Synergistic sterilization composition

Abstract

To provide a novel fungicidal composition showing broader activity and synergistic effect.SOLUTION: The present invention provides a synergistic fungicidal composition. The synergistic fungicidal composition comprises a strobilurin-based compound, validamycin, and a compound A selected from the group comprising thifluzamide, hexaconazole, propiconazole, tricyclazole and difenoconazole.SELECTED DRAWING: None

Description

Detailed Description of the Invention

[0001] [Field of the Invention] The present invention relates to a synergistic bactericidal composition. More specifically, the present invention relates to a synergistic bactericidal composition comprising a strobilurin compound, validamycin, and Compound A selected from the group consisting of difenoconazole, hexaconazole, propiconazole, tricyclazole, and difenoconazole. The present invention also relates to a method for producing such a composition.

[0002] [Background of the Invention] Various compositions have been developed for controlling fungi and are actually used as single agents or mixtures. Practical agricultural experience has shown that repeated and exclusive application of individual active compounds in the control of harmful fungi often leads to the rapid selection of fungal strains that are naturally or adaptively resistant to the active compound in question. Effective control of these fungi using the active compound in question is very difficult in such cases.

[0003] European Patent Application No. 1872658A1 provides a composition for preventing harmful organisms. The composition contains a diamine derivative represented by formula (1).

[0004] [Chemical Formula]

[0005] In the formula, R1 represents a hydrocarbon having 1 to 6 carbon atoms substituted with a halogen, etc., R2 and R7 each independently represent a hydrogen atom, a hydrocarbon having 1 to 6 carbon atoms, etc., R3 and R4 each independently represent a hydrogen atom, an optionally substituted hydrocarbon having 1 to 6 carbon atoms, etc., or R3 and R4 represent a cycloalkyl group to which carbon atoms having 3 to 6 carbon atoms are bonded, R5 and R6 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, etc., and R8 represents an optionally substituted arylalkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. The composition further comprises, as an active ingredient, one or more compounds selected from the group consisting of other fungicides, insecticides, and acaricides.

[0006] International Publication No. 2008075454 provides a composition comprising a compound of formula 1 or 5 in combination with an insecticide.

[0007] [ka]

[0008] In formulas (1) and (5), A1, A2, A3, and A4 each represent a carbon atom, a nitrogen atom, or a nitrogen oxide atom; R1 and R2 independently represent a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 alkylcarbonyl group; G1 and G2 independently represent an oxygen atom or a sulfur atom; and X may be the same or different, represent a hydrogen atom, a halogen atom, a C1-C3 alkyl group, or a trifluoromethyl group. This provides a long list of insecticides, including metminostrobilurin, validamycin, tricyclazole, hexaconazole, propiconazole, or tifluzamide.

[0009] European Patent No. 2094087 relates to an insecticidal composition comprising an anthranilamide compound or a salt thereof, as well as other insecticides and / or fungicides.

[0010] To reduce the risk of selecting resistant strains, mixtures of various active compounds are conventionally used today to control harmful fungi. By combining active compounds with different mechanisms of action, it is possible to ensure effective control over relatively long periods.

[0011] Therefore, there is a need to develop novel fungicide compositions that exhibit broader activity and synergistic effects in order to minimize the amount of chemicals released into the environment, reduce treatment costs, and avoid or control the emergence of resistant strains to the active ingredients or mixtures of known active ingredients used by agricultural workers. Synergistic compositions that are physicochemically compatible formulations that are storage stable, safely packaged, and available in ready-to-use formulations are also needed.

[0012] [Summary of the Invention] The inventors of the present invention have surprisingly found that a composition comprising a strobilurin compound, validamycin, and compound A selected from the group including tifluzamide, hexaconazole, propiconazole, tricyclazole, and difenoconazole provides an enhanced synergistic bactericidal effect.

[0013] Accordingly, the present invention provides a synergistic composition comprising a strobilurin compound, validamycin, compound A selected from the group including tifluzamide, hexaconazole, propiconazole, tricyclazole, and difenoconazole, and at least one excipient.

[0014] In one embodiment, the composition of the present invention contains a strobilurin compound in an amount of 0.1 to 20% w / w, validamycin in an amount of 0.1 to 12% w / w, and compound A in an amount of 0.1 to 35% w / w.

[0015] In another embodiment, the composition of the present invention comprises a strobilurin compound selected from the group consisting of azoxystrobin, dimoxystrobin, enstroburin, fluoxastrobin, kresoxime-methyl, metminostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, and enstroburin.

[0016] In one preferred embodiment, the strobilurin compound in the composition of the present invention is metminostrobin.

[0017] In one embodiment of the present invention, when compound A is tifluzamide, the amount of tifluzamide present in the composition is 5-14% w / w. In an alternative embodiment of the present invention, when compound A is hexaconazole, the amount of hexaconazole present in the composition is 0.1-10% w / w. In an alternative embodiment of the present invention, when compound A is propiconazole, the amount of propiconazole present in the composition is 8-15% w / w. In an alternative embodiment of the present invention, when compound A is tricyclazole, the amount of tricyclazole present in the composition is 15-30% w / w. In an alternative embodiment of the present invention, when compound A is difenoconazole, the amount of difenoconazole present in the composition is 5-10% w / w.

[0018] In yet another embodiment, the composition of the present invention is a) Metminostrobin, validamycin, tifluzamide and at least one excipient, b) Metminostrobin, validamycin, hexaconazole and at least one excipient, c) Metminostrobin, validamycin, propiconazole and at least one excipient, d) Metminostrobin, validamycin, tricyclazole and at least one excipient, or e) Metminostrobin, validamycin, difenoconazole and at least one excipient, It is one of the following.

[0019] In one embodiment, the composition of the present invention is a) Metminostrobin present in an amount of 1-20% w / w, validamycin present in an amount of 0.1-12% w / w, tifluzamide present in an amount of 5-14% w / w, and at least one excipient, or b) Metminostrobin present in an amount of 1-20% w / w, validamycin present in an amount of 0.1-12% w / w, hexaconazole present in an amount of 0.1-10% w / w, and at least one excipient. It is one of the following.

[0020] In another embodiment, the composition of the present invention is a) Metminostrobin present in a 10% w / w amount, validamycin present in a 6% w / w amount, tifluzamide present in a 9% w / w amount, and at least one excipient, or b) Metminostrobin present in a 10% w / w amount, validamycin present in a 6% w / w amount, hexaconazole present in a 5% w / w amount, and at least one excipient, It is one of the following.

[0021] In another embodiment, the composition comprises a capsule suspension (CS), a dispersible concentrate (DC), a dustable powder (DP), powder for dry seed treatment (DS), an emulsifiable concentrate (EC), an emulsifiable granule (EG), an emulsion water-in-oil (EO), an emulsifiable powder (EP), an emulsion for seed treatment (ES), an emulsion oil-in-water (EW), a flowable concentrate for seed treatment (FS), granules (GR), a micro-emulsion (ME), an oil-dispersion (OD), and an oil-mixed flowable concentrate. Concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquidIt is formulated as a liquid, water dispersible granules (WG), wettable powder (WP), water dispersible powder for slurry seed treatment (WS), water dispersible tablet (WT), a mixed formulation of CS and SC (ZC), or a mixed formulation of CS and SE (ZE), or a mixed formulation of CS and EW (ZW).

[0022] In a preferred embodiment, the composition of the present invention is formulated as a suspension concentrate.

[0023] In one embodiment, the composition of the present invention comprises at least one excipient selected from the group consisting of a dispersant, a wetting agent, an antifreezing agent, an antifoaming agent, a biocide, and a thickener.

[0024] In yet another embodiment, the dispersant is selected from the group including but not limited to tris(tristyrylphenol) phosphate ethoxylated amine salt, acrylic copolymer, graft copolymer, and combinations thereof, and is present in an amount of 2 - 10% w / w.

[0025] In another embodiment, the wetting agent is selected from the group including but not limited to ethoxylated polyaryl phenol phosphate ester, dioctyl sulfosuccinate, nonionic ethoxylate, and combinations thereof, and is present in an amount of 1 - 5% w / w.

[0026] In one embodiment, the antifreezing agent is selected from the group including but not limited to propylene glycol, diethylene glycol, monoethylene glycol, and combinations thereof, and is present in an amount of 2 - 10% w / w.

[0027] In another embodiment, the defoaming agent is a dimethylpolysiloxane emulsion, present in an amount of 0.01 to 0.5% w / w.

[0028] In another embodiment, the biocicide is selected from the group including, but not limited to, a 20% dipropylene glycol aqueous solution of 1,2-benzoisothiazolin-3-one, formaldehyde, and combinations thereof, and is present in an amount of 0.01 to 0.50% w / w.

[0029] In another embodiment, the thickener is xanthan gum, present in an amount of 0.01 to 0.50% w / w.

[0030] In another embodiment, the present invention provides a method for producing a synergistic bactericidal composition, comprising the steps of mixing a strobilurin compound, validamycin, compound A selected from the group including tifluzamide, hexaconazole, propiconazole, tricyclazole, and difenoconazole, and at least one excipient.

[0031] [Brief explanation of the drawing] Figure 1 is a flowchart for preparing a synergistic bactericidal composition containing metminostrobin, validamycin, and tifluzamide in the form of suspension concentrates.

[0032] Figure 2 is a flowchart for preparing a synergistic bactericidal composition containing metminostrobin, validamycin, and hexaconazole in the form of suspension concentrates.

[0033] [Detailed description of the invention] Some representative embodiments of the present invention are described below. The present invention is not limited to specific details and representative methods in its broader embodiments. Illustrative examples relating to the embodiments and methods provided are described in this chapter. Various aspects of the present invention are specifically shown and explicitly claimed in the appended claims, taking into consideration this specification and appropriate equivalents.

[0034] When used in the specification and appended claims, the singular forms "a," "an," and "the" refer to multiple subjects unless the context clearly indicates otherwise. Therefore, for example, a reference to a composition containing "a compound" includes mixtures of two or more compounds. Also, the term "or" is generally used to mean "and / or" unless the context clearly indicates otherwise.

[0035] Unless otherwise specified, the various quantities expressed using the terms "%w / w" or "%" refer to a weight percentage of the total weight of the solution or composition.

[0036] As used herein, the terms “active ingredient” (ai) or “activator” refer to components of a composition used for the control of insects or pests.

[0037] Strobilurins are a group of compounds used as fungicides in agriculture. Strobilurins are part of a larger group of quinone external inhibitors (QoIs) that act to inhibit the respiratory chain at the complex III level. Strobilurins have an inhibitory effect on other fungi, reducing competition for nutrients. Strobilurins inhibit electron transport within mitochondria, disrupt metabolism, and hinder the growth of target fungi. Some examples of strobilurins include azoxystrobin, kresoxime-methyl, picoxystrobin, fluoxastrobin, oryzastrobin, dimoxystrobin, pyraclostrobin, trifloxystrobin, kumoxystrobin, enoxastrobin, fluphenoxystrobin, mandestrobin, phenaminostrobin, and metminostrobin.

[0038] Metminostrobin (IUPAC name: (E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)acetamide) acts by inhibiting the cytochrome pathway between cytochrome b and cytochrome c1 at the ubiquinol oxidation site. Metminostrobin is used in rice to control Pyricuaria oryzae.

[0039] Validamycin (IUPAC name: (1R,2R,3S,4S,6R)-2,3-dihydroxy-6-hydroxymethyl-4-[(1S,4R,5S,6S)-4,5,6-trihydroxy-3-hydroxymethylcyclohex-2-enylamino]cyclohexyl-β-D-glucopyranoside) is a non-penetrating antibiotic with bacteriostatic activity. Validamycin causes abnormal branching at the tips of pathogens, followed by cessation of further development. Validamycin inhibits trehalase, an enzyme that mediates the digestion of the carbohydrate trehalose and the transport of glucose to the hyphae. Validamycin controls Rhizoctonia solani, a fungus in rice, potatoes, vegetables, strawberries, tobacco, ginger, and other crops, as well as damping-off disease in cotton, rice, sugar beet, etc.

[0040] Tifluzamide (IUPAC name: 2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4-trifluoromethyl-1,3-thiazole-5-carboxanilide) is a fungicide commonly used to control basidiomycetes in rice, potatoes, corn, and amenity grass. Tifluzamide inhibits succinate dehydrogenase (complex II) in the tricarboxylic acid cycle.

[0041] Hexaconazole (IUPAC name: (RS)-2-(2,4-dichlorophenyl)-1-(1H-1,2,4-triazole-1-yl)hexane-2-ol) is a systemic fungicide with protective and therapeutic effects. Hexaconazole inhibits ergosterol biosynthesis (sterol demethylation inhibitor). Hexaconazole controls many fungi, particularly ascomycetes and basidiomycetes on apple, grapevine, coffee, peanut, banana, cucumber, pepper, and other crops.

[0042] Propiconazole (IUPAC name: 2RS,4RS; 2RS,4SR)-1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole) is a systemic foliar fungicide with prophylactic and curative effects that favorably translocates to xylem. Propiconazole is used to control various types of fungal species on cereals, bananas, rice, coffee, peanuts, drupes, and maize by acting as a sterol demethylation (ergosterol biosynthesis) inhibitor.

[0043] Tricyclazole (IUPAC name: 5-methyl-1,2,4-triazolo[3,4-b][1,3]benzothiazole) is a systemic fungicide that is rapidly absorbed by roots and leaves and moves to the xylem and apoplast within the plant. Tricyclazole is a melanin biosynthesis inhibitor (reduction of 1,3,8-trihydroxynaphthalene and permelone). Tricyclazole controls rice sprouts in transplanted and directly sown rice.

[0044] Difenoconazole (IUPAC name: 3-chloro-4-[(2RS,4RS;2RS,4SR)-4-methyl-2-(1H-1,2,4-triazole-1-ylmethyl)-1,3-dioxolan-2-yl]phenyl 4-chlorophenyl ether) is a systemic fungicide with prophylactic and therapeutic effects. Difenoconazole is absorbed by leaves via apical and strong transstratific translocation. By inhibiting sterol demethylation and cell membrane ergosterol biosynthesis, difenoconazole provides long-lasting prophylactic and therapeutic activity against cysts, basidiomycetes, and imperfect fungi, leading to the cessation of their development. Difenoconazole is used against disease complexes in grapes, pears, drupes, potatoes, sugar beets, rapeseed, bananas, cereals, rice, soybeans, ornamental plants, and vegetable crops.

[0045] The present invention provides a synergistic bactericidal composition comprising a strobilurin compound, validamycin, compound A selected from the group including tifluzamide, hexaconazole, propiconazole, tricyclazole, and difenoconazole, and at least one excipient.

[0046] In one embodiment, the composition according to the present invention contains a strobilurin compound in an amount of 0.1 to 20% w / w, validamycin in an amount of 0.1 to 12% w / w, and compound A in an amount of 0.1 to 35% w / w.

[0047] Non-limiting examples of strobilurin compounds according to the present invention may include azoxystrobin, dimoxystrobin, enstrobrin, fluoxastrobin, kresoxime-methyl, metminostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, and enstrobrin. In a preferred embodiment, the strobilurin compound is metminostrobin.

[0048] In one embodiment of the present invention, when compound A is tifluzamide, the amount of tifluzamide present in the composition is 5-14% w / w. In an alternative embodiment of the present invention, when compound A is hexaconazole, the amount of hexaconazole present in the composition is 0.1-10% w / w. In an alternative embodiment of the present invention, when compound A is propiconazole, the amount of propiconazole present in the composition is 8-15% w / w. In an alternative embodiment of the present invention, when compound A is tricyclazole, the amount of tricyclazole present in the composition is 15-30% w / w. In an alternative embodiment of the present invention, when compound A is difenoconazole, the amount of difenoconazole present in the composition is 5-10% w / w.

[0049] Non-limiting examples of preferred compositions according to the present invention include the following mixtures: a) Metminostrobin, validamycin, tifluzamide and at least one excipient, b) Metminostrobin, validamycin, hexaconazole and at least one excipient, c) Metminostrobin, validamycin, propiconazole and at least one excipient, d) Metminostrobin, validamycin, tricyclazole and at least one excipient, or e) Metminostrobin, validamycin, difenoconazole, and at least one excipient.

[0050] A preferred example of a suitable composition according to the present invention may be the following mixture: a) Metminostrobin present in an amount of 1-20% w / w, validamycin present in an amount of 0.1-12% w / w, tifluzamide present in an amount of 5-14% w / w, and at least one excipient, or b) Metminostrobin present in an amount of 1–20% w / w, validamycin present in an amount of 0.1–12% w / w, hexaconazole present in an amount of 0.1–10% w / w, and at least one excipient.

[0051] In its most preferred embodiment, the synergistic bactericidal composition comprises 10% w / w of metminostrobin, 6% w / w of validamycin, 9% w / w of tifluzamide, and at least one excipient.

[0052] In another most preferred embodiment, the synergistic bactericidal composition comprises 10% w / w of metminostrobin, 6% w / w of validamycin, 5% w / w of hexaconazole, and at least one excipient.

[0053] In one embodiment, the ratio of metminostrobin to (validamycin + tifluzamide) is 1:1 to 1:2. In a preferred embodiment, the ratio between validamycin and tifluzamide is 1:1 to 1:2.

[0054] In another embodiment, the ratio of metminostrobin:(validamycin + hexaconazole is 1:0.5 to 1:2. In a preferred embodiment, the ratio between validamycin and hexaconazole is 0.5:1 to 1.5:1.

[0055] In yet another embodiment, the synergistic composition of the present invention comprises a capsule suspension (CS), a dispersible concentrate (DC), a dustable powder (DP), powder for dry seed treatment (DS), an emulsifiable concentrate (EC), an emulsifiable granule (EG), an emulsion water-in-oil (EO), an emulsifiable powder (EP), and an emulsion for seed treatment (EG). Treatment (ES), Oil-in-Water Emulsion (EW), Flowable Concentrate for Seed Treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-Dispersion (OD), Oil Miscible Flowable Concentrate (OF), Oil Miscible Liquid (OL), Oil Dispersible Powder (OP), Suspension Concentrate (SC), Suspension Concentrate for Direct Application (SD), Suspo-Emulsion (SE), Water-Soluble Granule (SG), Soluble Concentrate (SL), Spreading Oil (SO), Water-Soluble Powder (SP), Water-Soluble Tablets Tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), A mixed formulation of CS and SC (ZC), A mixed formulation of CS and SE ( It can be formulated as a mixed formulation of CS and SE (ZE), or CS and EW (ZW).

[0056] In one preferred embodiment, the composition of the present invention is formulated as a suspension concentrate (SC). As used herein, the term “suspension concentrate” refers to a suspension of the active ingredient and excipients in a small amount of liquid, usually in water.

[0057] Generally, solid particles in liquids are observed to spontaneously aggregate and form clumps. Therefore, it is recommended to add a dispersant to prevent the aggregation of solid particles and to keep them suspended in the fluid. Accordingly, the compositions of the present invention contain dispersants such as tristyrylphenol ethoxylated amine salts, acrylic copolymers, graft copolymers, naphthalene sulfonates (sulfonates) of formaldehyde condensates, acrylic copolymers, and lignin sulfonates. One or more dispersants can be used in the synergistic compositions of the present invention. The dispersant is present in an amount of 2 to 10% w / w.

[0058] Wetting is the first step in dispersion, in which the air surrounding the granular composition is replaced with water. If the surface tension of the liquid is very high, wetting of the composition with water may not occur. Therefore, it is recommended to add a wetting agent to the composition to facilitate the dispersion process of granules in the liquid. Non-limiting examples of wetting agents that can be used in the present invention include ethoxylated polyarylphenol phosphates, dioctyl sulfosuccinates, nonionic ethoxylates, dioctyl sulfosuccinates, sodium lauryl sulfate, and naphthalene alkylaryl sulfonates. In alkylaryl sulfonates, the alkyl group contains about 1 to 5 carbon atoms, and the aryl nucleus is selected from the group consisting of benzene and naphthalene. One or more wetting agents can be used in the synergistic composition of the present invention. The wetting agent is present in an amount of 1 to 5% w / w.

[0059] To prevent aqueous compositions from freezing, antifreeze agents are generally added to the composition. Useful and suitable antifreeze agents as used herein include, but are not limited to, propylene glycol, diethylene glycol, monoethylene glycol, and combinations thereof. Preferably, the antifreeze agent is present in an amount of 2 to 10% w / w.

[0060] Defoaming agents are also called foam inhibitors. Since foam formation hinders the efficient filling of containers, defoaming agents are generally added to compositions. Preferably, the defoaming agent is a polydimethylsiloxane emulsion. In the composition of the present invention, the defoaming agent is present in an amount of 0.01 to 0.5% w / w.

[0061] The synergistic bactericidal composition contains a biocide. The biocide is selected from the group consisting of a 20% dipropylene glycol aqueous solution of 1,2-benzoisothiazolin-3-one, formaldehyde, and combinations thereof, and is present in an amount of 0.01 to 0.50% w / w. The biocide is added to the composition of the present invention for protection against spoilage from bacteria, yeasts, and fungi.

[0062] To reduce the tendency of the composition to disperse during spraying and to decrease the likelihood of it being washed off crops, it is necessary to add a thickening agent to the composition. Preferably, the synergistic fungicide composition contains xanthan gum as a thickening agent in an amount of 0.01 to 0.50% w / w. The xanthan gum used in this invention is obtained from a commercial source.

[0063] The compositions according to the present invention may further contain additional components such as surfactants, agriculturally acceptable supports, carriers or fillers, protective colloids, adhesives, thixotropes, penetrants, stabilizers, and chelating agents.

[0064] In one embodiment, the present invention provides a method for producing a synergistic bactericidal composition. The method comprises mixing a strobilurin compound, validamycin, a compound selected from the group including tifluzamide, hexaconazole, propiconazole, tricyclazole, or difenoconazole, and at least one excipient.

[0065] In another embodiment, the present invention provides a method for producing a synergistic bactericidal composition in the form of a suspension concentrate. The method comprises diluting a dispersant and a wetting agent in deionized water and solubilizing them by high-shear mixing to obtain a solution. To the solution, an active ingredient, an antifreeze, an antifoaming agent, and a biocide are added and mixed to obtain a homogeneous mass. The mass is then pulverized in a mill to obtain an average particle size of less than 5 microns. An aqueous solution of a thickener is added to the pulverized mass under low stirring to obtain the synergistic bactericidal composition of the present invention in the form of a suspension concentrate.

[0066] The synergistic compositions of the present invention have been found to be effective in controlling a wide range of fungal diseases, such as blast (neck and leaf), sheath blight, and bacterial leaf blight in paddy fields. The synergistic compositions are also effective in controlling white mold, early and late blight, and rot in fruits and vegetables, grains, and other crops.

[0067] The inventors have surprisingly found that the compositions of the present invention are synergistic in nature. The synergistic compositions of the present invention are more effective than their individual counterparts, or when the two active substances are incorporated together. The synergistic compositions of the present invention also allow the use of significantly smaller amounts of active ingredients compared to their individual counterparts. This makes it possible to substantially reduce the application rate of each of these active ingredients while maintaining good efficacy. The reduction in application rates lowers processing costs for farmers and also reduces the environmental burden from both waste generation and the residue of chemicals that protect crops.

[0068] The synergistic fungicidal composition of the present invention provides broad-spectrum control of fungi, delays the emergence of resistant strains, minimizes the risk of resistance development, and achieves effective and economical control of undesirable fungi.

[0069] The synergistic composition of the present invention offers many other advantages. • During the trial period, the efficacy was improved compared to other formulations tested. • It is economically beneficial for farmers because it reduces the number of spraying applications and improves crop yields. • The reduced frequency of spraying decreases the risk to farmers from occupational exposure. • Has storage stability, • Not plant-toxic, • Environmentally friendly.

[0070] Since numerous modifications and variations within the scope of the present invention will be apparent to those skilled in the art, embodiments of the present invention are described in more detail in the following examples, which are intended merely as illustrations. Unless otherwise noted, all parts, percentages and ratios reported in the following examples are by mass, and all reagents used in these examples are obtained from or available from chemical suppliers.

[0071] [Examples] Table 1 shows the synergistic bactericidal compositions of the present invention in the form of suspension concentrates, comprising metminostrobin, validamycin, and tifluzamide. The units for each component of the composition are expressed as "%w / w," i.e., a weight percentage relative to the total weight of the solution or the total weight of the composition.

[0072] [Table 1]

[0073] Table 2 provides the amounts of active ingredients and raw materials filled to produce the synergistic composition of the present invention in SC form. The active ingredients are industrial grade. The entries in Table 1 are for 100% pure compounds, while the entries in Table 2 are for industrial products with a certain percentage of impurities; therefore, the entries for active ingredients in Table 2 differ from those in Table 1. Accordingly, 100% pure metminostrobin 10% w / w, validamycin 6% w / w, and tifluzamide 9% w / w in Table 1 correspond to 99% pure metminostrobin 10.10 g, 64% pure validamycin 9.38 g, and 95% pure tifluzamide 9.47 g in Table 2.

[0074] [Table 2]

[0075] [Example 1: Method for producing a synergistic insecticidal composition in the form of a suspension concentrate (SC) containing metminostrobin, validamycin, and tifluzamide] All components were weighed as shown in Table 2. The graft copolymer (5 g) and nonionic ethoxylate (3 g) were diluted with deionized water and solubilized by high-shear mixing. Then, propylene glycol (4 g), metminostrobin (10.10 g), validamycin (9.38 g), tifluzamide (9.47 g), dimethylpolysiloxane emulsion (0.15 g), and a 20% dipropylene glycol aqueous solution of 1,2-benzoisothiazolin-3-one (0.20 g) were added and mixed to obtain a homogeneous mass. The homogeneous mass was pulverized using a bead mill. Pulverization was continued until an average particle size of less than 5 (D-90) microns was obtained. After pulverization, a 2% aqueous solution of xanthan gum was added under low stirring to obtain the indicated bactericidal composition.

[0076] [Table 3]

[0077] Table 4 provides the amounts of active ingredients and raw materials filled to produce the synergistic composition of the present invention in SC form. The active ingredients are industrial grade. The entries in Table 3 are for 100% pure compounds, while the entries in Table 4 are for industrial products with a certain percentage of impurities; therefore, the entries for active ingredients in Table 4 differ from those in Table 3. Accordingly, 10% w / w metminostrobin, 6% w / w validamycin, and 5% w / w hexaconazole in Table 3 correspond to 10.10 g of 99% pure metminostrobin, 9.38 g of 64% pure validamycin, and 5.44 g of 92% pure hexaconazole in Table 4.

[0078] [Table 4]

[0079] [Example 2: Method for producing a synergistic insecticidal composition in the form of a suspension concentrate (SC) containing metminostrobin, validamycin, and hexaconazole] All components were weighed as shown in Table 4. The graft copolymer (5 g) and nonionic ethoxylate (3 g) were diluted with deionized water and solubilized by high-shear mixing. Then, propylene glycol (5 g), metminostrobin (10.10 g), validamycin (9.38 g), hexaconazole (5.44 g), dimethylpolysiloxane emulsion (0.12 g), and a 20% dipropylene glycol aqueous solution of 1,2-benzoisothiazolin-3-one (0.20 g) were added and mixed to obtain a homogeneous mass. The homogeneous mass was pulverized using a bead mill. Pulverization was continued until an average particle size of less than 5 (D-90) microns was obtained. After pulverization, a 2% aqueous solution of xanthan gum was added under low stirring to obtain the indicated bactericidal composition.

[0080] [Evaluation of the synergistic effect of the sterilization composition of the present invention] A synergistic effect exists whenever the combined effect of the active ingredients is greater than the sum of the effects of the individual ingredients. The synergistic effect was calculated using Colby's method, Weeds, vol.15, No.1 (Jan, 1967), pp.20-2.

[0081] The expected synergistic effect for a given combination of two active ingredients can be calculated as follows:

[0082]

number

[0083] The expected synergistic effect for a given combination of three active ingredients can be calculated as follows:

[0084]

number

[0085] During the ceremony, E represents the expected rate of fungicidal control for a combination of three fungicides at specified doses (e.g., equal to x, y, and z respectively). X is the percentage of fungicidal control observed by compound (I) at a specified dose (equal to x), Y is the percentage of fungicidal control observed by compound (II) at a specified dose (equal to y), Z is the percentage of fungicidal control observed by compound (III) at a specified dose (equal to z).

[0086] A synergistic effect exists when the observed rate of fungicidal control for a combination is greater than the expected rate.

[0087]

number

[0088] [Greenhouse experiments on synergistic effects] To evaluate the synergistic effect, test plants (rice seedlings) are cultivated in a greenhouse. The seedlings are transplanted into trays measuring 1 mts × 0.5 mts and grown for one week before application of the test compound. The test plants are inoculated with blast cells (neck and leaves), sheath blight, and bacterial leaf blight. The treated plants are maintained at 21°C to 28°C in the greenhouse throughout the experiment.

[0089] The test compounds were weighed according to the treatment details provided in Tables 5 and 6. The required amount of sample was diluted with demineralized water. The mixture was prepared within 0.5 hours before spraying. The test compounds were applied as foliar sprays 6 days after inoculation. For each treatment, approximately 20 ml of spray washing solution was sprayed into each of the four trays in a spray chamber. After drying, the plants were returned to the greenhouse and maintained at 20°C to 25°C. The treated plants were compared to the control (untreated plants) to evaluate disease control.

[0090] The percentage of infected leaf area is estimated for three separate leaves per pot. The percentage of disease control for each treatment is determined using the formula shown below.

[0091]

number

[0092] For all combinations, the expected percentage of control is calculated using Colby's formula described above.

[0093] Tables 5 and 6 summarize the synergistic effects of the compositions of the present invention, namely metminostrobin 10% + validamycin 6% + tifluzamide 9% SC and metminostrobin 10% + validamycin 6% + hexaconazole 5% SC.

[0094] [Table 5] JPEG0007884056000012.jpg197169

[0095] [Table 6] JPEG0007884056000014.jpg149169

[0096] Tables 5 and 6 clearly show that the bactericidal compositions of the present invention (metminostrobin 10% + validamycin 6% + tifluzamide 9% SC, and metminostrobin 10% + validamycin 6% + hexaconazole 5% SC) have a synergistic effect.

[0097] [Biological efficacy of the sterilizing composition of the present invention] Experiment details Field trials were conducted in paddy fields to evaluate the control of diseases, namely leaf and neck bud disease, sheath blight, and bacterial leaf blight, using metminostrobin, validamycin, tifluzamide, and hexaconazole individually, as a two-component mixture (tank mix), and as a three-component mixture applied to the leaves. The three-component mixture was prepared according to the methods described in Examples 1 and 2. Specifically, the formulations metminostrobin 20% SC, validamycin 3% L, tifluzamide 24% SC, and hexaconazole 5% SC were diluted with water to the specified concentrations of the active compounds. Details of the treatment are shown in the second column of Tables 7 and 8.

[0098] The experiment was designed in a randomized block design (RBD) with four replicates. The plot size was 25 square meters. All recommended agricultural practices were followed throughout the planting period. Application was carried out using a household sprayer equipped with a pressure regulator and a hollow cone nozzle. The application rate was 500 l / ha for all trials. Various fungicide compositions listed in Tables 7 and 8 were sprayed into paddy fields to evaluate their control of leaf and neck bud disease, sheath blight, and bacterial leaf blight. Based on various dosages, weighed amounts of the test material were dissolved in 1.25 liters of water per treatment and sprayed uniformly twice at 15-day intervals. After each application, the disease index percentage (PDI) per hill was evaluated at 14 days post-application (DAA) on 10 hills per plot. The average of the disease index percentages (PDI) after two applications was recorded and is shown in the table below. Yields were also recorded.

[0099] [Table 7] JPEG0007884056000016.jpg30169

[0100] [Table 8] JPEG0007884056000018.jpg30169

[0101] [Plant toxicity effects] In the field tests described above, plant toxicity was evaluated for the synergistic compositions of the present invention. In the plant toxicity evaluation in paddy fields, the following observations were made by observing temporary or long-term leaf damage, i.e., leaf damage at the tip and leaf surface, wilting, vein removal, necrosis, upward and downward growth, after 3, 5, 7, and 14 DAS of the synergistic fungicide compositions of the present invention. The average scores are shown in the table. Crop damage was observed using a visual evaluation scale from 1 to 10, as shown in Table 9. Table 10 shows the plant toxicity effects of the synergistic compositions of the present invention in paddy fields.

[0102] [Table 9]

[0103] [Table 10]

[0104] The synergistic fungicide composition of the present invention provided better control of fungal diseases compared to the reference article. Furthermore, the use of the synergistic fungicide composition resulted in better crop conditions, namely fresh green leaves, and did not cause any symptoms of plant toxicity in the plants.

[0105] From the above, it will be recognized that numerous modifications and variations can be made without departing from the exact spirit and scope of the novel concept of the present invention. It should be understood that it is not intended and should not be inferred that the invention is limited to the specific embodiments described. All such modifications and improvements have been omitted from this specification for the sake of brevity and readability, but should be understood to be appropriate within the following claims. [Brief explanation of the drawing]

[0106] [Figure 1] This is a flowchart for preparing a synergistic bactericidal composition containing metminostrobin, validamycin, and tifluzamide in the form of suspension concentrates. [Figure 2] This is a flowchart for preparing a synergistic bactericidal composition containing metminostrobin, validamycin, and hexaconazole in the form of suspension concentrates.

Claims

1. A formulation comprising metminostrobin present in an amount of 1 to 20% w / w, validamycin present in an amount of 0.1 to 12% w / w, tifluzamide present in an amount of 5 to 14% w / w, and at least one excipient, wherein the ratio of metminostrobin:(validamycin + tifluzamide) is 1:1 to 1:2, and the ratio between validamycin and tifluzamide is 1:1 to 1:

2. A synergistic sterilization composition characterized by its use on rice seedlings.

2. A compound comprising metminostrobin present in an amount of 1 to 20% w / w, validamycin present in an amount of 0.1 to 12% w / w, hexaconazole present in an amount of 0.1 to 10% w / w, and at least one excipient, wherein the ratio of metminostrobin:(validamycin + hexaconazole) is 1:0.5 to 1:2, and the ratio between validamycin and hexaconazole is 0.5:1 to 1.5:

1. A synergistic sterilization composition characterized by its use on rice seedlings.

Images