RU2661392C1 - Fungicidal composition (versions) - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: group of inventions relates to fungicides, specifically fungicidal compositions against pathogenic fungi, containing active compounds from groups of strobilurins and triazoles, which are used to increase plant yield. Fungicidal composition according to the first version comprises the following components, g/l: azoxystrobin 150–220, prothioconazole 100–150, difenoconazole 50–100, triethanolamine salt of tristyrylphenyl polyglycol ether of phosphoric acid Soprophor FL (wetting agent – dispersant) 30–60, ethoxylated fatty amine Witcamine 4130A (activity enhancer) 20–80, ethoxylated castor oil Tagat V20 (emulsifier) 20–60, propylene glycol (antifreeze) 10, aerosil R812 (rheological additive) 10, methyl esters of fatty acids or vegetable oil up to 1 l (solvent) to 1 l. Fungicidal composition of the second version comprises the following components, g/l: azoxystrobin 150–220, prothioconazole 50–100, difenoconazole 50–100, block copolymer of ethylene oxide and propylene oxide Tensiofix DB08 (dispersant) 10–25, butyl block copolymer Atlas G5002L (dispersant) 5–15, propylene glycol (antifreeze) 75-100, aerosil 200 (stabiliser) 5, Penta 465 (defoamer) 2, Rhodopol 23 (thickener) 2, 1,2-benzisothiazolin-3-one (biocide) 2, polyvinyl alcohol 10 wt% aqueous solution (wetting agent – adhesive) 40, water (solvent) up to 1 l.

EFFECT: wider range of fungicidal agents with prolonged phytopathogenic activity, as well as maintaining low resistance of strains of pathogens.

2 cl, 4 tbl

Description

The invention relates to the field of fungicides, specifically to fungicidal compositions against pathogenic fungi, containing active compounds from the groups of strobilurins and triazoles, which are used to increase plant productivity.

The combined use of representatives of these groups of fungicides increases the spectrum of action, increases the efficiency of processing and allows to reduce the resistance of pathogens of powdery mildew and gray rot of various species on vegetable and cereal crops due to the simultaneous action of different mechanisms of damage to fungi.

Known compositions with pronounced fungicidal activity, allowing to influence the growth of phytopathogens containing compounds from the group of derivatives of strobilurins and triazoles, in particular azoxystrobin and diphenoconazole, and auxiliary components [Pat. CN 102669111, IPC A01N 25/04, A01N 43/54, A01N 43/653, A01P 3/00, 2012; Pat. CN 103461383, IPC A01N 25/12, A01N 43/54, A01N 43/653, A01N 61/00, A01P 3/00, 2013; Pat. CN 102870785, IPC A01N 25/04, A01N 43/54, A01N 43/653, A01P 3/00, 2013; Pat. WO 2015062358, IPC A01N 37/36, A01N 43/647, A01N 43/653, A01P 3/00, 2015].

Known compositions, including azoxystrobin and prothioconazole, which are well manifested against diseases of cereals, vegetables and fruit trees [Pat. CN 104621130, IPC A01N 43/54, A01N 43/653, A01P 3/00, 2015, Pat. CN 106889091, IPC A01N 43/54, A01N 47/18, A01P 3/00, 2017].

A common drawback of these compositions based on two active ingredients - azoxystrobin from the group of scrubirulins and one of the compounds of the triazole class - diphenoconazole or prothioconazole is that they do not provide complete control over diseases of cultivated plants or require increased consumption rates during processing.

Known compositions comprising a mixture of two triazole fungicides, in particular prothioconazole and diphenoconazole, which are effective against a wide range of plant diseases [Pat. W02003073851, A01N 43/653, A01N 55/10, 2003, Pat. CN 102578102, IPC A01N 43/653, А01Р 3/00, 2012, Pat. CN 102640748, IPC A01N 25/06, A01N 37/34, A01N 37/46, A01N 43/28, A01N 43/653, A01N 43/84, A01N 47/24, A01P 3/00, 2012], including for controlling the incidence of crops with septoria leaf spot [Application for US Pat. WO 2017162557, IPC A01N 43/653, А01Р 3/00, 2017], which allows for effective control of the incidence of grain [Pat. CN 105918336, IPC A01N 43/653, A01N47 / 18, A01P 3/00, 2015], vegetable crops and fruit trees [Pat. CN 104621126, IPC A01N 43/653, A01P 3/00, 2015].

The disadvantage of all known compositions based on two or more triazole derivatives, despite their better efficiency compared to single-component preparations, is the inability to significantly avoid or control the development of the resistance of microorganism strains to active active substances, which forces agricultural producers to increase the dosage of drugs and leads to increase the cost of processing.

Known compositions containing a fungicide from the group of strobilurins and two fungicides from the class of triazoles: azoxystrobin, diphenoconazole and ciproconazole [US Pat. CN 101911940, IPC A01N 43/54, A01N 43/653, A01P 3/00, 2010] for the prevention and control of diseases of crops, grapes, fruit trees and other crops, effectively suppressing powdery mildew, rust, downy mildew, alternariosis, late blight, rhizoctoniosis, various types of scab and other plant diseases, or azoxystrobin, diphenoconazole and tebuconazole [Handbook of pesticides and agrochemicals approved for use in the Russian Federation, Moscow, Agrorus, 2017, Oplot Trio, in the form of VSK from ZAO Fir and "August"] system for etching a growth stimulating effect of cereal seeds.

However, the lack of complete data on the biological testing of patented compositions does not allow us to evaluate their effectiveness and environmental load, and the effect of the Oplot Trio preparation does not cover the chemical protection of cultivated plants at the development and growth stage.

The closest is a fungicidal composition containing one of the five active substances from the group of amides of pyridinecarboxylic acid and a fungicidal system, including including azoxystrobin and / or prothioconazole and / or diphenoconazole. The composition may contain water, oil, antifreeze, wetting agent, dispersing and emulsifying agents, and is prepared by mixing the components in the form of an aqueous dispersion, suspension, oil-in-water emulsion, wettable powder or granules [US Pat. RU 2547554, IPC A01N 43/64, 2015].

The disadvantage of this composition is the low commercial availability of the main active substances - derivatives of pyridinecarboxylic acid amides, which complicates the practical use of fungicidal compositions based on them. In addition, the examples described in the patent have a narrowly targeted effect, and there is no assessment of the therapeutic activity of multicomponent mixtures.

The objective of the invention is the creation of a fungicidal composition for plant protection, which allows to reduce the environmental burden by minimizing the doses of chemicals introduced into the environment while maintaining the high efficiency of the protective treatments.

The technical result is the expansion of fungicidal action due to the proposed effective composition with prolonged phytopathogenic activity, as well as maintaining low resistance of pathogen strains.

The technical result is achieved according to the first embodiment when using a fungicidal composition containing a fungicidal system consisting of azoxystrobin, prothioconazole and diphenoconazole, and antifreeze propylene glycol, contains rheosol R812 as a rheological additive, and triethanolamine phenylpolyphosphoric triethanolamine salt is a wetting dispersant. as an activity enhancer - ethoxylated fatty amine Witcamine 4130A, as an emulsifier - castor ethoxylated Tagat V20 oil and in as a solvent - methyl esters of fatty acids or vegetable oil, in the following ratio of components, g / l: azoxystrobin 150-220, prothioconazole 100-150, diphenoconazole 50-100, triethanolamine salt of tristyrylphenylpolyglycol ester of phosphoric acid Soprophor FL 30-60, ethoxylated fatty amine Witcamine 4130A 20-80, castor ethoxylated Tagat V20 20-60 oil, propylene glycol 10, Aerosil R812 10, methyl esters of fatty acids or vegetable oil - up to 1 liter.

According to the second variant, the technical result is achieved using a fungicidal composition containing a fungicidal system consisting of azoxystrobin, prothioconazole and diphenoconazole, and propylene glycol antifreeze, contains 1,2-benzisothiazolin-3-one as a biocide, Aerosil 200 as a stabilizer, and wetting agent-polyvinyl alcohol in the form of 10 mass. % aqueous solution, as a dispersing agent - a mixture of a block copolymer of ethylene oxide and propylene oxide Tensiofix DB08 and butyl block copolymer Atlas G5002L, as a defoamer - Penta 465, as a thickening agent - Rhodopol 23 and as a solvent - water in the following ratio of components, g / l: azoxystrobin 150-220, protioconazole 100-150, diphenoconazole 50-100, block copolymer of ethylene oxide and propylene oxide Tensiofix DB08 10-25, butyl block copolymer Atlas G5002L 5-15, propylene glycol 75-100, aerosil 200 5, Penta 465 2, Rhodopol 23 2, 1,2-benzisothiazolin-3-one 2, polyvinyl alcohol (10 wt.% bottom solution) 40, water - up to 1 liter.

The essence of the composition is that its composition, proposed for processing crops, contains the active substances azoxystrobin, prothioconazole and diphenoconazole as part of a single composition, which has an enhanced effect due to the synergistic action of the active substances and the effect on various vital systems of pathogens, which makes it possible to a large extent Avoid the development of resistance of pathogen strains to active ingredients.

Moreover, as auxiliary additives, the composition may contain water, vegetable oil and its chemically modified derivatives, antifreeze, wetting agent, dispersing and emulsifying agents, thickener stabilizer, rheological additives.

The claimed compositions of the fungicidal composition are characterized by significant amounts of hydrophobic adjuvants and provide a reduction in the toxic load on the environment with increased fungicidal efficacy.

The preparation of the fungicidal composition is carried out by mixing the appropriate weight amounts of its components and bringing the resulting mixture to a volume of 1 liter by adding a solvent (vegetable oil or methyl esters of fatty acids, or water).

Examples of fungicidal compositions in the form of oil dispersions are presented in table 1.

Examples of fungicidal compositions in the form of suspension concentrates are presented in table 2.

The following components are used to prepare the composition:

Azoxystrobin is a fungicide of the strobilurin group (supplier Zhechem (China)). Prothioconazole is a fungicide from the class of triazole compounds (supplier Zhechem (China)). Difenoconazole is a fungicide from the class of triazole compounds (manufacturer Zhechem (China)).

The triethanolamine salt of tristyrylphenylpolyglycol ether of phosphoric acid, for example Soprophor FL, serves as a wetting and dispersing agent (manufacturer Rhodia Chem. Com. (Import)).

Ethoxylated fatty amine, for example Witcamine 4130A, enhances the activity of triazole fungicides (manufacturer Akzo Nobel Surface Chem. (Import)).

Castor ethoxylated oil, for example Tagat V20, acts as an emulsifier (manufacturer Evonik Industries AG (importation)).

A block copolymer of ethylene oxide and propylene oxide, for example Tensiofix DB08 - dispersing agent (manufacturer Omnichem (importation)).

Butyl block copolymer, for example Atlas G5002L - dispersing agent (manufacturer Croda Europe Ltd. (importation)).

Aerosil A200 and Aerosil R812 - stabilizer and rheological modifier (manufacturer: Evonik Industries AG (importation)).

Fatty acid methyl ester (manufacturer of Grodno Azot OJSC) or vegetable oil (for example: sunflower oil (producer of Rusagro Group of Companies LLC, soybean oil (manufacturer of Amuragrocentr LLC)), castor oil (manufacturer of ElGroup Company LLC), rapeseed oil (manufacturer OJSC "Kosulinskoye", LLC "ProFet") perform the functions of a solvent.

Propylene glycol - antifreeze (manufacturer (import, China)).

Polyvinyl alcohol - wetting and sticking agent (manufacturer Hebei Smart Chemicals Co. Ltd. (import)) - in the form of 10 mass. % aqueous solution.

Penta 465 - defoamer (manufacturer of Penta-91 LLC).

Rhodopol 23 - a derivative of xanthan gum - thickener-stabilizer (manufacturer RhodiaChem. Com. (Import)).

1,2-Benzisothiazolin-3-one biocide (importation).

The effect of the obtained fungicidal compositions was tested on strains MFG58984 Botrytis cinerea and MFP439011 Pyrenophora graminea, provided by the laboratory of mycology and phytopathology of the All-Russian Institute for Plant Protection.

To obtain a static culture of phytopathogenic fungi, 100 μl of a spore suspension of the fungus containing 10 ³ CFU was added to sterile flasks with 50 ml of sterile liquid nutrient medium. Fungicide solutions were added to these flasks. Mycelium was grown for 14 days. Then the culture fluid and mycelium were filtered through pre-dried at a temperature of 55 ° C and suspended filters (white or red ribbon), the resulting filters with mycelium were dried at a temperature of 55 ° C to constant weight, re-weighed and the mass of mycelium was calculated.

To account for phytotoxicity, segments of wheat leaves 12-15 mm long were used. The yellowing of the middle of the segment was taken into account. The experiments were carried out in 2-3 replicates, including 15-20 segments of leaves. The leaves were washed in running water with the addition of detergents to remove surface microflora. To simulate drought, leaf segments were placed for 1 hour in a 0.5 M glucose solution (osmotic potential of -12.38 atm at 25 ° C) with the addition of PEG600 polyethylene glycol to improve the wettability of the leaves until loss of turgor. Then, leaf segments were placed for 30 min in a 0.3 M sucrose solution (osmotic potential - 7.43 atm at a temperature of 25 ° C) containing fungicide in the studied dose. The change in the osmotic potential of water ensured the absorption of water and fungicide by cells. The processed leaf segments were transferred to Petri dishes with 1-2 ml of a fungicide solution prepared in a 0.3 M sucrose solution. The cups were set obliquely so that the leaves were covered with a solution. After 2-3 days, the number of green and yellowed leaves was taken into account, expressed as a percentage, the data were processed statistically. The criterion of phytotoxicity of fungicides on wheat leaves was yellowing.

For comparison, fungicidal compositions were tested corresponding to the compositions of tables 1 and 2, with the exception of the use of one or two active substances (AI) selected from azoxystrobin, prothioconazole and diphenoconazole.

The test results of fungicidal compositions in the form of oil dispersions are presented in table 3.

* The mass of mycelium in mg / 50 ml of liquid nutrient medium in an accumulative culture

The test results of fungicidal compositions in the form of suspension concentrates are presented in table 4.

* The mass of mycelium in mg / 50 ml of liquid nutrient medium in an accumulative culture.

As can be seen from tables 3 and 4, Botrytis cinerea is a less sensitive crop than Pyrenophora graminea.

All compositions with combinations of active substances (DV) effectively inhibit the growth of mycelium compared to the control, their effectiveness increases with increasing content of DV. Of the active substances, diphenoconazole is most effective, then - prothioconazole, the least effective in azoxystrobin. Compositions with combinations of two active ingredients are more effective than individual active ingredients. A composition with a combination of prothioconazole and diphenoconazole is more effective. Compositions with a combination of three active ingredients have the highest efficiency, the emergence effect is clearly visible. Compounds No. 3, 4, 7, and 8 were highly effective.

All drugs have phytotoxic properties. The most toxic is azoxystrobin, the least is prothioconazole. With an increase in the dose of all drugs, phytotoxicity increased as well as when using combinations of two and three DVs.

When comparing tables 3 and 4 it is seen that the effectiveness of the oil dispersion is slightly lower than the effectiveness of the suspension concentrate, and phytotoxicity is higher. In this embodiment, the phytotoxicity of drug No. 4 increased sharply (Table 3). Optimal is the oil dispersion of composition No. 3, because this composition has a significantly greater efficiency compared with compounds No. 1 and 2, and its phytotoxicity slightly differs from compounds No. 1 and 2.

The effectiveness of the suspension concentrate (Table 4) increased with an increase in the DV content more significantly than the efficiency of the oil dispersion. The phytotoxicity of the suspension concentrate was lower than the phytotoxicity of the oil dispersion. Based on the table. 4, the suspension concentrate of composition No. 8 is optimal, which had the greatest efficiency compared to compounds No. 5, 6, and 7, and its phytotoxicity did not increase compared to compounds No. 6 and No. 7.

Thus, fungicidal compositions containing a fungicidal system consisting of azoxystrobin, prothioconazole and diphenoconazole, and propylene glycol antifreeze, as well as 1,2-benzisothiazolin-3-one, aerosil 200, polyvinyl alcohol, a mixture of a block copolymer of ethylene oxide and butylene butylene -polymer, Penta 465 and Rhodopol 23 in water or Aerosil R812, triethanolamine salt of tristyrylphenylpolyglycol ether of phosphoric acid, ethoxylated fatty amine and castor ethoxylated oil in methyl ester of fatty acids or in vegetable oil e, at the stated ratio of components can extend fungicidal agents have an effective and prolonged phytopathogenic activity and provide a low resistance strains of pathogens.

Claims (4)

1. A fungicidal composition containing a fungicidal system consisting of azoxystrobin, prothioconazole and diphenoconazole, and antifreeze propylene glycol, contains rheosol R812 as a rheological additive, and triethanolamine salt of tristyrylphenylpolyglycolic acid phosphoric acid as an activity enhancer, is used as a wetting agent; Witcamine 4130A fatty amine, Tagat V20 castor ethoxylated oil as an emulsifier and fatty acid methyl esters or vegetable as a solvent ASO in the following ratio, g / l: Azoxystrobin 150-220 Prothioconazole 100-150 Diphenoconazole 50-100 Triethanolamine salt of tristyrylphenylpolyglycolic phosphoric acid ester Soprophor FL 30-60 Ethoxylated Fatty Amine Witcamine 4130A 20-80 Castor Ethoxylated Tagat V20 Oil 20-60 Propylene glycol 10 Aerosil R812 10 Fatty acid methyl esters or vegetable oil up to 1 l 2. A fungicidal composition containing a fungicidal system consisting of azoxystrobin, prothioconazole and diphenoconazole, and propylene glycol antifreeze, contains 1,2-benzisothiazolin-3-one as a biocide, aerosil 200 as a stabilizer, and polyvinyl alcohol as a wetting agent in the form of 10 mass. % aqueous solution, as a dispersing agent - a mixture of a block copolymer of ethylene oxide and propylene oxide Tensiofix DB08 and butyl block copolymer Atlas G5002L, as a defoamer - Penta 465, as a thickening agent - Rhodopol 23 and as a solvent - water in the following ratio of components, g / l: Azoxystrobin 150-220 Prothioconazole 100-150 Diphenoconazole 50-100 Block copolymer of ethylene oxide and propylene oxide Tensiofix DB08 10-25 Butyl block copolymer Atlas G5002L 5-15 Propylene glycol 75-100 Aerosil 200 5 Penta 465 2 Rhodopol 23 2 1,2-benzisothiazolin-3-one 2 Polyvinyl alcohol 10 mass. % water solution 40 Water up to 1 l