RU2460292C1 - Fungicidal mixture, fungicidal means and method for control pathogenic fungi on their basis - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: invention relates to agriculture. Fungicidal mixture contains thiabendazole (I) and prochloraze (II) or its complex salt in weight ratios in terms of prochloraze from 1:25 to 25:1. Fungicidal agent additionally contains at least one surfactant and one solvent and, if necessary, auxiliaries. Fungicidal means can be represented in the form of suspension or emulsion. The above said mixture and the means are used to combat phytopathogenic fungi on plants, seeds, tubers and soil.

EFFECT: invention improves the efficiency of control fungi.

7 cl, 2 ex, 5 tbl

Description

The present invention relates to the field of agriculture.

The subject of the present invention is a fungicidal mixture containing thiabendazole and prochloraz as active substances, a fungicidal agent based on this mixture, as well as a method for controlling phytopathogenic fungi using the fungicidal mixture mentioned above and a fungicidal crop protection agent.

Thiabendazole (I) is the common name for the chemical compound 2- (thiazol-4-yl) benzimidazole, which is known from US Pat. No. 3,017415. Thiabendazole is a systemic fungicidal substance against a wide range of pathogens of fungal diseases of the following types: Aspergillus, Botrytis, Ceratoxystis, Cercospora, Cladosporium, Colletotrichum, Corticium, Diaporthe, Diplodia, Fusarium, Gibberella, Gloeosporium, Oospora, Penicillium, Phoma, Podosphaera leucotricha, Rhizoctonia, Sclerotinia, Septoria, Thielaviopsis, et al., 2006. p. 1019). The biological effect of thiabendazole is based on the inhibition of the mitosis process due to the binding of tubulin. Due to its wide spectrum of action, thiabendazole is an active substance of various fungicidal preparations, most often in a mixture with other active substances, for example, triazole derivatives such as tebuconazole (patent RU 2264711), ciproconazole (international application WO 2005/029960). Various commercial preparations were registered on the basis of thiabendazole, for example, the drug Vial TT, VSK (80 g / l thiabendazole + 60 g / l tebuconazole) CJSC August; Vincit, SC (25 g / l thiabendazole + 25 g / l flutriafol) Keminova A / C; Treasure, KS (60 g / l tebuconazole + 80 g / l thiabendazole + 60 g / l imazalil) LLC Agro Expert Group et al. (“List of pesticides and agrochemicals approved for use in the Russian Federation. 2010” , Moscow, 2010).

Prochloraz (II) is the common name for the chemical compound N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] -1H-imidazole-1-carboxamide, which is known from US Pat. No. 3,991,071, US 4,080,462. Prochloraz is a substance of systemic fungicidal action against a wide range of pathogens of fungal diseases of the following species in various cultures: Pseudocercosporella, Pyrenophora, Rhynchosporium, Septoria, Erysiphe, Alternaria, Botrytis, Pyrenopeziza, Sclerotinia, etc. (The Pesticide Manual 14th edition, 2006 , p. 860). The biological effect of prochlorase is based on the mechanism of inhibition of ergosterol. The combined use of prochlorase and its complex salts with other active substances is known, for example with tebuconazole, US patent 4845111 and application CN 101019545, ciproconazole of EP 714605 and GB 2191401. Various commercial preparations, for example, Mirage, KS (450 g / l prochlorase, have been registered on the basis of prochlorase). ) Makteshim-Agan Industries Ltd., Kinto Duo, KS (20 g / l of triticonazole + 60 g / l of prochlorase contained in a complex with zinc chloride (+2)) BASF Agro B.V. (“List of pesticides and agrochemicals approved for use in the Russian Federation. 2010”, Moscow, 2010).

The objective of the present invention is to expand the spectrum of biological action and increase the biological effectiveness of the above compounds.

In the present invention, the term "prochlorase" also encompasses its complex salts, of which the most preferred is a complex of prochlorase with manganese chloride with an oxidation state of manganese (+2).

The problem is solved by creating a fungicidal mixture containing, as active substances, a mixture of thiabendazole (I) and prochlorase (II) or its complex salt, taken in effective ratios, and the mass ratio (in terms of prochlorase) of substances (I) to (II) is 1:25 to 25: 1. It was unexpectedly found that the fungicidal effect of such a mixture of biologically active substances according to the present invention is higher than the sum of the action of the same substances used individually. Thus, there is a synergistic effect, and not a simple additive summation of their action.

Another object of the present invention is to provide a fungicidal agent consisting of thiabendazole (I) and prochlorase (II) or its complex salt, and containing at least one solvent (diluent) and one surfactant and, if necessary, auxiliary additives improving the properties of such agents. In this case, the mass ratio (in terms of cool) of the substances (I) to (II) is from 1:25 to 25: 1.

The fungicidal agent exhibits greater biological efficacy compared to the selected comparison drugs, including at lower consumption rates of the active ingredients in the composition of the agent, which results in a decrease in the environmental load on the environment. At the same time, through the use of active substances with different biological mechanisms of action, the risk of resistance in pathogenic organisms is reduced. The fungicidal agent in accordance with the present invention can be presented in the form of a suspension, preferably in the form of a suspension concentrate (abbreviation for SC) or emulsion, preferably in the form of an emulsion concentrate (abbreviated CE), nanoemulsion concentrate (abbreviated CNE) and microemulsion concentrate (abbreviated designation KME).

Suspension concentrates can be obtained by grinding a mixture of active substances with a diluent, surfactants in bead mills to achieve the desired particle size. After grinding, auxiliary additives are added to the suspension - acidity regulator, thickener, dye or biocide.

Microemulsion concentrates (CME) and nanoemulsion concentrates (CNE) are obtained by selecting the components of the organic phase and their quantitative content to obtain a thermodynamically stable product over time. When preparing spraying solutions (working solutions), these formulations form micro- and nanoemulsions (respectively) and are stable and transparent solutions with a particle size of 200-300 nm for CME and up to 200 nm for CNE. Fungicidal agents in accordance with the present invention retain their original physicochemical properties and biological activity under the influence of high or low temperatures during storage for a long period of time.

Fungicidal agents in accordance with the present invention retain their original physicochemical properties and biological activity under the influence of high or low temperatures during storage for a long period of time. As the main components of fungicidal agents can be used:

1) solvents (diluents) such as oil distillation products, in particular aromatic hydrocarbons, preferably C ₈ -C ₁₂ fractions, such as xylene mixtures or substituted naphthalenes; phthalic acid esters such as dibutyl or dioctyl phthalate; aliphatic hydrocarbons such as cyclohexane; or paraffins, alcohols and glycols, as well as their ethers and esters, such as ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; ketones like cyclohexanone; mineral or vegetable oils; polar solvents such as M-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylformamide, water;

2) surfactants - both nonionic and cationic and / or anionic surfactants with emulsifying, dispersing and wetting properties, it is also possible to use a mixture of surfactants. In particular, ethoxylated (di) tristyrylphenols, ethoxylated tristyrylphenol sulfates (phosphates), salts of ethoxylated tristyrylphenol sulfates (phosphates), ethoxylated alkylphenols, condensed alkylnaphthalenesulfonates, alkylbenzene, alkyl diphenylsulfonyl (alkylene diphenylsulfonyl) -phenyl sulfonates aryl) sulfonates, ethylene / propylene oxide block copolymers, ethoxy (propoxylated) polyarylphenols, polycarboxylate salts, polyethylene glycol fatty acid esters and m polyhydric alcohols.

As auxiliary additives, the described fungicidal agents may contain:

- antifreezes, due to which an increase in the stability of the product is achieved under long-term storage at high and low temperatures. As antifreeze agents, it is preferable to use glycolic antifreeze agents or glycerol. When using glycerin, it is also a homogenizing agent for the mineral or vegetable oil introduced into the composition of the composition;

- mineral or vegetable oils, the addition of which ensures the formation of a uniform film on the objects treated with a fungicidal agent, which determines the uniform distribution of fungicides over their entire surface;

- acidity regulators (or buffer additives) necessary to maintain the acidity range of the medium (pH value); citric acid and its salts, as well as salts of inorganic acids, preferably alkali metals of inorganic acids, such as sodium carbonate or sodium bicarbonate, can be used as such;

- antifoams to reduce foaming, preferably organosilicon, such as Penta 469 polydimethylsiloxane antifoam (Penta, Russia), Rodorsil (Rodia, Italy), Amersil (Ametec, Italy);

- dyes such as varnishes, for example Irgalit Rubin, Lac Rubin 2SK and Lac Rubin SK, which are calcium salts of 2-hydroxy-4 - [(4-methyl-2-sulfo (phenyl)] - azo-2-naphthalene carboxylic acid ( GOST 7436-74), the purpose of which is to ensure uniform coloring of the processed object;

- thickeners, which can be used xanthan gum, mineral substances, as well as polysaccharides, including cellulose thickeners;

- mold inhibiting biocides, such as 1,2-benzisothiazolin-3-one (CAS No. 2634-33-5) and 1,3,5-tris (2-hydroxyethyl) hexahydro-1,3,5-triazine (CAS No. 4719-04-4).

Patented fungicidal agents contain, in g / l, usually from 15 to 440 thiabendazole, from 10 to 440 prochlorase (based on prochlorase), from 5 to 215 surfactants or mixtures of surfactants, the rest is solvent and, if necessary, auxiliary additives, up to 1 l.

Another object of the present invention is a method of combating phytopathogenic fungi, characterized in that phytopathogenic fungi, their habitat or requiring protection from plants, seeds, tubers, soil or agricultural areas are treated with a fungicidal mixture or a fungicidal agent based on thiabendazole and prochlorase.

The following are examples of fungicidal preparations, their characteristics and evaluations of their effectiveness. The following examples illustrate but do not limit the present invention.

EXAMPLE No. 1

Obtaining sample No. 1 in the form of a suspension concentrate.

231.6 g of water, 55 g of diethylene glycol, 27.5 g of antifoaming agent and 5 g of sodium alkylaryl sulfonate are loaded into the reactor, 33 g of ethylene propylene oxide block copolymer preheated to a temperature of 45-60 ° C are added with stirring. Stirred for 10-15 minutes, after which 440 g of thiabendazole and 440 g of the prochlorase salt complex in terms of prochlorase were added. Mix thoroughly until a homogeneous suspension is formed and grind in a bead mill. 3.3 g of acidity regulator, 1.1 g of dye, 33 g of thickener and 0.5 g of biocide are added to the resulting product, after which the physicochemical parameters of the preparation are determined.

Similarly receive samples No. 5-10 and 12.

EXAMPLE No. 2

Obtaining sample No. 2 in the form of an emulsion concentrate.

751.9 g of cyclohexanone are charged into the reactor and 15 g of thiabendazole, 100 g of prochlorase are added, with stirring, heated to a temperature of 45-50 ° C. 80 g of alkylbenzenesulfonate, 5.5 g of ethoxy (propoxylated) fatty alcohol and 11 g of polyethylene glycol fatty acid ester and polyhydric alcohol. Stirred for 20-30 minutes until a homogeneous clear liquid was obtained, then 8.8 g of an acidity regulator and 8 g of antifoam were added. Filter through a filter and determine the physico-chemical characteristics of the drug.

In a similar manner, emulsion samples No. 3-4 and 11 of various kinds are obtained.

Table No. 1 presents the compositions of the obtained samples of fungicidal agents.

Evaluation of the quality indicators of fungicidal agent samples was carried out as follows: the viscosity of the obtained drug samples was determined on a Brookfield viscometer, stability was determined according to GOST 16484-79 and the CIPAC MT 161 method, dispersion was determined on a Fritsch Analysette 22 laser particle analyzer according to the CIPAC MT 187 method, the pH value was according to GOST R 50550.

Table No. 2 presents the physicochemical properties of the obtained samples.

As can be seen from these results, the samples obtained have high stability and dispersion.

Synergistic Evaluation

The effectiveness for a mixture of two biologically active substances in% was calculated according to the Colby formula and is determined as follows (COLBY LR "Calculating synergistic and antagonistic responses of herbicide combinations" ("Calculation of the synergistic and antagonistic expected action of mixtures of herbicides"). Weeds 15, p.20- 22, 1967), (LIMPEL et al. 1962 "Weeds control by. Certain combinations". Proc. NEWCL. Vol.16, pp. 48-53):

E _xy = (X + Y) - (X · Y) / 100,

where X is the biological effectiveness when using thiabendazole with a consumption rate of m, g / ha;

Y - biological effectiveness when using prochlorase with a consumption rate of n, g / ha;

E _xy - biological effectiveness with the combined use of thiabendazole and prochlorase with consumption rates of m and n, g / ha.

An efficacy of 0% corresponds to an efficacy without fungicide treatment, an efficacy of 100% means a complete suppression of pathogens. A synergistic effect always exists if the fungicidal effect of a mixture of biologically active substances is greater than the sum of the actions of the individual biologically active substances used.

From the examples in table No. 3 it can be seen that in all cases the actual effectiveness for the mixture of active substances is higher than that calculated by the Colby formula, i.e. there is a synergistic effect.

Biological Efficiency Assessment

Field tests of the obtained samples to assess the biological effectiveness were carried out by treating winter wheat plants (Dei cultivar) against septoria and winter wheat seeds (Krasnodar 99 cultivar) against root rot. The tests were carried out in comparison with known commercial preparations, such as Mirage, CE; VIAL TT, VSK and Kinto Duo, KE. The tests were carried out in accordance with the "Methodological guidelines for registration testing of fungicides in agriculture", ed. V.I.Dolzhenko, St. Petersburg, VIZR, 2009

During the growing season, the test samples were sprayed at the heading phase. Spraying was carried out with a backpack sprayer. The working fluid flow rate is 200 l / ha. The experiment was repeated four times, the area of each plot was 10 m ² . The degree of damage to plants by the pathogen of septoria at the date of registration was evaluated by the surface area covered by the disease.

Biological effectiveness (%) was evaluated by the formula:

where BE - biological effectiveness,%;

About - the degree of damage to plants on the date of accounting,%;

To - the degree of damage to plants in the control on the date of accounting,%.

The data of the test results are shown in table No. 4.

Evaluation of the effectiveness of the test samples as dressing agents was carried out by dressing the seeds with moisture before sowing. The flow rate of the working fluid is 10 l / t of seeds. The experiment was repeated four times, the area of each plot was 10 m ² . On each plot, the counts were carried out three times: in the autumn in the tillering phase and in the spring in the tillering phase and in the phase of formation of the 2nd node.

The development of the disease (%) was evaluated by the formula:

where R is the development of the disease,%;

a is the number of plants with the same lesion score (b);

N is the total number of plants;

K - the highest score of the accounting scale, equal to 4.

Biological effectiveness (%) was evaluated by the formula:

where BE - biological effectiveness,%;

Rk - the development of the disease in the control,%;

Rb is the development of the disease in the experiment,%.

The results are shown in table No. 5.

Claims (7)

1. A fungicidal mixture containing thiabendazole (I) and prochlorase (II) or its complex salt, and the mass ratio in terms of prochlorase of thiabendazole to prochlorase is from 1:25 to 25: 1. 2. The fungicidal mixture according to claim 1, containing thiabendazole (I) and prochlorase (II) or its complex salt in a synergistically effective amount. 3. A fungicidal agent containing thiabendazole (I) and prochlorase (II) or its complex salt at a weight ratio in terms of prochlorase of thiabendazole to prochlorase from 1:25 to 25: 1 and at least one surfactant and one solvent / diluent and, if necessary, auxiliary additives. 4. The fungicidal agent according to claim 3, containing, g / l:
thiabendazole from 15 to 440,
prochloraz or its complex salt from 10 to 440,
surface-active substance
or a mixture of surfactants from 5 to 215,
solvent / diluent and, if necessary, auxiliary additives up to 1 l. 5. The fungicidal agent according to claim 3 or 4, containing dye or antifreeze as an auxiliary additive. 6. The fungicidal agent according to claim 3 is presented in the form of a suspension or emulsion. 7. A method for controlling phytopathogenic fungi, characterized in that phytopathogenic fungi, their habitat or requiring protection from damage to plants, seeds, tubers, soil, agricultural areas are treated with the fungicidal mixture or fungicidal agent according to any one of claims 1 to 6.