UA155365U - Method of preparation of fungicidal composition - Google Patents

Abstract

A method for obtaining a fungicidal composition in the form of an emulsion concentrate containing propiconazole, pyraclostrobin, boscalid and auxiliary agents. The method comprises dissolving boscalid, pyraclostrobin and propiconazole in an organic solvent at an elevated temperature, adding auxiliary agents and mixing the mixture to obtain an emulsion concentrate.

Description

The useful model belongs to the field of chemical protection of agricultural crops, in particular, it concerns fungicidal compositions intended for the protection of cultivated plants, in particular, grain crops from diseases of fungal etiology and the method of their production.

Fungicides (from the Latin rypadi - mushroom and saido - 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 drugs was established in the 18th 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 in the middle of 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 a poisoner are: the spectrum of fungicidal activity, especially against powdery mildew diseases, the peculiarities of the spread of pathogens in this region, phytoexpertise of seed material, 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 processing plants 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 by the formula:

SI o o

SI

M

(AND

M /

Propiconazole was first described in patent 50 649316 (priority 18.11.1974), the applicant

Janssen Pharmaceutika N.V., (MI). 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|IoxymethylIphenyl|-M-methoxycarbamate), is characterized by the following structural formula: -- сг 97

M

-sh- M o. t sn, o

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 suppresses the respiration of the pathogen, accumulates on the surface of the leaf, then is gradually redistributed into the 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 No. 48138 (date of filing 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. US patent 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 should 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, expanding the spectrum of action, increasing activity due to synergistic action, reducing 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 Shchi xx

Because Mo belongs to the class of carboxamides and blocks the key stage of mitochondrial respiration of cells that cause diseases. Boscalid 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).

Ukrainian patent No. 65601 described a fungicidal combination containing, in particular, a combination of boscalid and propiconazole. But as it follows from the data of the conducted studies, although this combination shows a synergistic effect, the level of activity against Voiguii5 Sipegea is quite low, only 3595. In OA 54425, the effect of combinations of boscalid and propiconazole with

With different ratios of active substances for different pathogens.

The basis of a useful model is the task of expanding the range of fungicidal compositions for the protection of cultivated plants from various diseases and pathogens, in particular, to prevent the development of such diseases as helminthosporous spots, septoriosis, powdery mildew, rust diseases, etc.

The inventors discovered that the combination of propiconazole, pyraclostrobin and boscalid in certain proportions provides a fungicidal composition with 3 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, along with this, will provide an increase in the yield of wheat, barley, sunflower, soybean, rapeseed, etc.

The task is solved in the method of obtaining a fungicidal composition in the form of an emulsion concentrate containing propiconazole, pyraclostrobin, boscalid and auxiliary agents, in which boscalid, pyraclostrobin and propiconazole are dissolved in an organic solvent at elevated temperature, auxiliary agents are added and the mixture is mixed to obtain an emulsion concentrate.

In one of the implementation options of the useful model, a mixture of carboxylic acid amide and carboxylic acid ester is used as an organic solvent.

In another variant, a mixture of dimethylformamide and ethyl acetate is used as an organic solvent.

In addition, the dissolution of boscalid, pyraclostrobin and propiconazole in an organic solvent is carried out at a temperature of 40-60 2.

In one of the variants of the implementation of the useful model, propiconazole, pyraclostrobin, boskalid and auxiliary agents are mixed, with the following ratio of components, by weight. 9: propiconazole 15.0-25.0 pyraclostrobin 10.0-20.0 boscalid 7.0-15.0 auxiliary agents the rest.

In another version of the implementation of the useful model, propiconazole, pyraclostrobin, boscalid and auxiliary agents are mixed, with the following ratio of components, by weight. 9: propiconazole 17.0-23.0 pyraclostrobin 12.0-18.0 boscalid 9.0-13.0 auxiliary agents the rest.

In another version of the implementation of the useful model, propiconazole, pyraclostrobin, boscalid and auxiliary agents are mixed, with the following ratio of components, by weight. 9: propiconazole 18.0-20.0 pyraclostrobin 14.0-16.0 boscalid 11.0-13.0 auxiliary agents the rest.

In another version of the implementation of the useful model, propiconazole, pyraclostrobin and boscalid are mixed in a ratio of 1.1-1.3:0.9-1.1:0.7-0.9.

In yet another implementation of the useful model, 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, a result was found when using a combination of propiconazole, pyraclostrobin and boscalid in a ratio of 1.2:1.0:0.8. This combination provides not only improved control of fungal diseases, but also provides 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.

An effective way to solve the problem of recrystallization is the introduction into the composition

From the formulations of additional components that 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.

In the course of research, a fungicidal composition containing propiconazole, pyraclostrobin and boscalid was obtained in the form of an emulsion concentrate.

Dimethylformamide and ethyl acetate acted as a medium for this emulsion concentrate, which, in combination with suitable emulsifiers, made it possible to create a stable, highly concentrated emulsion of propiconazole, pyraclostrobin, and boscalid.

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, for example, 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; glycol 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 surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, substances that promote 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 alkylnaphthalenes 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 alkylbenzene sulfonates are sodium,

Calcium or triethylammonium salts of dodecylbenzenesulfonic acid, in particular Kpodasayu 70/38 (7095 calcium dodecylbenzenesulfonate in n-butanol), EPodasakyus b0O/BE (6095 calcium dodecylbenzenesulfonate in 2-ethylhexanol) and VPodasayu 2283 (7095 ammonium dodecylbenzenesulfonate), Arnodia company StrN , phenylsulfonate CA 100 (4095 calcium dodecylbenzenesulfonate in Seporo! X-060 and boimevz5o 200) of Siagapi StrN or

MapzaF EMM 70/2E (5795 linear dodecylbenzenesulfonate in 2-ethylhexanol) of AiBbgidny and MOP.

Suitable nonionic surfactants are alkoxylates, M-substituted fatty acid amides, amine 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 alkylpolyglycosides. Examples of polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vinyl alcohol or vinyl acetate.

Suitable cationic surfactants are quaternary surfactants, for example, 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 oxylates 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 (for example, 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 Ffungicidal composition of the useful model is silicon dioxide

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

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

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; phosphates of alkali and alkaline earth metals, such as sodium phosphate,

From 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), and 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 fungicidal composition is a suspoemulsion and an emulsion concentrate.

The 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 with different contents of active ingredients were obtained and studied, namely:

Composition 1. Suspoemulsion (CE)

Ripakovaoliya.d 77771717 Emulator.7///// | 6677 methylisothiazolinone oon they vv butylhydroxytoluene in natural Antioxidant 0.08 refined deodorized oil omega-hydroxy-polyglycol ether

Citric acid 77777771 Koreorrn/-/ | 77,009 sh-::

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 45-507C. 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 fungicide composition are intended only to illustrate and explain the useful model and are not intended to limit it in any way.

Determining the biological effectiveness of active substances and their combinations on sunflower and soybean crops for protection against a wide range of diseases consisted in setting up field studies in fourfold repetition.

To conduct the study, 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 cultures; harvest accounting was carried out.

The research was carried out according to generally accepted methods (Methodology of testing and application of pesticides / edited by Prof. S.O. Tribelia, Kyiv, "Svit" - 2001; Fundamentals of scientific research in agronomy // Moiseichenko V.F., Yeshchenko V.O. - K. Higher School, 1994. p. - 334;

Determination of 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. S. - Zb)

Example 1. Field tests of combinations of active substances against a complex of diseases in winter barley crops. 1.1 The period of the experiment: April - July 2021. 2. 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" p. w. 30211713" in 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-grained-medium loamy by mechanical composition on carbonate loess. 1.2 Scheme of the experiment:

Table 1

Control (unprocessed) /-/-/://111111

Boskald.'i ////777777711111111111111111111111111111111111180сссСс2 1.3 Technology of using the experimental drug: Time of treatments (application): 04/20/2021. Multiplicity of treatments: 1. Method of application: spraying vegetative 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 an experiment to test the studied combinations of fungicidal active substances for spraying vegetative plants of winter barley, it was established that the preparation 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 investigated 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, in comparison with 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 2

The effectiveness of the investigated combinations against net spotting of barley leaves in 2021 (Cherkas,

Bilotserkivsky district, Kyiv region)

MS stv asan t chassis d.r. Sativity, 90 Sativity, because Sativity, 90

Prothioconazole --

Propiconazole yah

Pyraclostrobin | 100-100-80 24.8 62.1 26.7 61.6 29.7 61.3

Boscalid

Propiconazole yah

Pyraclostrobin | 120-100-80 19.6 75.0 19.6 71.8 23.7 691

Boscalid

Propiconazole yah

Pyraclostrobin | 100--120--80 21.6 67.0 23.1 66.8 26.3 65.8

Boscalid

Propiconazole yah

Pyraclostrobin -| 100--100--400 23.7 63.8 26.1 62.4 29.6 61.5

Boscalid

Tebuconazole w

Pyraclostrobin | 200-100-80 24.9 61.9 26.9 61.3 30.4 60.4

Boscalid

Tebuconazole w

Propiconazole yah

Propiconazole yah

Boskald. | 80 | 455 | 304 | 525 | 245 | 61 | 204

Control | (| 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 investigated combinations in 2021 (Cherkas village,

Bilotserkivsky district, Kyiv region)

Rate per hectare, gdr. | Crop capacity,

R AR. c/ha 120460

Propiconazole w

Propiconazole w

Propiconazole w

Propiconazole w

Tebuconazole

Tebuconazole

Propiconazole w

Table C

The yield of winter barley when applying the investigated combinations in 2021 (Cherkas village,

Bilotserkivsky district, Kyiv region)

Yield, to |Nornentetde Mu! thanks r

Propiconazole w

Praostobm 00000000 1699062

Boskald. С Я777771717117801111111111115371111124 | 47

Boskald. 77/77/1100 17711548 3.5 | 68

Zhkontrol.//////7777777171Ї7717171717171711111111111111111513 111010

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 - 25.5905), 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 a different ratio of active substances has been found to have an effective effect on crop preservation, giving an increase of 20.3-25.595, respectively, while the use of a combination of Tebuconazole and Pyraclostrobin and Boskalid gives an increase in yield only at the level of 12.395, in 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. Thus, the combination of Propiconazole and Pyraclostrobin and Boscalid (1204-100-80) provides a yield increase of 25,595, while the combination of Propiconazole and Pyraclostrobin (120-100) provides a yield increase of 16,295, Boscalid (80) provides a yield increase of 4,795, which is evidence of the excellent effectiveness of the proposed combination Propiconazole Zh

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 4924134" N. N. 3021173 " 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-grained and medium-loamy in mechanical composition on carbonate loess. 2.2. Scheme of the experiment:

Table 4

Control (unprocessed). 111111

2.3. Technology of application of the experimental drug: Time of treatments (application): 12.05.2021 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 studied 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, in comparison with 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 5

The effectiveness of the researched combinations against winter wheat diseases in 2021 (Cherkas,

Bilotserkivsky district, Kyiv region...)

Normanagh 22-53. Sbeptoroz./////////7777111111111c and

D " Roz-Efek- Roz-Efek- Roz-Efek- "V. origin, 95 | tivity, 95 | origin, 95 |tivity, 9Uo| turn, to | tiveness, 9Uo

Propiconazole w

Pyraclostrobin (792199) 128 73 143 70.9 15 70.0

Boscalid

Propiconazole w

Pyraclostrobin r 10.8 778 115 76.6 113 716

Boscalid

Propiconazole w

Boscalid

Propiconazole w

Pyraclostrobin in 125 7377 13.6 723 142 718

Boscalid

Tebuconazole

Pyraclostrobin o 141 703 162 67.0 174 vv

Boscalid

Tebuconazole

Propiconazole w

Propiconazole w

Control | -(G,Y 475 | 0 2 | 491 | 0 | 504| 0

Table 5 (continued)

Pyrenophorosis

Norm that " Effectiveness Effectiveness Effectiveness Dr. origin, 95 Effectiveness, 95| Effectiveness, 95 | Effectiveness, Uo| Effectiveness, to | Effectiveness, 9Uo

Propiconazole w

Pyraclostrobin I | 179129| 424 75.2 144 718 132 75; -100

Boscalid

Propiconazole w

Boscalid

Propiconazole w

Pyraclostrobin I | 1791501 446 762 13.6 723 11.8 778; -100

Boscalid

Propiconazole w

Pyraclostrobin I | 179129) 419 75.6 13.5 72.5 13.7 742 - 125

Boscalid

Tebuconazole

Pyraclostrobin I |290125| 435 723 144 718 144 73A; -100

Boscalid

Tebuconazole

Propiconazole w

Propiconazole w

Control | | 488 | 0 | 491 | 0 | 53 | 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 6).

Table 6

The yield of winter barley when applying the investigated combinations in 2021 (Cherkas village,

Bilotserkivsky district, Kyiv region)

Rate per 1 ha, g| Productivity Addition to the harvest d.r. c/ha in Boscalid in Boscalid in Boscalid -- Boscalid in Boscalid

Tebuconazole and pyraclostrobin 2504125 | 696 | 101 | 145

Propiconazole and pyraclostrobin 125-125

Propiconazole and pyraclostrobin 150-125

Zhkontrol.///////7777777771111111111111111111111Ї111171595.. | OO | 0 "(

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 c/ha (20.3 - 25.5965), compared to the control.

The use of the researched combination (propiconazole and pyraclostrobin and boskalid) with different ratios of active substances in winter wheat crops helps to reduce damage by pests (septoriasis, pyrenophorosis) and increases crop productivity.

When processing winter wheat crops with the investigated combination (Propiconazole and

Pyraclostrobin and Boscalid) with different ratios of active substances has been found to have an effective effect on crop preservation, giving an increase of 18.8-26,495, respectively, while the use of a combination of Tebuconazole and Pyraclostrobin and Boscalid gives an increase in yield only at the level of 15,695, in 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 74.095, the biological effectiveness of Boskalid (for 21 days) is 21.395, and the calculated effectiveness according to Kolb the combination of Propiconazole and Pyraclostrobin and Boscalid is 79,595, while the observed effectiveness of the combination of Propiconazole and

Pyraclostrobin and Boscalid is 84.295.

The results of these studies should be considered in the long term and in view of the increase in yield. Thus, the combination of Propiconazole and Pyraclostrobin and Boscalid (150-4125-100) provides a yield increase of 21,395, while the combination of Propiconazole and Pyraclostrobin (150-125) provides a yield increase of 11,695, Boscalid (100) provides a yield increase of 2,195, which indicates an excellent effectiveness of the combination of Propiconazole and Pyraclostrobin

Boskalid and 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. N. 3021173 " 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 (unprocessed).i /-/-/:///11111 3.3. Technology of application of the experimental drug: Time of treatments (application): 12.05.2021 Multiplicity of treatments: 1. Method of application: spraying of vegetative plants. Used equipment: Nagdi MAZTEK RGIV tractor sprayer. Rate of 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 an experiment to test the investigated 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 pathogens.

When using the studied combinations (Propiconazole and Pyraclostrobin and Boskalid) of active substances with different ratios, the highest efficiency indicators were obtained, in comparison with 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 researched combinations against winter wheat diseases in 2021 (Cherkas,

Bilotserkivsky district, Kyiv region)

The norm is 1

Responsiveness, 90 Responsiveness, 90 Responsiveness, 90

Propiconazole w

Cyproconazole | 834-27-33 14.8 68.8 15.5 68.4 17.6 64.7

Solatenol

Propiconazole w

Cyproconazole «| 104-33-42 13.7 71.2 14.3 70.9 15.4 69.4

Solatenol

Propiconazole w

Cyproconazole «| 125-40-50 122 74.3 13.5 72.5 143 71.6

Solatenol

Propiconazole w

Pyraclostrobin | 80-67-53 14.3 15.6 68.2 18.1 641 in Boskalid

Propiconazole w

Pyraclostrobin | 100-84-67 121 74.5 14.5 70.5 14.7 70.8 in Boskalid

Table 8

The effectiveness of the researched combinations against winter wheat diseases in 2021 (Cherkas,

Bilotserkivsky district, Kyiv region)

The norm is 1

Responsiveness, 90 Responsiveness, 90 Responsiveness, 90 - | 1 g 71 in Boskalid still rye ze p) meto ev| t

Pyraclostrobin |140-117-93| 10.9 717 122 75.2 12.6 75.0 in Boskalid

Propiconazole is the same as in Boskalid

Propiconazole same mon nn in Boskalid

Control | (P | 475 | 0 | 491 | 0 | 504 | 0

Table 8 (continued)

The norm is 1

Zo tivity, 9bo | turn, 95 | tivity, 905 | turn, 95 | tivity, 90

Shesreeitvyutmo ze te. zvo te me) ve

Cyproconazole 834-27-33 13.2 73.0 13.8 71.9 17.8 66.5

Solatenol

Propiconazole w

Solatenol

Shesreyuit evnovo zvoveo poten) tv

Cyproconazole « | 125-40-50 79.9 11.1 717.4 14.9 71.9

Solatenol

First, we call ze te |z, oti i) tv

Pyraclostrobin | 80-67-53 12.8 73.8 13.7 721 14.7 72.3 in Boskalid

Peshdee women zeove svv | t

Pyraclostrobin | 100-84-67 12.8 73.8 12.9 73.7 141 73.4 in Boskalid

Pedene zno pz theo. zvo ve) in

Pyraclostrobin I120-100-80| 11.5 76.4 12.5 74.5 13.4 74.8 in Boskalid

Ped zhyuinno not your pi that || she

Pyraclostrobin I140-117-93| 11.8 75.8 11.7 76.2 121 77.2 -- Boskalid

Propiconazole is the same as in Boskalid

Propiconazole is the same as in Boskalid

Control | (| 488 | 0 | 491 | 0 | 5 | 0

The most important indicators of cereal grain crops are the obtained yield level. Application of the studied combination (Propiconazole and Pyraclostrobin and Boskalid)

with a different ratio 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 investigated combinations in 2021 (Cherkas village,

Bilotserkivskyi district, Kyiv region) ssh SHE teach ha, g d.r. c/ha

Solatenol olathenol

Propiconazole is the same as Cyproconazole ov 40150) 7707 1757

Solatenol oskalide

Propiconazole same as Pyraclostrobin same | 0, 84467 6420

Boscalid oskalid

Propiconazole and pyraclostrobin. 50.147193 7702 1752

Boscalid

Propiconazole same as Pyraclostrobin same |. 41344106 87.70 28.20

Boscalid

Propiconazole and pyraclostrobin. 83.1504120 88.00 28.50 oskalid

Control.//////7777777711111Ї11111с1 at 59.50 7.0 1 0

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 2.03-28.2 t/ha (3.3-32.4905), compared to the control.

The use of the researched combination (propiconazole and pyraclostrobin and boskalid) with different ratios of active substances in winter wheat crops helps to reduce damage by pests (septoriasis, pyrenophorosis) and increases crop productivity.

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

Pyraclostrobin i- Boscalid) with different ratios of active substances has been found to have an effective effect on crop preservation, giving an increase of 3.3-32.295, respectively, while the use of the combination Propiconazole i- Cyproconazole i- Solatenol gives an increase in yield only at the level of 6 ,7-22,895, in comparison with 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 49241734" N. N. 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-grained-medium loamy by mechanical composition on carbonate loess.

4.2. Scheme of the experiment:

Table 10. . The rate of spending on ooovaandouu/ de M aedv

Control (unprocessed). (:::ГС77777777с7ссс-1111111111111111111111Ї111111- 4.3. Technology of application of the experimental drug: Time of treatments (application): 12.05.2022. Multiplicity of treatments: 1. Method of application: spraying of vegetative plants. Used equipment: tractor sprayer Nagaii MA5TEK RI Sh5. Worker's rate 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 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, in comparison with 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 11

The effectiveness of the studied combinations against net spotting of spring barley leaves in 2021 (p.

Cherkas, Bilotserkiv district, Kyiv region) sen li OB DE EN ntkreya

Sha turn, to |tivity, 90 sotivity, 9o | turn, 95 | tiveness, 9o

Bakova Propiconazole same mixture Pyraclostrobin 100-84-67 11.9 82.3 13.8 80.4 17.8 791 in Boskalid

Bakova Propiconazole and a mixture of Pyraclostrobin 150-125-100| 170.8 84.0 12.4 82.4 15.4 81.9 in Boskalid seter en ze in | me| the same) then

Me812 0.5 | Pyraclostrobin! 100-84-67 12.5 81.4 14.5 79.4 18.5 78.3 (KE) t Boscalid

The language of the ram is the language of the world

Mo812 Pyraclostrobin I150--125--100| 11.3 83.2 13.9 80.2 17.9 79.0 0.75(KE)| from Boscalid

Happy birthday! zvoteneteo in t

Me813 0.5 | Pyraclostrobin! 100-84-67 12.5 81.4 14.5 79.4 19.5 771

The same Boskalid

Moshenu me ve | | still) you

Me813 Pyraclostrobin 150-125-100| 10.9 83.8 183.1 81.4 16.1 81.1 0.75 (SE) t Boscalid

Her account 77717171 6793 | 0 | 7035 | 0 | 853| 0

The use of the studied combination (propiconazole, 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 studied combination (Propiconazole Zh

Pyraclostrobin and Boscalid) in different forms provided comparable activity.

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

Claims (9)

USEFUL MODEL FORMULA 1. The method of obtaining a fungicidal composition in the form of an emulsion concentrate containing propiconazole, pyraclostrobin, boscalid and auxiliary agents, in which boscalid, pyraclostrobin and propiconazole are dissolved in an organic solvent at elevated temperature, auxiliary agents are added and the mixture is mixed to obtain an emulsion concentrate. 2. The method according to claim 1, which differs in that a mixture of carboxylic acid amide and carboxylic acid ester is used as an organic solvent. 3. The method according to claim 1, which differs in that a mixture of dimethylformamide and ethyl acetate is used as an organic solvent. 4. The method according to claim 1, which differs in that the dissolution of boscalid, pyraclostrobin and propiconazole in an organic solvent is carried out at a temperature of 40-60 "С. 5. 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. 6. 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. 7. 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. 8. 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. 9. 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.