized by significant stability in the soil. If the infection is inside the seed, a systemic drug that moves well up the plant is needed. In this case, preference is given to a fungicide with a wide spectrum of action, as well as with several active substances. To improve the quality of processing, you should use preparations with an adhesive. In addition, the criteria for the correct selection of the poison are: the spectrum of fungicidal activity, especially against powdery mildew diseases, the features of the spread of pathogens in this region, the phytoexpertise of the seed material, the phytosanitary situation in the previous season. To prevent the emergence of resistant populations, it is necessary to provide for the alternation of fungicides from different chemical groups.

Today, the problem of protecting plants and creating 60 favorable conditions for their development is acute in agriculture. At this stage of agricultural development, the cultivation of plant products on an industrial scale is impossible without the use of chemical plant protection agents. Fungicides, which effectively control fungal diseases, are an important component of measures aimed at increasing the yield of agricultural crops.

Today, the market of Ukraine offers a wide range of various domestic and foreign preparations for the treatment of plants in order to control the causative agents of fungal diseases. However, among the wide list of drugs, only some can be classified as highly effective.

Propiconazole can be mentioned among the effective fungicidal agents that are widely used today.

Propiconazole, which has the chemical name -1-(2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl|methyl/)|-1,2,4-triazole, and is characterized by the following structural formula:

SI because o

SI M

7

M

Propiconazole was first described in patent 50649316 (priority 18.11.1974), the applicant

Janssen Pharmaceutika N.V., (MO). Propiconazole is a triazole fungicide, also known as a demethylation-inhibiting fungicide, because it binds to the enzyme 14-alpha-demethylase and inhibits the demethylation of the precursor to ergosterol. Without this demethylation step, ergosterols are not incorporated into the cell membranes of growing fungi, and cell growth ceases. Propiconazole is used in agriculture as a systemic fungicide for a variety of crops such as wheat, mushrooms, corn, rice, peanuts, almonds, sorghum, oats, etc.

Pyraclostrobin is also widely used in Ukraine to combat fungal diseases.

Pyraclostrobin, which has the chemical name - methyl /M-(2-(1-(4-chlorophenyl)pyrazol-3-yl|oxymethylI|phenyl|-M-methoxycarbamate), is characterized by the following structural formula: o sn -U. y 07

M

-6- M o

From ten, about

Pyraclostrobin is a fungicide of contact and deep action and belongs to the class of strobilurins, which have activity against various fungal pathogens. It has a long-lasting protective effect. Pyraclostrobin inhibits the respiration of the pathogen, accumulates on the surface of the leaf, then

Zo is gradually redistributed in internal tissues. It was reported that pyraclostrobin, affecting mitochondria, blocks the supply of energy to cells, which causes the death of spores and mycelium of the fungus. Pyraclostrobin was first described in patent A48138 (submission date 06/21/1995), applicant: BASF AG, (OE)

Ukrainian patent OA 54425 described a fungicidal combination containing, in particular, a combination of pyraclostrobin and propiconazole. But, as it follows from the data of the conducted research, this combination did not show a satisfactory fungicidal effect, in particular on powdery mildew. Also, this combination was not classified as a preferred combination for use as a fungicide. The patent PA 54425 did not report on the synergistic effect of the combination of propiconazole and pyraclostrobin and did not investigate the effect of combinations of propiconazole and pyraclostrobin with different ratios of active substances on different pathogens.

Therefore, there is still an urgent need to research and expand the spectrum of action of known compositions, to increase their activity and expand the scope of application. At the same time, it should be taken into account that the new compositions being developed must be safe for the environment and have a reduced harmful effect on useful plants, soil and people.

In this regard, it is useful to strengthen the effectiveness and expand the spectrum of action due to the search for combinations of fungicidally active agents that show synergistic activity.

Such combined use has a number of significant advantages, namely the expansion of the spectrum of action, increase in activity due to synergistic action, reduction of the content of active ingredients in the composition while maintaining activity, etc.

Therefore, the search and development of new combined compositions with improved activity is an urgent need for the development of modern means of protection of agricultural crops.

Among the potential and promising component agents for use in combined fungicidal compositions, boscalid can be mentioned.

Boscalid, which has the chemical name -2-chloro-M-(2-(4-chlorophenyl)phenyl|pyridine-3-carboxamide), is characterized by the following structural formula:

SI

M SI Also

WITH

S. M. o

Belongs to the class of carboxamides and blocks the key stage of mitochondrial respiration of cells that cause diseases. Boskalid inhibits the germination of spores and growth tubes, which precedes the formation of appressoria, and has a translaminar effect. Boscalid is active against almost all types of fungal diseases (powdery mildew, gray mold, root rot, sclerotinia and other types of fungal diseases. It is mainly used for the prevention and control of diseases related to rape, grapes, fruit trees, vegetables and field crops (sunflower, soybean).

US patent 65601 described a fungicidal combination containing, in particular, a combination of boscalid and propiconazole. But as it follows from the data of the conducted research, although this combination shows a synergistic effect, the level of activity against Voiguii5 Sipegea is quite low, only 35 95. The US patent 54425 did not investigate the effect of combinations of boskalid and propiconazole with different ratios of active substances on different pathogens.

The useful model is based on the task of expanding the range of fungicidal compositions to protect cultivated plants from various diseases and pathogens, in particular, to prevent the development of diseases such as helminthosporosis spots, septoriosis, powdery mildew, rust diseases, etc.

It was found that the combination of propiconazole, pyraclostrobin and boscalid in certain

From the proportions, it provides a fungicidal composition with unique properties, which exhibits a synergistic effect with a high activity index, has a wide spectrum of action to prevent the development of various diseases, which was not characteristic of known compositions of a similar composition, and has much greater activity.

The combination of boskalid with fungicides of the triazole and strobilurin series makes it possible to create a fungicidal complex that will be active against a wide range of fungal pathogens and, at the same time, will increase the yield of wheat, barley, sunflower, soybean, rapeseed, etc.

The task is solved by the fact that the method of obtaining a fungicidal composition in the form of a suspoemulsion containing propiconazole, pyraclostrobin, boscalid and auxiliary agents, which includes the following stages: a) in the first reactor, boscalid and pyraclostrobin are combined in an acidic aqueous solution and the resulting mixture is dispersed, b) oil and propiconazole are mixed in the second reactor to obtain an emulsion, c) the dispersion of boscalid and pyraclostrobin from the first reactor is mixed with the propiconazole emulsion from the second reactor to obtain a suspoemulsion.

Organic acid is used to create an acidic environment.

Monocarboxylic, dicarboxylic or tricarboxylic acid is used as an organic acid.

As an organic acid, an acid selected from the following group is used: formic acid, acetic acid, propionic acid, oxalic acid, malic acid, malonic acid, succinic acid, citric acid or trifluoroacetic acid.

Citric acid is used as an organic acid. The pH of the fungicidal composition is 4.2-5.5.

Preparation of dispersion of boscalid and pyraclostrobin in the first reactor and emulsion of propiconazole in the second reactor is carried out in the presence of auxiliary agents.

Mix propiconazole, pyraclostrobin, boscalid and auxiliary agents at the following ratio of components, by weight. 9o: propiconazole 15.0-25.0 pyraclostrobin 10.0-20.0 boscalid 7.0-15.0 auxiliary agents the rest.

Mix propiconazole, pyraclostrobin, boscalid and auxiliary agents at the following ratio of components, by weight. 95 propiconazole 17.0-23.0 pyraclostrobin 12.0-18.0 boskalid 9.0-13.0 auxiliary agents the rest.

Mix propiconazole, pyraclostrobin, boscalid and auxiliary agents at the following ratio of components, by weight. 95 propiconazole 18.0-20.0 pyraclostrobin 14.0-16.0 boscalid 11.0-13.0 auxiliary agents the rest.

Propiconazole, pyraclostrobin and boscalid are mixed in a ratio of 1.1-1.3:0.9-1.1:0.7-0.9.

Propiconazole, pyraclostrobin and boscalid are mixed in a ratio of 1.2:1.0:0.8.

The combination of 3 active substances from different chemical classes with different properties (solubility, lipophilicity) contributes to the accumulation of an effective concentration of fungicides in culture cells, due to which a long protective effect (up to 4 weeks) and a quick "stop effect" is achieved. Thanks to the unique combination of active substances, a strategy of anti-resistant protection of plants is provided.

In the course of the research, an unexpected result was found when using a combination of propiconazole, pyraclostrobin and boscalid in a ratio of 1.2:1.0:0.8. This combination provided not only improved control of fungal diseases, but also provided a significant increase in yield.

However, the use of boscalid and pyraclostrobin in the same formulation is limited, primarily due to their insufficient solubility and tendency to recrystallization. At the same time, the additional introduction of propiconazole, which under normal conditions is a viscous liquid, into the composition of the composition further increases the above-mentioned problems and prevents the realization of the advantages of the simultaneous combination of these fungicides.

З An effective way to solve the problem of recrystallization is the introduction of additional components into the formulations, which would restrain the recrystallization of boscalid with pyraclostrobin, as well as emulsify propiconazole.

This problem of limited solubility can be solved by choosing solvents that dissolve active substances and do not mix with water, since such mixing leads to crystallization of aromatic boscalid.

The conducted studies made it possible to choose the optimal composition of active agents, propiconazole, pyraclostrobin and boscalid, which show their activity most fully and safely for the surrounding environment, and the used auxiliary agents made it possible to form them into a suspoemulsion with excellent characteristics regarding storage and use.

The preparation of the suspoemulsion takes place in two stages, because it was unexpectedly found that the grinding of boscalid and pyraclostrobin together with propiconazole leads to the formation of a loamy viscous substance that does not disperse in the solvent. In addition, obtaining a suspoemulsion with a pH value greater than 6 causes rapid recrystallization of boscalid, so the pH value of the combination should be 4.2-5.5.

At the first stage, boscalid and pyraclostrobin are added to the aqueous solution of surfactants and carboxylic acid. After that, the mixture is dispersed and ground.

In parallel, a mixture of surfactants, oil and propiconazole is prepared.

At the second stage, a boscalid suspension with pyraclostrobin and propiconazole emulsions are mixed to obtain a boscalid, pyraclostrobin and propiconazole suspoemulsion.

The proposed suspoemulsion was created on a water basis, which made it possible to abandon the use of organic solvents and carriers, and to increase the safety of the product, namely to give it "greenness".

Another advantage of suspoemulsion is the ease of diluting them with water when preparing tank mixes.

The combination of boscalid, pyraclostrobin and propiconazole in high concentrations requires the selection of appropriate surface-active substances for their wetting and rheology modifiers that would prevent syneresis of the composition in an acidic environment.

The active substances of the proposed fungicidal composition, such as propiconazole, pyraclostrobin and boscalid, were obtained from commercial sources.

As common auxiliary agents, the developed fungicidal composition may contain emulsifier(s), antifreeze(s), thickener(s), adjuvant(s), stabilizer(s), defoamer(s), solvent(s), and preservative(s). .

In addition to the auxiliary agents mentioned above, other auxiliary agents such as surfactants, dispersants, wetting agents, solubilizers, substances promoting penetration, binding agents, thickeners, fillers, moisturizers, antifreezes, dyes, tackifiers, pH correctors, etc.

Suitable solvents are water and organic solvents, such as petroleum fractions with a medium to high boiling point, such as kerosene, diesel fuel; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, for example toluene, paraffin, tetrahydronaphthalene, alkylated naphthalene; alcohols, for example ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, for example cyclohexanone; esters, for example, lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, for example M-methylpyrrolidone, dimethylamides of fatty acids; and their mixtures. The preferred solvent for this useful model is water, dimethylformamide, ethyl acetate.

Suitable surface-active substances are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surface-active substances, block polymers, polyelectrolytes and mixtures thereof. Such surface-active substances can be used as an emulsifier, dispersant, solubilizer, wetting agent, substance that promotes penetration.

Suitable anionic surfactants are alkaline, alkaline earth, or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefinsulfonates, ligninsulfonates, fatty acid and oil sulfonates, ethoxylated alkylphenols sulfonates, alkylated arylphenols sulfonates, condensed naphthalene sulfonates, dodecyl and tridecylbenzene sulfonates, naphthalene and alkylnaphthalene sulfonates, sulfosuccinate or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, ethoxylated alkylphenols, alcohols, ethoxylated alcohols, or fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates.

Particularly suitable anionic surfactants are alkylbenzenesulfonates, such as, for example, the sodium, calcium or triethylammonium salts of alkylbenzenesulfonic acid. The most preferred alkylbenzenesulfonates are the sodium, calcium or triethylammonium salts of dodecylbenzenesulfonic acid, in particular KPodasa|F 70/38 (7095 calcium dodecylbenzenesulfonate in n-butanol), EPodasakyu b0/BE (60 95 calcium dodecylbenzenesulfonate in 2-ethylhexanol) and KPpodasayu 2283 (7095 dode Cylbenzene sulfonate ammonium), Apodia StrN company, phenylsulfonate CA 100 (4095 calcium dodecylbenzenesulfonate in Scheporo!i X-060 and boime 550 200) Siapapi StnN company or

MapzaF EMM 70/2E (57 95 linear dodecylbenzenesulfonate in 2-ethylhexanol) of AiBbgidni and MOP.

Suitable nonionic surfactants are alkoxylates, M-substituted fatty acid amides, amino oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols,

alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters. Ethylene oxide and/or propylene oxide can be used for alkylation, preferably ethylene oxide.

Examples of M-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are esters, glycerol esters or monoglycerides of fatty acids. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitans, sucrose and glucose esters, or alkyl polyglycosides. Examples of polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vinyl alcohol or vinyl acetate.

Suitable cationic surfactants are quaternary surfactants, such as quaternary ammonium compounds with one or two hydrophobic groups or salts of long-chain primary amines. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacidic combined polymers. Examples of polybases are polyvinylamines or polyethyleneamines.

Preferred alcohol alkoxylates are monobranched alcohol ethoxylates such as

AiriizF MBA 11-7 (ethoxylate of a branched alcohol with 7 ethoxy chains) of Opideta or

Separoku X-60 (alcohol ethoxylate with 6 ethoxy chains) by Siagapi.

Suitable thickeners are polysaccharides (eg xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates and silicates.

Suitable fillers are mineral and synthetic mineral compounds such as quartz, silica gel, silica, silicates, talc, kaolin, limestone, carbon black, lime, chalk, lime clay, clay, dolomite, diatomite, calcium sulfate, magnesium sulfate, magnesium oxide, as well as products of vegetable origin such as grain flour, tree bark flour, tree flour and nut shell flour, cellulose powders, or other solid fillers.

The preferred filler for the fungicidal composition of the utility model is silicon dioxide

Suitable antifreezes are ethylene glycol, propylene glycol, urea and glycerin.

Suitable defoamers are silicones, siloxanes, long-chain alcohols and salts and esters

From fatty acids.

Suitable dyes (eg red, blue or green) are pigments with low water solubility and water-soluble dyes. Examples are inorganic dyes (eg iron oxide, titanium oxide, iron hexacyanoferrate) and organic dyes (eg alizarin, azo and phthalocyanine dyes), etc.

Suitable tackifiers or binding agents are polyvinylpyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

Acids or bases can act as pH correctors.

Examples of suitable bases are inorganic compounds such as hydroxides of alkali and alkaline earth metals and hydroxides of other metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and aluminum hydroxide; oxides of alkali metals and oxides of alkaline earth metals and oxides of other metals, such as lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide and magnesium oxide, iron oxide, silver oxide; hydrides of alkali and alkaline earth metals, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, formates, acetates of alkali and alkaline earth metals and salts of other metals with carboxylic acids, such as sodium formate, sodium benzoate, lithium acetate, sodium acetate, acetate potassium, magnesium acetate and calcium acetate; carbonates of alkali and alkaline earth metals, such as lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate and calcium carbonate, as well as alkali metal bicarbonates (bicarbonates), such as lithium bicarbonate, sodium bicarbonate, potassium bicarbonate; alkaline and alkaline earth metal phosphates, such as sodium phosphate, potassium phosphate and calcium phosphate; alkoxides of alkali and alkaline earth metals, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, potassium tert-pentoxide.

Examples of suitable acids are inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, sulfuric acid, p-toluenesulfonic acid; Lewis acids such as boron trifluoride, aluminum chloride, ferric chloride (II), stannous chloride (IM), titanium chloride (IM) and zinc chloride (II), organic acids such as formic acid, acetic acid can also be used , propionic acid, oxalic acid, malic acid, malonic acid, succinic acid, citric acid, methylbenzenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, trifluoroacetic acid.

The choice of any supporting agent cannot be a limitation of this useful model.

The obtained fungicidal composition is a suspoemulsion and an emulsion concentrate.

The resulting composition is used to treat crops of cultivated plants to prevent disease damage. The specified composition in the form of a suspension concentrate is used at a consumption rate of 0.5-1.0 l/ha.

A number of fungicidal compositions of a useful model with different contents of active ingredients were obtained and studied, namely:

Composition 1

Suspoemulsion (SE) (Rapeseed oil/////777777171717171717171717111111111111111111111111111111 17171717" Emulator7/7/:/./О|Ї 66 natural refined deodorized oil

ICitric acid 77777771 71717171 KoretorrH/// | 009 22

Suspoemulsion is obtained as follows.

In the first reactor, boscalid and pyraclostrobin are added to the aqueous solution of some auxiliary agents and citric acid with a pH in the range of 4.2-5.5. After that, the mixture is dispersed and ground to obtain a suspension.

In the second reactor, another part of auxiliary agents, rapeseed oil and propiconazole are combined. The resulting mixture is well mixed to obtain an emulsion.

Combine the mixture from the first reactor and the second reactor, mix well to obtain a suspoemulsion of boscalid, pyraclostrobin and propiconazole.

Composition 2

Emulsion concentrate (KE)

The emulsion concentrate is prepared as follows.

Boskalid, propiconazole and pyraclostrobin are dissolved in a mixture of dimethylformamide and ethyl acetate at a temperature of 45-50 "C. After that, auxiliary agents are added and well emulsified to obtain an emulsion concentrate.

The developed composition is used in the form of an aqueous suspension or emulsion obtained by diluting the composition in a suitable amount of water.

The following examples of biological studies of the developed fungicidal composition are intended only to illustrate and explain the proposed useful model and are not intended to limit it in any way.

Determination of the biological effectiveness of active substances and their combinations on cultures

Of sunflowers and soybeans for protection against a wide range of diseases was the establishment of field studies in fourfold repetition.

To conduct the research, drugs based on combinations of active substances (propiconazole - pyraclostrobin and propiconazole with pyraclostrobin and boscalid) were used, as well as combinations of comparison of various commonly used fungicidal substances.

Weather conditions were monitored during the research; observed the development of pathogens on the studied crops; harvest accounting was carried out.

Research was carried out according to generally accepted methods (Methodology of testing and application of pesticides / edited by Prof. S.O. Tribel. - K.: "Svit", 2001; Fundamentals of scientific research in agronomy // Moiseichenko V.F., Yeschenko V. O. - K.: Vyshcha shkola, 1994. - 334 p.; Determination of the biological effectiveness of pesticides and agrochemicals. Methodical instructions/ Chabanyuk

Ya.V., Sherstoboyeva O.V., Tkach E.D., Bunas A.A., Starodub V.I., Dovgich K.I., Dmytruk D.M. - K., 2013. - 36 p.)

Example 1: Field tests of combinations of active substances against a complex of diseases in winter barley crops 1.1 Period of conducting the experiment: April - July 2021 2. Place of conducting the experiment: research and demonstration center of "Alfa Smart Agro" LLC (Cherkas village, Bilotserkivskyi district -n., Kyiv region), coordinates 49241734" N. W. 30211713" E. d.. Soil and climate zone:

Right-bank forest-steppe of Ukraine. Target objects: helminthosporiosis spots, septoriosis, powdery mildew, rust diseases. Culture: winter barley. Grade: Ninth Val. Planting density (seed sowing rate): 4 million similar seeds per 1 ha (150 kg/ha). Sowing (planting) date: 09/23/2020. Seedling emergence date: 10/02/2020. Phase of plant development during processing: tillering.

Type of experiment: field. Soil (type, mechanical composition, humus content (95), pH): chernozem with little humus, coarse dust - medium loam by mechanical composition on a carbonate loam. 1.2 Scheme of the experiment:

Table 1 (Control (untreated).d //11111111111111ЙГ111111

Boscalid. //////7777777771111111111111111111111111111111111Ї111111111111111111111111180сс 1.3 Technology of using the experimental drug: Time of treatments (application): 20.04.2021. Multiplicity of treatments: 1. Method of application: spraying vegetation flowering plants. Used equipment: Nagaii MA5TEK RI Sh5 tractor sprayer. Rate of working solution: 200 l/ha.

Accounting dates: 04/27/2021, 05/03/2021, 05/10/2021 1.4. Test results and their analysis:

In the course of conducting an experiment on testing the studied combinations of fungicidal agents

From the substances for spraying vegetative plants of winter barley, it was established that the drug is effective against net spotting of winter barley, the development of which was observed in the tillering phase in the experimental plots.

Thus, in the course of the conducted research, it was established that when using the studied combinations (propiconazole, pyraclostrobin, and boskalid) of active substances with different ratios, a positive effect was obtained in terms of stopping the development and spread of pathogens.

When using the studied combinations (Propiconazole and Pyraclostrobin and Boskalid) of active substances with different ratios, the highest efficiency indicators were obtained, compared to other studied combinations. The presented results testify to the high biological efficiency of the studied combination (Propiconazole and Pyraclostrobin and

Boskalid) with different ratios of active substances.

Table 2

The effectiveness of the studied combinations against net spotting of barley leaves in 2021 (Cherkas village, Bilotserkivsky district, Kyiv region)

The norm for 1 - - - as MTK rennya rovy rovy rovy tent o o o o

Prothioconazole Bixafen| 120-600

Propiconazole w

Pyraclostrobin I 100-100-80 24.8 621 25.7 61.6 29.7 61.3

Boscalid

Propiconazole w

Pyraclostrobin I 120-100-80 19.6 75.0 19.6 71.8 23.7 69.1

Boscalid

Propiconazole w

Pyraclostrobin I 100-20-80 21.6 67.0 23.1 66.8 26.3 65.8

Boscalid

Propiconazole w

Pyraclostrobin I 100-100-100 23.7 653.8 26.1 62.4 29.6 61.5

Boscalid

Tebuconazole w

Pyraclostrobin I 200-100-80 24.9 61.9 265.9 61.3 30.4 60.4

Boscalid

Tebuconazole w

Propiconazole w

Propiconazole I 1204100 241 631 26.1 62.4 284 63.0

Pyraclostrobin o Boskalid | 80 2 | 455 | 304 | 5205 | 245 | 611 | 204 (

Kontgol./-| | | 654 | 0 | 655 | 0 | 768 | 0

The most important indicators of cereal grain crops are the obtained yield level. The use of the studied combination (propiconazole and pyraclostrobin and boskalid) with different ratios of active substances has a positive effect on the preservation and increase of productivity (Table 3).

Table C

The yield of winter barley when applying the studied combinations in 2021 (Cherkas village, Bilotserkivskyi district, Kyiv region) or dk | Normanattayede | Yield ca

Prothioconazole Bixafen 120460

Propiconazole "I Pyraklostrobin w

Boscalid 100-00-80 64.4 18.1 20.3

Propiconazole "I Pyraklostrobin w

Boscalid 120-00-80 68.9 17.6 25.5

Propiconazole "I Pyraklostrobin w

Boscalid 100-20-80 64.7 15.4 20.7

Propiconazole "I Pyraklostrobin w

Boscalid 100-100-100 64.5 15.2 20.5

Tebuconazole "I Pyraklostrobin w

Boscalid 200-100-80 58.5 7.2 12.3

Tebuconazole x Pyraclostrobin 2004100 5 | 77717668 | whether

Propiconazole and pyraclostrobin 1004100 7573 | 60 2 YUDShshch | 105

Propiconazole and pyraclostrobin 120-100 and 612 | 99 | be 1111111 Boskald///////// | 777777 80777717171717171171111111537 11241147 11111111 Boskald////////// | 7777/7007 1777171711175487 77735 | 68 g F (11111111 Control /:/:|//ОЙ 77777771 11111011 Й11101 in

As a result of the use of the studied combination (Propiconazole i- Pyraclostrobin i

Boskalid) with different ratios of active substances, the preservation of grain yield, respectively, was 13.1-17.6 t/ha (20.3-25.5 95), compared to the control.

The use of the researched combination (propiconazole and pyraclostrobin and boskalid) with different ratios of active substances in winter barley crops helps to reduce damage by pests (barley leaf spotting) and increases the yield of the crop.

When processing winter barley crops with the studied combination (Propiconazole Zh

Pyraclostrobin and Boscalid) with different ratios of active substances have been found to effectively affect crop preservation, giving an increase of 20.3-25.5 95, respectively, while the use of a combination of Tebuconazole and Pyraclostrobin and Boscalid gives an increase in yield only at the level of 12.3 95, compared to the control variant.

The results of these studies should be considered in the long term and in view of the increase in yield. So, the combination of Propiconazole and Pyraclostrobin and Boscalid (120-100-80) provides an increase in yield of 25.5 965, while the combination of Propiconazole and Pyraclostrobin (120-100) provides a yield increase of 16.2 95, Boscalid (80) provides a yield increase of 4.7 96, which is evidence of the excellent effectiveness of the proposed combination of Propiconazole and

Pyraclostrobin and Boskalid and prospects for its use.

Example 2: Field tests of combinations of active substances against a complex of diseases in winter wheat crops 2.1. The period of the experiment: May - July 2021. The place of the experiment: the research and demonstration center of the company "Alfa Smart Agro" LLC (Cherkas village, Bilotserkivskyi district, Kyiv region), coordinates 49241734" N. W. 30211713" in. d. Soil and climate zone:

Right-bank forest-steppe of Ukraine. Target objects: helminthosporiosis spots, septoriosis, powdery mildew, rust diseases, powdery mildew. Culture: winter wheat. Sort:

Charodoyka Bilotserkivska. Planting density (seed sowing rate): 3.5 million similar seeds per 1 ha (200 kg/ha). Sowing (planting) date: 09/23/2020. Seedling emergence date: 10/02/2020. Phase of plant development during processing: tillering. Type of experiment: field. soil (type, mechanical composition, humus content (95), pH): chernozem with little humus, coarse dust - medium loam by mechanical composition on carbonate loess. 2.2. Scheme of the experiment:

Table 4 (Control (untreated).й/-/:///111111111111111ЙГ111t 2.3. Technology of using the research drug: Terms of treatments (application): 05/12/2021

From r. Multiplicity of treatments: 1. Method of application: spraying of vegetative plants. Used equipment: Nagaii MA5TEK RI Sh5 tractor sprayer. Rate of working solution: 200 l/ha.

Accounting dates: 05/19/2021, 05/26/2021, 06/02/2021 2.4. Test results and their analysis:

In the course of an experiment to test the tested combinations of fungicidal active substances for spraying vegetative plants of winter wheat, it was established that the drug is effective against septoriosis and pyrenophorosis of winter wheat, the development of which was observed in the flag leaf in the experimental plots.

Thus, in the course of the conducted research, it was established that when using the studied combinations (propiconazole, pyraclostrobin, and boskalid) of active substances with different ratios, a positive effect was obtained in terms of stopping the development and spread of pathogens.

When using the studied combinations (Propiconazole and Pyraclostrobin and Boskalid) of active substances with different ratios, the highest efficiency indicators were obtained, compared to other studied combinations. The presented results testify to the high biological efficiency of the studied combination (Propiconazole and Pyraclostrobin and

Boskalid) with different ratios of active ingredients.

Table 5

The effectiveness of the studied combinations against winter wheat diseases in 2021 (Cherkas village, Bilotserkivsky district, Kyiv region)

Rate per 1 ha, g d.r. Development, IEfficiency, Development, 96 Efficiency, | Development, | Efficiency, to to to to to

Propiconazole w

Pyraclostrobin same 125-125-100 12.8 781 14.3 70.9 15.1 70.0

Boscalid

Propiconazole w

Pyraclostrobin same 150-1-5-100 10.8 77.3 11.5 76.6 11.3 77.6

Boscalid

Propiconazole w

Pyraclostrobin I 125-50-00 12.3 741 144 70.7 14.8 70.6

Boscalid

Propiconazole w

Pyraclostrobin I 125-125-125 12.5 73.7 13.6 72.3 142 71.68

Boscalid

Tebuconazole w

Pyraclostrobin I 50-125-100 14.1 70.3 16.2 67.0 171 66.1

Boscalid

Tebuconazole w

Propiconazole w

Propiconazole is about Kontvol/:.:/// | 7/1 1475 | 0 | 4 | 0 | 5041 2 fshkhkfneio

Propiconazole w

Pyraclostrobin I 125-125-00 121 75.2 141 71.3 15.2 75.1

Boscalid

Propiconazole w

Pyraclostrobin I 150-25-00 10.3 78.9 11.2 77.2 8.4 842

Boscalid

Propiconazole w

Pyraclostrobin I 125-50-00 11.6 76.2 13.6 72.3 11.8 77.8

Boscalid

Propiconazole w

Pyraclostrobin I 125-125-125 11.9 75.6 13.5 72.5 13.7 742

Boscalid

Tebuconazole w

Pyraclostrobin I 50-125-100 13.5 72.3 141 71.3 141 73.4

Boscalid

Tebuconazole same 2504125 13.7 71.9 14.6 70.3 14.8 72

Pyraclostrobin

Propiconazole w

Propiconazole w

Kontvol /:|:. | (HER 4858 | 0 2 | 4 | 0 | 5 | 0

The most important indicators of cereal grain crops are the obtained yield level. The use of the studied combination (propiconazole and pyraclostrobin - Boskalid) with different ratios of active substances has a positive effect on the preservation and increase of productivity (Table 6).

Table 6

The yield of winter barley when applying the studied combinations in 2021 (Cherkas village, Bilotserkivskyi district,

Kyiv region) as 0000 Deventyatyae yuyuintt reve nene (Tebuconazole and Pyraklostrobin.y | 2504125 | 6956 | 01 | 145 (Control.///////777777777771111111111Ї111717171717111111Г111715855... |. .ЮЙЛо4 HER 4.ЮЙЮЙ20

As a result of the use of the studied combination (Propiconazole i- Pyraclostrobin i

Boskalid) with different ratios of active substances, the preservation of grain yield, respectively, was 13.1-017.6 c/ha (20.3-25.5 Fo), compared to the control.

The use of the researched combination (Propiconazole - Pyraclostrobin and Boskalid) with different ratios of active substances in winter wheat crops helps to reduce damage by pests (septoriasis, pyrenophorosis) and increases the yield of the crop.

When processing winter wheat crops with the studied combination (Propiconazole Zh

Pyraclostrobin and Boscalid) with a different ratio of active substances has been found to have an effective effect on crop preservation, giving an increase of 18.8-26.4 95, respectively, while the use of a combination of Tebuconazole and Pyraclostrobin and Boscalid gives an increase in yield only at the level of 15.6 95, compared to the control variant.

The obtained results can be explained by the synergistic effect of the developed combination.

For a combination of two active compounds, there is a synergistic effect if the activity of the composition containing both active compounds exceeds the sum of the activity of the two active compounds used separately. The expected activity for a given combination of two active compounds can be calculated using the so-called "Colby equation" (see 5.8. Soiru, "SaIsshatspa zZupegaiiviis apa Apiadopiviis Nezropzez oi Negriside Sotbipayiopv", UUeyedz 1967,15, 20-22):

E-AzB-(AkhB/100), where

A - the percentage of activity of compound A, if active compound A is used according to application rates in g/ha;

B - the percentage of activity of compound B, if the active compound B is used according to application rates in g/ha;

E - the percentage of the calculated activity, if compounds A and B are used together at application rates in g/ha;

If the actual activity observed for the combination of compounds A and B is greater than calculated, then the activity of the combination is superadditive, i.e. synergistic.

In this case, the combination of Propiconazole and Pyraclostrobin was taken as compound A, and Boskalid was taken as compound B. During the research, the activity of the combination of Propiconazole and Pyraclostrobin and Boscalid was separately investigated and their activity was compared with the activity of the combination of Propiconazole and Pyraclostrobin and Boscalid.

Indicative in this regard is the effectiveness in winter barley crops (see Table 5), where the biological effectiveness against Pyrenophorosis of the combination of Propiconazole and Pyraclostrobin (for 21 days) is 74.0 95, the biological effectiveness of Boskalid (for 21 days) is 21.3 95, and the calculated efficiency according to Kolbi of the combination Propiconazole w- Pyraclostrobin i- Boskalid is 79.595, while the observed efficiency of the combination Propiconazole w

Pyraclostrobin - Boscalid is 84.2 95.

The results of these studies should be considered in the long term and in view of the increase in yield. Yes, the combination of Propiconazole and Pyraclostrobin and Boskalid (150-4125-4-100)

provides an increase in yield of 21.3 95, while the combination of Propiconazole and Pyraclostrobin (1504-4125) provides an increase in yield of 11.6 95, Boskalid (100) provides an increase in yield of 2.7 U", which indicates the excellent effectiveness of the proposed combination Propiconazole w

Pyraclostrobin and Boscalid and the prospects of its use.

Example 3: Field tests of combinations of active substances against a complex of diseases in winter wheat crops 3.1. The period of the experiment: May - July 2021. The place of the experiment: the research and demonstration center of the company "Alfa Smart Agro" LLC (Cherkas village, Bilotserkivskyi district, Kyiv region...), coordinates 4924134" N. W. 30211713" in d. Soil and climate zone:

Right-bank forest-steppe of Ukraine. Target objects: helminthosporiosis spots, septoriosis, powdery mildew, rust diseases, powdery mildew. Culture: winter wheat. Sort:

Charodoyka Bilotserkivska. Planting density (seed sowing rate): 3.5 million similar seeds per 1 ha (200 kg/ha). Sowing (planting) date: 09/23/2020. Seedling emergence date: 10/02/2020. Phase of plant development during processing: tillering. Type of experiment: field. 3.2. Scheme of the experiment:

Table 7 (Control (no treatment) /-:///111111111111111ЙГ111t 3.3. Technology of application of the experimental drug: Periods of treatment (application): 12.05.2021. Multiplicity of treatments: 1. Method of application: spraying of vegetative plants. Used equipment: tractor sprayer Nagdi MAZTEK RHY5V.The norm of the working solution: 200 l/ha.

Accounting dates: 05/19/2021, 05/26/2021, 06/02/2021 3.4. Test results and their analysis:

In the course of conducting an experiment to test the studied combinations of fungicidal active substances for spraying vegetative plants of winter wheat, it was established that the preparation is effective against septoriosis and pyrenophorosis of winter wheat, the development of which was observed in the flag leaf in the experimental plots.

Thus, in the course of the conducted research, it was established that when using the studied combinations (propiconazole and pyraclostrobin and boskalid) of active substances with different ratios, a positive effect was obtained in terms of stopping the development and spread

Of the causative agents of diseases.

When using the studied combinations (Propiconazole and Pyraclostrobin and Boskalid) of active substances with different ratios, the highest efficiency indicators were obtained, compared to other studied combinations. The presented results testify to the high biological efficiency of the studied combination (Propiconazole and Pyraclostrobin and

Boskalid) with different ratios of active ingredients.

Table 8

The effectiveness of the studied combinations against winter wheat diseases in 2021 (Cherkas village, Bilotserkivsky district, Kyiv region)

Rate for 1 0 o nev neinth tre 9 9 9 9 9 iraklostobnBoskalid| Z0'67nBO | pz | in | is | in | zi | art

Continuation of table 8

Propiconazole w

Propiconazole w

Propiconazole is about Propiconazole 6031344106th 97 79.6 10.8 78.0 IR 78.0

Pyraclostrobin - Boskalid

Propiconazole same 11 Control/-/:. /U/| 77777777 | 475 1777/7071 | 491 | 2 sh(0 | 504 | 0

Propiconazole w

Propiconazole w

Propiconazole w

Propiconazole w

Propiconazole w

Propiconazole w

Propiconazole w

Propiconazole w

Propiconazole w

Control/-:| / // | -(K | 488 | (0 | 491 | 0 | 5m | 0

The most important indicators of cereal grain crops are the obtained yield level. The use of the studied combination (propiconazole and pyraclostrobin and boskalid) with different ratios of active substances has a positive effect on the preservation and increase of productivity (Table 9).

Table 9

The yield of winter wheat when applying the studied combinations in 2021 (Cherkas village, Bilotserkivskyi district, Kyiv region) d.r.

Solatenol

Propiconazole « Cyproconazole w

Soplatenol 104-33-42 656.43 6.93 10.4

Propiconazole « Cyproconazole w

Soplatenol 125-40-50 77.07 17.57 22.8

Propiconazole and Pyraclostrobin - Boskalid| 8046753 61.53

Propiconazole and Pyraclostrobin - Boskalid| 100-84-67 64.20

Propiconazole i Pyraclostrobin 4 Boscalid| 120--100--80 66.88

Propiconazole « Pyraclostrobin - Boskalid| 140--117-93 77.02 17.52

Propiconazole and pyraclostrobin and boscalid /160--134--106 87.70 28.20

Propiconazole « Pyraclostrobin - Boskalid|. 180--150--120 88.00 28.50 (11111111 Control /:.:..-:-|::-::6.::/ | | 59.50 70 1 0

As a result of the use of the studied combination (Propiconazole and Pyraclostrobin and

Boscalid) with different ratios of active substances, the preservation of grain yield, respectively, was 2.03-28.2 c/ha (3.3-32.4 95), compared to the control.

The use of the studied combination (Propiconazole - Pyraclostrobin and Boskalid) with different ratios of active substances in winter wheat crops helps to reduce damage by pests (septoriasis, pyrenophorosis) and increases crop yield.

When processing winter wheat crops with the investigated combination (Propiconazole

Pyraclostrobin i- Boscalid) with different ratios of active substances has been found to have an effective effect on crop preservation, giving an increase of 3.3-32.2 95, respectively, while the use of the combination Propiconazole i- Cyproconazole i- Solatenol gives an increase in yield only at the level of 6.7-22.8 90, compared to the control variant.

Example 4. Field tests of combinations of active substances against a complex of diseases in spring barley crops 4.1. The period of the experiment: April - August 2022. The place of the experiment: the research and demonstration center of the company "Alfa Smart Agro" LLC (Cherkas village, Bilotserkivskyi district, Kyiv region...), coordinates 4924134" N. W. 30211713" in d. Soil and climate zone:

Right-bank forest-steppe of Ukraine. Target objects: helminthosporiosis spots, septoriosis, powdery mildew, rust diseases. Culture: spring barley. Grade: Ninth Val. Planting density (seed sowing rate): 4 million similar seeds per 1 ha (150 kg/ha). 5.3. Sowing (planting) date: 04/23/2022. Seedling emergence date: 05/02/2022. Phase of plant development during treatment: tillering. 6.

Type of experiment: field. Soil (type, mechanical composition, humus content (95), pH): chernozem with little humus, coarse dust - medium loam by mechanical composition on a carbonate loam. 4.2. Scheme of the experiment:

Table 10 melons (22222222 as De o Control (untreated).//| 77777711 4.3. Technology of application of the experimental drug: Periods of treatments (application): 12.05.2022. Multiplicity of treatments: 1. Method of application: spraying of vegetative plants. Used equipment: tractor sprayer Nagdi MAZTEK RIG. Rate of working solution: 200 l/ha.

Accounting dates: 05/19/2021, 05/26/2021, 06/02/2021 4.4. Test results and their analysis:

In the course of an experiment to test the studied combinations of fungicidal active substances for spraying vegetative plants of spring barley, it was established that the drug is effective against septoriosis and pyrenophorosis of spring barley, the development of which was observed in the flag leaf in the experimental areas.

Thus, in the course of the conducted studies, it was established that when using the investigated combinations (Propiconazole and Pyraclostrobin and Boskalid) of active substances with different ratios, a positive effect was obtained in terms of stopping the development and spread

Of the causative agents of diseases.

When using the studied combinations (Propiconazole and Pyraclostrobin and Boskalid) of active substances with different ratios, the highest efficiency indicators were obtained, compared to other studied combinations. The presented results testify to the high biological effectiveness of the studied combination (Propiconazole and Pyraclostrobin and

Boskalid) with different ratios of active substances.

Table 11

The effectiveness of the studied combinations against net spotting of spring barley leaves in 2021 (Cherkas village, Bilotserkivsky district, Kyiv region...)

Valy de |Movyue! Geoznok Efottnvnet vovnok Efestvnietyu Roztk efestvnit

Option Development, Efficiency, | Development, IEfficiency,| Development, IEfficiency;

Propiconazole and Boskalid

Propiconazole w - Boskalid x 0.5 (KE) - Boskalid x 515 (KV - Boskalid x z (SV) - Boskalid x 15 (CE) - Boskalid

Kontvoli | - | (RF | 673 | 0 2 (| 7031 0 | 853| 0

The use of the researched combination (propiconazole and pyraclostrobin and Boskalid) with different ratios of active substances in spring barley crops helps to reduce damage by pests (septoriasis, pyrenophorosis) and increases the yield of the crop.

When processing spring barley crops with the investigated combination (Propiconazole and

Pyraclostrobin and Boscalid) in different forms of execution provided comparable activity.

The above results of field studies showed significant effectiveness and advantages of the obtained combination of fungicidal substances Propiconazole and Pyraclostrobin and Boscalid compared to known two-component and three-component fungicidal combinations, which makes it an effective product for protecting agricultural crops in field conditions.

Claims (12)

USEFUL MODEL FORMULA 1. The method of obtaining a fungicidal composition in the form of a suspoemulsion containing propiconazole, pyraclostrobin, boscalid and auxiliary agents, which includes the following stages: a) in the first reactor, boscalid and pyraclostrobin are combined in an acidic aqueous solution and the resulting mixture is dispersed, b) in the second reactors mix oil and propiconazole to obtain an emulsion, c) mix the dispersion of boscalid and pyraclostrobin from the first reactor with propiconazole emulsion from the second reactor to obtain a suspoemulsion. 2. The method according to claim 1, which differs in that an organic acid is used to create an acidic environment. Q. The method according to claim 2, which differs in that monocarboxylic, dicarboxylic or tricarboxylic acids are used as an organic acid. 4. The method according to claim 3, which differs in that the organic acid is an acid selected from the following group: formic acid, acetic acid, propionic acid, oxalic acid, malic acid, malonic acid, succinic acid, citric acid or trifluoroacetic acid. Zo 5. The method according to claim 4, which differs in that citric acid is used as an organic acid. 6. The method according to claim 1, which differs in that the pH of the fungicidal composition is 4.2-5.5. 7. The method according to claim 1, which differs in that the preparation of the dispersion of boscalid and pyraclostrobin in the first reactor and the emulsion of propiconazole in the second reactor is carried out in the presence of auxiliary agents. 8. The method according to claim 1, which differs in that propiconazole, pyraclostrobin, boscalid and auxiliary agents are mixed in the following ratio of components, by weight. 9o: propiconazole 15.0-25.0 pyraclostrobin 10.0-20.0 boscalid 7.0-15.0 auxiliary agents the rest. 9. The method according to claim 1, which differs in that propiconazole, pyraclostrobin, boscalid and auxiliary agents are mixed in the following ratio of components, by weight. 9o: propiconazole 17.0-23.0 pyraclostrobin 12.0-18.0 boskalid 9.0-13.0 auxiliary agents the rest. 10. The method according to claim 1, which differs in that propiconazole, pyraclostrobin, boscalid and auxiliary agents are mixed in the following ratio of components, by weight. 9o: propiconazole 18.0-20.0 pyraclostrobin 14.0-16.0 boskalid 11.0-13.0 auxiliary agents the rest. 11. The method according to claim 1, which differs in that propiconazole, pyraclostrobin and boscalid are mixed in a ratio of 1.1-1.3:0.9-1.1:0.7-0.9. 12. The method according to claim 1, which differs in that propiconazole, pyraclostrobin and boscalid are mixed in a ratio of 1.2:1.0:0.8.