A herbicidal composition and use thereof

Abstract

The present application relates to the technical field of pesticides, and discloses a herbicidal composition of a mixture of tribenuron, sodium 2-methyl-4-chloro and tebuconazole, wherein the mass ratio of the composition of active ingredient A (tribenuron and sodium 2-methyl-4-chloro) to active ingredient B (tebuconazole) is 0.5-30:1.The herbicidal composition has obvious synergistic effect on agricultural weeds, is good in quick-acting property, and is low in toxicity to human beings and livestock; in addition, the mechanism of action of tribenuron, sodium 2-methyl-4-chloro and tebuconazole is different, and the herbicidal composition can delay the drug resistance of weeds, and is an ideal herbicide.

Description

Technical Field

[0001] This invention belongs to the field of pesticide technology, especially the field of herbicide technology, and specifically relates to a composition of bensulfuron-methyl, sodium 2,4-D and tebuconazole, and its application in controlling agricultural weeds. Background Technology

[0002] Wheat is one of my country's important food crops, but weeds in wheat fields reproduce rapidly and grow in high density, encroaching on the aboveground and underground space, affecting wheat photosynthesis, aggravating the growth of wheat pathogens, harming wheat growth, and seriously affecting wheat yield, with yield losses generally exceeding 10%.

[0003] In my country, bensulfuron-methyl is widely used to control various broadleaf weeds in wheat fields. To address the resistance issues arising from its single-use application, most products are formulated with it to broaden the weed control spectrum and improve efficacy. To date, bensulfuron-methyl has been used for over 20 years. Due to continuous use and improper application techniques, the dosage has been increasing year by year, while the weed control effect has been decreasing. Finding highly effective herbicides for rational formulation has become an effective way to improve the control of broadleaf weeds in wheat fields and slow down the development of weed resistance. A search on the China Pesticide Information Network revealed that the main compound herbicides containing bensulfuron-methyl include: acetamiprid·bensulfuron-methyl, ethoxysulfuron·bensulfuron-methyl, thiophene·bensulfuron-methyl, chlorpyrifos·bensulfuron-methyl, fluoxetine·bensulfuron-methyl, fluoxetine·bensulfuron-methyl, benzylpyrifos·bensulfuron-methyl, bensulfuron-methyl·isoproturon, bensulfuron-methyl·isoproturon, bensulfuron-methyl·clodinafop-propargyl, benzyl·azole·chlorpyrifos, benzyl·azole·chlorpyrifos, benzyl·azole·2-methyl sodium, etc.

[0004] Most current research focuses on the synergistic effects of different types of herbicides, with the mixture of bensulfuron-methyl and 2,4-D sodium being widely used in Hebei Province. Furthermore, because weed control and disease control in wheat occur simultaneously, the practice of mixing herbicides and fungicides is common. Jia Min's research (a study on wheat phytotoxicity caused by the mixture of the herbicide clopyralid and triazole fungicides) touched upon the safety of mixed application of herbicides and fungicides on wheat, but no research has been found on the synergistic effects of combining herbicides and fungicides. Summary of the Invention

[0005] This invention provides a herbicidal composition with good control efficacy against broadleaf weeds in wheat fields. It combines commonly used herbicides bensulfuron-methyl and sodium 2,4-D with fungicide tebuconazole, and utilizes the synergistic effect of bensulfuron-methyl, sodium 2,4-D and fungicide tebuconazole to improve the control efficacy against weeds in farmland.

[0006] The present invention provides a herbicidal composition comprising active ingredients A and B, wherein active ingredient A is a combination of the herbicides bensulfuron-methyl and sodium 2,4-D, and active ingredient B is tebuconazole, wherein the mass ratio of active ingredients A and B is 0.5 to 30:1.

[0007] The bensulfuron-methyl used in this invention, chemically named methyl 2-[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylaminocarbamate sulfonyl]benzoate, is a herbicide mainly used to control broadleaf weeds in wheat (winter wheat, spring wheat, barley, etc.) fields. After being absorbed through the roots, stems, and leaves of plants, it is rapidly translocated, inhibiting the activity of acetolactate synthase (ALS), hindering the biosynthesis of valine and isoleucine, resulting in stunted growth and plant death within 1-3 weeks. The technical grade bensulfuron-methyl is a white solid with very low toxicity to warm-blooded animals and low toxicity to wild animals and fish.

[0008] The sodium 2,4-methylphenoxyacetate (2,4-chloro-2-methylphenoxyacetic acid sodium salt) in this invention is a hormone-type selective herbicide. It can be absorbed and translocated by plant roots, stems, and leaves; it is safe for gramineous crops but sensitive to broadleaf crops; and it effectively controls broadleaf weeds and sedges.

[0009] The tebuconazole used in this invention belongs to the triazole fungicide class and is a highly efficient systemic fungicide used for seed treatment or foliar spraying of important economic crops. It can effectively control various rust, powdery mildew, net blotch, root rot, Fusarium head blight, smut, and seed-borne leaf spot diseases in cereal crops, as well as tea leaf spot and banana leaf spot.

[0010] This invention achieves a synergistic effect by combining the above three agents with different mechanisms, thereby improving the control efficacy of herbicides and delaying the development of herbicide resistance in weeds.

[0011] Preferably, the mass ratio of active ingredients A and B in this invention is 0.5 to 25:1, more preferably 2 to 16:1, and even more preferably 2 to 4:1.

[0012] In the herbicidal composition of the present invention, the mass ratio of bensulfuron-methyl to sodium 2,4-D is preferably 1:1 to 60, more preferably 1:5 to 40, and even more preferably 1:10 to 30.

[0013] The herbicidal composition of this invention can be processed into any pesticide-acceptable formulation, such as suspension emulsions, microemulsions, water-in-oil emulsions, emulsifiable concentrates, oil suspensions, suspensions, wettable powders, dry suspensions, granules, water-dispersible granules, powders, oils, and microcapsule suspensions. Preferred formulations are suspension emulsions, water-in-oil emulsions, and microemulsions. In the aforementioned pesticide formulations, benzsulfuron-methyl, 2,4-D sodium chloride, and tebuconazole account for 1% to 80% of the total mass, preferably 10% to 60%, more preferably 25% to 45%, with the remainder being pesticide-acceptable adjuvants and / or carriers.

[0014] The pesticides described in this invention include, but are not limited to: solvents, cosolvents, emulsifiers, dispersants, stabilizers, defoamers, thickeners, density adjusters, pH adjusters, antifreeze agents, preservatives, carriers, wetting agents, penetrants, etc.

[0015] In this invention, when the herbicidal composition is formulated as a suspension emulsion, it preferably comprises the following components and mass contents: benzsulfuron-methyl 1%–20%, sodium 2,4-D chlorothalonil 3%–60%, tebuconazole 1%–20%, solvent 10%–50%, emulsifier 5%–8%, dispersant 0.1%–3%, thickener 0.1%–5%, pH adjuster 0.1%–5%, and water to make up the balance. More preferably, it comprises the following components and mass contents: benzsulfuron-methyl 2%–10%, sodium 2,4-D chlorothalonil 10%–40%, tebuconazole 1%–10%, solvent 20%–30%, emulsifier 6%–7%, dispersant 0.5%–2%, thickener 0.5%–3%, pH adjuster 0.5%–2%, and water to make up the balance. The water is preferably deionized water.

[0016] The above-mentioned suspension emulsion can be prepared by mixing benzsulfuron-methyl and sodium 2,4-methyl chloride technical materials with dispersant, thickener and deionized water to obtain benzsulfuron-methyl-2,4-methyl chloride sodium suspension; or by mixing tebuconazole technical material, solvent and emulsifier and then emulsifying it directly into the above suspension using a high-speed stirrer.

[0017] In this invention, when the herbicidal composition is formulated into an emulsion, it preferably contains the following components and their mass contents: benzyl sulfide 1%–20%, sodium 2,4-D chlorpyrifos 3%–60%, tebuconazole 1%–20%, solvent 10%–30%, emulsifier 8%–10%, dispersant 0.1%–8%, antifreeze 5%–10%, defoamer 0.1%–3%, preservative 0%–1%, thickener 0.1%–5%, density adjuster 0%–5%, pH adjuster 0.1%–5%, and water to make up the balance. Further preferred formulations include the following components and their mass percentages: benzyl sulfonate 2%–10%, sodium 2,4-methyl chloride 10%–40%, tebuconazole 1%–10%, solvent 15%–25%, emulsifier 8%–10%, dispersant 0.5%–3%, antifreeze 6%–8%, defoamer 0.5%–2%, preservative 0%–0.05%, thickener 0.5%–3%, density adjuster 0%–3%, pH adjuster 0.5%–3%, and water to make up the balance. The water is preferably deionized water.

[0018] The above-mentioned water-in-oil emulsion can be prepared by adding the technical grade of benzsulfuron-methyl, sodium 2,4-methyl chloride, and tebuconazole together with solvent, emulsifier, dispersant, defoamer, and thickener to form a homogeneous oil phase. Water, antifreeze, preservative, density adjuster, and pH adjuster are then mixed together to form a homogeneous aqueous phase. Under high-speed stirring, the aqueous phase is added to the oil phase to form a well-dispersed water-in-oil emulsion.

[0019] In this invention, when the herbicidal composition is formulated as a microemulsion, it preferably comprises the following components and mass contents: benzsulfuron-methyl 1%–20%, sodium 2,4-D chlorothalonil 3%–60%, tebuconazole 1%–20%, solvent 10%–30%, emulsifier 8%–10%, stabilizer 0.5%–3%, pH adjuster 0.1%–5%, antifreeze 2%–10%, and water to make up the balance. More preferably, it comprises the following components and mass contents: benzsulfuron-methyl 2%–10%, sodium 2,4-D chlorothalonil 10%–40%, tebuconazole 1%–10%, solvent 15%–25%, emulsifier 8%–10%, stabilizer 1%–2%, pH adjuster 0.5%–3%, antifreeze 4%–8%, and water to make up the balance. The water is preferably deionized water.

[0020] The preparation method of the above-mentioned microemulsion can be, for example, as follows: fully mixing the technical grade of benzsulfuron, sodium 2,4-methyl chloride and tebuconazole with solvent, emulsifier, stabilizer and antifreeze to form a uniform and transparent oil phase; fully mixing the pH adjuster with deionized water to form a uniform and transparent aqueous phase; and slowly adding the aqueous phase to the oil phase under stirring to form a water-in-oil microemulsion.

[0021] In this invention, the solvent may be one or more of the following: deionized water, chloroform, isopropanol, toluene, xylene, acetone, acetonitrile, ethyl acetate, cyclohexanone, methanol, ethanol, propanol, butanol, ethylene glycol, polyethylene glycol (200-600), polypropylene glycol (200-600), diethyl ether, butyl ether, methyl oleate, dimethylformamide, and dimethyl sulfoxide. When it is a combination of multiple components, the proportion of each component added is not limited.

[0022] The cosolvent can be any one or more combinations of acetone, cyclohexanone, isophorone, diesel, butanediol, castor oil, pine oil, halogenated hydrocarbons, low molecular weight amides, methanol, dimethyl sulfoxide, polymethylsiloxane, tributyl phosphate, polyvinyl alcohol, and triglycerides. When it is a combination of multiple components, the proportion of each component added is not limited.

[0023] The emulsifier may be one or more of the following: dodecylbenzene sulfonate, alkylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether-OP, benzyl biphenol polyoxyethylene ether, C15 alkyl sulfate sodium salt, phenethylphenol polyoxyethylene polyoxypropylene ether, ethylene oxide-propylene oxide block copolymer, ethoxylated alkylbenzene ether, cyclohexylphenol polyoxyethylene polyoxypropylene ether, and nonylphenol polyoxyethylene ether-NP.

[0024] The dispersant may be one or more of the following: lignin sulfonate, high molecular weight carboxylate, alkylphenol polyoxyethylene ether, alkyl naphthalene sulfonate formaldehyde condensate, sodium dibutylnaphthalene sulfonate, polyvinyl alcohol, gum arabic, and sodium methyl aminoethyl sulfonate oleate.

[0025] The stabilizer may be one or more of 3-chloro-1,2-epoxypropane, butyl glycidyl ether, phenyl glycidyl ether, tolyl glycidyl ether, polyvinyl glycol diglycidyl ether, potassium sorbate, and sodium sorbate.

[0026] The defoamer may be one or more of the following: mineral oil, vegetable oil, isooctanol, isoamyl alcohol, lauric acid, stearic acid, fatty acid amide, fatty acid ester, and silicon dioxide.

[0027] The thickener may be one or more of the following: hydroxymethyl cellulose, xanthan gum, gelatin, gum arabic, magnesium aluminum silicate, polyacrylate, natural polysaccharide, xanthan gum, diatomaceous earth, silica, and bentonite.

[0028] The density regulator can be one or more of urea, NaCl, and CaCl2.

[0029] The pH adjuster may be one or more of borax, sodium hydroxide, sodium carbonate, disodium hydrogen phosphate, and sodium bicarbonate.

[0030] The antifreeze agent may be one or more of ethylene glycol, propylene glycol, polyethylene glycol, glycerol, ammonium sulfate, glycerol, NaCl, and CaCl2.

[0031] The preservative may be one or more of sodium salicylate, sodium benzoate, 1,2-benzothiazolin-3-one, 2-hydroxybiphenyl, p-hydroxybenzaldehyde, sorbic acid, benzoic acid, and benzaldehyde.

[0032] The carrier can be one or more of the following: kaolin, diatomaceous earth, attapulgite, silica, bentonite, talc, pyrophyllite, and clay.

[0033] The wetting agent may be one or more of the following: pull-apart powder, sodium alkylbenzene sulfonate, sodium lauryl sulfate, alkyl sulfonate, sodium dioctyl succinate sulfonate, sodium diisopropyl naphthalene sulfonate, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, tridecyl alcohol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether.

[0034] The penetrant may be one or more of sodium lauryl sulfate, alkyl sulfonate, sodium dioctyl succinate sulfonate, sodium diisopropyl naphthalene sulfonate, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, tridecyl alcohol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether.

[0035] A third aspect of the present invention relates to the use of the above-described herbicidal composition in the control of agricultural weeds.

[0036] Preferably, the herbicidal composition is used to control broadleaf weeds in wheat fields, such as shepherd's purse, shepherd's purse, wild wheatgrass, purslane, lambsquarters, small lambsquarters, bindweed, field bindweed, morning glory, thistle, knotweed, velvetleaf, burdock, cocklebur, kochia, potgum, small-flowered mustard, hop, purslane, speedwell, creeping celery, and eupatorium. The wheat fields include, but are not limited to, winter wheat, spring wheat, barley, barley, oats, rye, buckwheat, and barley fields, which are grasses.

[0037] More preferably, the herbicidal composition is used to control shepherd's purse and wild shepherd's purse in wheat fields.

[0038] In the application described in this invention, the field application rate of the active ingredient in the herbicidal composition is 20–350 g / hm². 2 Preferred concentration: 100–200 g / hm 2 .

[0039] All raw materials and reagents used in this invention are commercially available and readily available. For example, benzyl sulfide technical grade can be purchased from Shanghai DuPont Agrochemicals Co., Ltd., 2,4-D sodium chloride from Jiangsu Yongkai Chemical Co., Ltd., and tebuconazole from Shandong Binnong Technology Co., Ltd.

[0040] The beneficial effects of this invention are:

[0041] 1. The herbicidal composition of this invention exhibits significantly better weed control effects than the herbicides bensulfuron-methyl and MCPA sodium alone. The herbicidal composition of this invention includes the fungicide tebuconazole, which has an additive or synergistic effect with bensulfuron-methyl and MCPA sodium, significantly reducing the dosage and cost.

[0042] 2. The active ingredients bensulfuron-methyl, sodium 2,4-D and tebuconazole in the herbicide composition of the present invention kill weeds through three different mechanisms, thereby rapidly reducing weed resistance and extending the service life of the herbicide.

[0043] 3. The herbicidal composition of the present invention has high safety. Due to its good efficacy, the dosage of the herbicide can be controlled, thereby improving the safety of the herbicide for wheat and subsequent crops while enhancing its efficacy. Detailed Implementation

[0044] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0045] Unless otherwise specified, all reagents or instruments used in the following examples are conventional products that can be purchased from legitimate channels. Unless otherwise specified, all percentages in all examples of this invention refer to weight percentages.

[0046] (I) Formulation Examples

[0047] Formulation Example 1: 30% bensulfuron-methyl·2,4-chlorosodium·tebuconazole suspension emulsion

[0048] 2.13% benzyl sulfonate, 21.2% sodium 2,4-methyl chloride, 6.67% tebuconazole, 20% acetone, 6% calcium dodecylbenzenesulfonate, 1% lignin sulfonate, 0.3% xanthan gum, 0.5% isoamyl alcohol, 5% ethylene glycol, 0.5% sodium benzoate, 0.5% borax, 0.012% sodium hydroxide, 0.01% disodium hydrogen phosphate, and deionized water to make up the balance.

[0049] Lignosulfonate, xanthan gum, isoamyl alcohol, ethylene glycol, sodium benzoate, borax, sodium hydroxide, disodium hydrogen phosphate, and deionized water were mixed evenly under high-speed shearing. Then, bensulfuron-methyl and sodium 2,4-methyl chloride technical grade were added, and the mixture was ball-milled for 2–3 hours until all particles were below 5 μm in diameter and the average particle size was less than 3 μm, thus obtaining a bensulfuron-methyl-2,4-methyl chloride sodium suspension. Tebuconazole technical grade, acetone, and calcium dodecylbenzenesulfonate were mixed evenly and then directly emulsified into the bensulfuron-methyl-2,4-methyl chloride sodium suspension using a high-speed stirrer to obtain a 30% bensulfuron-methyl-2,4-methyl chloride sodium tebuconazole suspension emulsion.

[0050] Formulation Example 2: 37% benzylsulfuron-methyl·2,4-chlorosodium·tebuconazole suspension emulsion

[0051] 2.96% benzyl sulfonate, 29.42% sodium 2,4-methyl chloride, 4.63% tebuconazole, 20% acetone, 6% alkylphenol polyoxyethylene ether, 2% lignin sulfonate, 0.3% xanthan gum, 0.5% fatty acid ester, 5% glycerol, 0.5% sodium benzoate, 0.5% borax, 0.012% sodium hydroxide, 0.01% disodium hydrogen phosphate, and deionized water to make up the balance.

[0052] Lignosulfonate, xanthan gum, fatty acid esters, glycerol, sodium benzoate, borax, sodium hydroxide, disodium hydrogen phosphate, and deionized water were mixed evenly under high-speed shearing. Then, bensulfuron-methyl and sodium 2,4-methyl chloride technical were added, and the mixture was ball-milled for 2–3 hours until all particles were below 5 μm in diameter and the average particle size was less than 3 μm, thus obtaining a bensulfuron-methyl-2,4-methyl chloride sodium suspension. Tebuconazole technical, acetone, and alkylphenol polyoxyethylene ether were mixed evenly and then directly emulsified into the bensulfuron-methyl-2,4-methyl chloride sodium suspension using a high-speed mixer to obtain a 37% bensulfuron-methyl-2,4-methyl chloride sodium tebuconazole suspension emulsion.

[0053] Formulation Example 3: 45% Bensulfuron-methyl·2,4-D sodium·Tebuconazole suspension emulsion

[0054] 3.89% benzyl sulfonate, 39.26% sodium 2,4-D, 1.85% tebuconazole, 10% isopropanol, 20% acetone, 8% dodecylbenzenesulfonate, 2% lignin sulfonate, 0.3% gelatin, 0.5% isoamyl alcohol, 5% ethylene glycol, 0.5% sodium benzoate, 0.5% borax, 0.012% sodium hydroxide, 0.01% disodium hydrogen phosphate, deionized water to make up the balance.

[0055] Lignosulfonate, gelatin, isoamyl alcohol, ethylene glycol, sodium benzoate, borax, sodium hydroxide, disodium hydrogen phosphate, and deionized water are mixed evenly under high-speed shearing. Then, bensulfuron-methyl and sodium 2,4-methyl chloride technical grade are added, and the mixture is ball-milled for 2–3 hours until all particles are below 5 μm in diameter and the average particle size is less than 3 μm, thus obtaining a bensulfuron-methyl-2,4-methyl chloride sodium suspension. Tebuconazole technical grade, acetone, and calcium dodecylbenzenesulfonate are mixed evenly and then directly emulsified into the bensulfuron-methyl-2,4-methyl chloride sodium suspension using a high-speed stirrer to obtain a 45% bensulfuron-methyl-2,4-methyl chloride sodium tebuconazole suspension emulsion.

[0056] Formulation Example 4: 30% benzylsulfuron-methyl·2,4-chlorosodium·tebuconazole aqueous emulsion

[0057] 2.13% benzyl sulfonate, 21.2% sodium methyl 4-chlorothiazide, 6.67% tebuconazole, 8% acetone, 10% xylene, 7% dodecylbenzenesulfonate, 1% isooctyl alcohol, 0.5% gelatin, 3% hydroxymethyl cellulose, 3% propylene glycol, 0.5% benzoic acid, 0.5% borax, 0.02% sodium hydroxide, 1% sodium chloride, and deionized water to make up the balance.

[0058] The technical grade bensulfuron-methyl, sodium 2,4-methyl chloride, and tebuconazole were thoroughly mixed to form a homogeneous oil phase. Deionized water, propylene glycol, benzoic acid, borax, sodium hydroxide, and sodium chloride were thoroughly mixed to form a homogeneous aqueous phase. Under high-speed stirring, the aqueous phase was added to the oil phase to prepare a 30% bensulfuron-methyl, sodium 2,4-methyl chloride, and tebuconazole aqueous emulsion.

[0059] Formulation Example 5: 37% benzylsulfuron-methyl·2,4-chlorosodium·tebuconazole aqueous emulsion

[0060] 2.96% benzyl sulfonate, 29.42% sodium methyl 4,63% tebuconazole, 8% acetone, 10% acetonitrile, 7% alkylphenol polyoxyethylene ether, 1% isoamyl alcohol, 0.5% gum arabic, 3% hydroxymethyl cellulose, 3% propylene glycol, 0.5% benzoic acid, 0.5% borax, 0.02% sodium hydroxide, 1% sodium chloride, and deionized water to make up the balance.

[0061] The technical grade bensulfuron-methyl, sodium 2,4-methyl chloride, and tebuconazole were thoroughly mixed to form a homogeneous oil phase. Deionized water, propylene glycol, benzoic acid, borax, sodium hydroxide, and sodium chloride were thoroughly mixed to form a homogeneous aqueous phase. Under high-speed stirring, the aqueous phase was added to the oil phase to prepare a 37% bensulfuron-methyl, sodium 2,4-methyl chloride, and tebuconazole aqueous emulsion.

[0062] Formulation Example 6: 45% benzylsulfuron-methyl·2,4-chlorosodium·tebuconazole aqueous emulsion

[0063] 3.89% benzyl sulfonate, 39.26% sodium 2,4-D, 1.85% tebuconazole, 8% acetone, 15% acetonitrile, 8% alkylphenol polyoxyethylene ether, 1% isoamyl alcohol, 0.5% gum arabic, 3% hydroxymethyl cellulose, 3% propylene glycol, 0.5% benzoic acid, 0.5% borax, 0.025% sodium hydroxide, 1% sodium chloride, and deionized water to make up the balance.

[0064] The technical grade bensulfuron-methyl, sodium 2,4-methyl chloride, and tebuconazole were thoroughly mixed to form a homogeneous oil phase. Deionized water, propylene glycol, benzoic acid, borax, sodium hydroxide, and sodium chloride were thoroughly mixed to form a homogeneous aqueous phase. Under high-speed stirring, the aqueous phase was added to the oil phase to prepare a 45% bensulfuron-methyl, sodium 2,4-methyl chloride, and tebuconazole aqueous emulsion.

[0065] Formulation Example 7: 30% bensulfuron-methyl·2,4-chlorosodium·tebuconazole microemulsion

[0066] 2.13% benzyl sulfonate, 21.2% sodium methyl 4-chlorothiazide, 6.67% tebuconazole, 15% isopropanol, 8% phenethylphenol polyoxyethylene polyoxypropylene ether, 3% potassium sorbate, 3% ethylene glycol, 0.5% borax, 0.025% sodium hydroxide, and deionized water to make up the balance.

[0067] The technical grade bensulfuron-methyl, sodium 2,4-methyl chloride, tebuconazole, isopropanol, phenethylphenol polyoxyethylene polyoxypropylene ether, potassium sorbate, and ethylene glycol were thoroughly mixed to form a homogeneous and transparent oil phase. Deionized water, borax, and sodium hydroxide were thoroughly mixed to form a homogeneous and transparent aqueous phase. Under high-speed stirring, the aqueous phase was slowly added to the oil phase to prepare a 30% bensulfuron-methyl, sodium 2,4-methyl chloride, and tebuconazole microemulsion.

[0068] Formulation Example 8: 37% benzylsulfuron-2,4-methylchlorosodium-tebuconazole microemulsion

[0069] 2.96% benzyl sulfonate, 29.42% sodium methyl 4,63% tebuconazole, 8% acetone, 15% acetonitrile, 8% alkylphenol polyoxyethylene ether, 3% toluene glycidyl ether, 2% glycerol, 0.1% disodium hydrogen phosphate, 0.02% sodium hydroxide, and deionized water to make up the balance.

[0070] The technical grade bensulfuron-methyl, sodium 2,4-methyl chloride, and tebuconazole were thoroughly mixed to form a homogeneous and transparent oil phase. Deionized water, disodium hydrogen phosphate, and sodium hydroxide were thoroughly mixed to form a homogeneous aqueous phase. Under high-speed stirring, the aqueous phase was slowly added to the oil phase to prepare a 37% bensulfuron-methyl, sodium 2,4-methyl chloride, and tebuconazole microemulsion.

[0071] Formulation Example 9: 45% benzylsulfuron-methyl·2,4-chlorosodium·tebuconazole microemulsion

[0072] 3.89% benzyl sulfonate, 39.26% sodium 2,4-D, 1.85% tebuconazole, 8% acetone, 15% chloroform, 8% alkylphenol polyoxyethylene ether, 3% toluene glycidyl ether, 2% polyethylene glycol, 0.1% borax, 0.02% sodium hydroxide, and deionized water to make up the balance.

[0073] The technical grade bensulfuron-methyl, sodium 2,4-methyl chloride, and tebuconazole were thoroughly mixed to form a homogeneous and transparent oil phase. Deionized water, borax, and sodium hydroxide were thoroughly mixed to form a homogeneous aqueous phase. Under high-speed stirring, the aqueous phase was slowly added to the oil phase to prepare a 45% bensulfuron-methyl, sodium 2,4-methyl chloride, and tebuconazole microemulsion.

[0074] (II) Indoor Biometrics Example

[0075] The indoor biological testing of this invention was conducted from March to May 2019 in the solar greenhouse of the Institute of Plant Protection, Hebei Academy of Agricultural and Forestry Sciences.

[0076] Test pesticides: 75% bensulfuron-methyl water-dispersible granules (Qingdao Hansheng Biotechnology Co., Ltd.), 56% MCPA sodium soluble powder (Shandong Binnong Technology Co., Ltd.), 12.5% ​​tebuconazole emulsifiable concentrate (Hebei Guanlong Agrochemical Co., Ltd.). Test weed: Desmodium styracifolium (collected in May 2018 from a wheat field in Wangzhuang Village, Jiaozhuang Township, Lianchi District, Baoding City, Hebei Province).

[0077] Test pathogen: Wheat powdery mildew

[0078] Dosage settings: Bensulfuron-methyl and sodium 2,4-methyl chloride are set as component A, and the ratio between them remains unchanged (1:11.2). Tebuconazole is set as component B. The ratios of A and B are 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 8:1, and 16:1, respectively. The specific dosage of active ingredients is shown in Table 1 and Table 2.

[0079] Indoor biological test example 1: Control efficacy against *Dendrobium nobile*

[0080] Select 12cm diameter plastic pots to cultivate *Impatiens balsamina* seedlings. When the weeds have two pairs of true leaves, thin the seedlings to 12 plants per pot. Apply a foliar spray, using the same volume of water as the control, at a concentration of 450L / hm². 2 Each treatment was repeated four times. The number of surviving seedlings was assessed 21 days after application, and the above-ground parts of the weeds were harvested and their fresh weight measured. The actual control efficacy E for each treatment was calculated.

[0081]

[0082] In the formula: PT—fresh weight of weeds in the herbicide treatment group;

[0083] CK – Blank control group: Fresh weight of weeds.

[0084] The Gowing method was used to evaluate the combined effect of two herbicides in a certain proportion on weeds. The theoretical control efficacy E0 of the combined herbicide was calculated using the following formula:

[0085]

[0086] In the formula: X — the efficacy of component A when the dosage is P;

[0087] Y—the efficacy of component B when the dosage is Q;

[0088] E0—The theoretical efficacy of mixing component A at a dosage of P and component B at a dosage of Q;

[0089] E – The actual preventive effect after mixing component A at a dosage of P and component B at a dosage of Q.

[0090] E–E0 > 10% indicates a synergistic effect; E–E0 < -10% indicates an antagonistic effect; -10% < E–E0 < 10% indicates an additive effect.

[0091] Biochemical tests showed that the E-E0 values ​​of component A (bensulfuron-methyl, sodium 2,4-methyl) and component B (tebuconazole) in the ratio range of 2 to 16:1 were 21.09 to 34.08, indicating that the three components had a significant synergistic effect when mixed within this range. When the amounts of benzsulfuron-methyl and sodium 2,4-methyl were constant, the higher the content of tebuconazole, the more pronounced the synergistic effect. The E-E0 values ​​of component A (bensulfuron-methyl, sodium 2,4-methyl) and component B (tebuconazole) in the ratio range of 2 to 4:1 were 30.25 to 34.08, indicating that the synergistic effect was most significant when mixed within this range, with the optimal ratio being 3:1.

[0092] Table 1. Results of bioassays on *Desmodium styracifolium* using different ratios of bensulfuron-methyl, sodium 2,4-D, and tebuconazole.

[0093]

[0094]

[0095] Indoor biological test example 2: Efficacy against powdery mildew

[0096] Wheat was planted in 12cm diameter plastic pots. Foliar spraying was applied to the wheat at the 3-leaf stage. Before application, seedlings were thinned to 25 uniform plants per pot. The pesticide treatment was the same as in Example 1 of the indoor bioassay. After application, the wheat was inoculated with powdery mildew. Inoculation was performed using the sweeping method: a pre-infected seedling with sufficient spores was gently shaken above the tested variety to dislodge the spores. The seedlings were then placed between rows to allow natural spread. The inhibition rate against wheat powdery mildew was investigated when the control group developed a large number of spore masses. The investigation method followed the guidelines in "Guidelines for Indoor Bioassay of Pesticides - Experiment on Control of Wheat Powdery Mildew (Pot Method)". The following grading method is adopted: Grade 0: No disease; Grade 1: Diseased area accounts for less than 5% of the total leaf area; Grade 3: Diseased area accounts for 6%-15% of the total leaf area; Grade 5: Diseased area accounts for 16%-25% of the total leaf area; Grade 7: Diseased area accounts for 26%-50% of the total leaf area; Grade 9: Diseased area accounts for more than 50% of the total leaf area.

[0097]

[0098]

[0099] The results of the biological test show that, referring to the mixing calculation method of Example 1 of the indoor biological test, the E–E0 value of component A (bensulfuron-methyl, sodium 2,4-methyl chloride) and component B (tebuconazole) in the ratio range of 0.5 to 16:1 is -1 to 4, indicating that the three components have an additive effect when mixed in the range of 0.5 to 16:1.

[0100] Table 2. Bioassay results of different ratios of bensulfuron-methyl, sodium 2,4-D, and tebuconazole against wheat powdery mildew.

[0101]

[0102]

[0103] (III) Field Efficacy Examples

[0104] The field efficacy test examples of this invention were conducted in accordance with the "Guidelines for Field Efficacy Tests of Pesticides (I) Herbicides for the Control of Weeds in Wheat Crops (GB / T 17980.41-2000)". Field plot trials were conducted to verify the results of the indoor bioassays and to clarify the field control efficacy of the three herbicides in a certain proportion against weeds. The test methods are as follows:

[0105] Foliar spraying of winter wheat after greening and before jointing, with a solution volume of 450 L / hm. 2 Each treatment was repeated 4 times, with a cell area of ​​20m². 2 Randomized block designation. A survey was conducted 30 days after drug administration, with four randomly selected sampling points from each block, each 1 meter apart. 2 The fresh weight of each weed was investigated separately, and the control efficacy E of each treatment was calculated:

[0106]

[0107] In the formula: PT—fresh weight of weeds in the treated area;

[0108] CK – Blank control area, weed freshness weight.

[0109] The experiment was conducted in Jiaozhuang Village, Lianchi District, Baoding City, Hebei Province. The targets were broadleaf weeds in wheat fields, including *Desmodium styracifolium* and *Capsella bursa-pastoris*. The dosage and efficacy of each herbicide in each treatment are shown in Table 3. Field efficacy trials showed that the herbicidal composition of this invention, at dosages lower than those of bensulfuron-methyl, sodium 2,4-D, and tebuconazole used alone, achieved control efficacy of 90.54%–98.58% against *Desmodium styracifolium*, 92.75%–98.25% against *Capsella bursa-pastoris*, and 91.65%–98.42% for the total control. These efficacy rates were significantly higher than those of the three herbicides used alone, indicating that the combined use of bensulfuron-methyl, sodium 2,4-D, and tebuconazole has a significant synergistic effect and can effectively control broadleaf weeds in wheat fields. Furthermore, the herbicidal composition of this invention also has advantages such as crop safety and rapid action, making it an ideal herbicide.

[0110] Table 3. Field efficacy trial results of the combined use of bensulfuron-methyl, sodium 2,4-D, and tebuconazole for controlling broadleaf weeds in wheat fields.

[0111]

[0112]

[0113] (iv) Comparative Examples

[0114] In wheat fields with uniformly growing *Dendrobium nobile*, a field plot trial was conducted. After the wheat turned green, pesticides were sprayed. These included 75% benzyl sulfide water-dispersible granules (Qingdao Hansheng Biotechnology Co., Ltd.), 56% 2,4-D sodium soluble powder (Shandong Binnong Technology Co., Ltd.), 12.5% ​​tebuconazole water-in-oil emulsion (Hebei Guanlong Agricultural Chemical Co., Ltd.), and 80% carbendazim wettable powder (Shaanxi Guofeng Chemical Co., Ltd.). Treatments included tebuconazole alone, carbendazim alone, a mixture of benzyl sulfide and 2,4-D sodium, a mixture of benzyl sulfide, 2,4-D sodium, and tebuconazole, and a mixture of benzyl sulfide, 2,4-D sodium, and carbendazim. A water control was also included. Each plot was 20 m². 2 The experiment was repeated four times. The plant control efficacy and fresh weight control efficacy against *Desmodium styracifolium* were investigated 30 days after application. The safety of the pesticide on wheat was observed throughout the experiment.

[0115] Table 4 shows the dosage and efficacy of each treatment. The results indicate that the fungicide tebuconazole showed better inhibitory effects on *Desmodium styracifolium* than carbendazim. Tebuconazole alone achieved 12.10% control per plant and 12.71% control per fresh weight of *Desmodium styracifolium*. When mixed with the herbicides bensulfuron-methyl and 2,4-D sodium, the control per plant and control per fresh weight were 94.00% and 95.05%, respectively, which were 13.66% and 12.34% higher than the treatment with bensulfuron-methyl and 2,4-D sodium alone. This demonstrates a significant synergistic effect between tebuconazole and the herbicides bensulfuron-methyl and 2,4-D sodium. No phytotoxicity symptoms were observed in wheat during the entire experiment.

[0116] Table 4. Effects of mixing herbicides with different fungicides on the control of *Desmodium styracifolium*.

[0117]

[0118] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A herbicidal composition, characterized in that, It includes active ingredients A and B, wherein active ingredient A is a combination of benzylsulfuron and sodium 2,4-methyl chloride, active ingredient B is tebuconazole, the mass ratio of active ingredients A and B is 2 to 16:1, and the mass ratio of benzylsulfuron and sodium 2,4-methyl chloride is 1:10 to 11.

2.

2. The herbicidal composition according to claim 1, characterized in that, The herbicidal composition is prepared into pesticide-acceptable formulations, including suspension emulsions, microemulsions, water-in-oil emulsions, emulsifiable concentrates, oil suspensions, suspensions, wettable powders, dry suspensions, granules, water-dispersible granules, powders, oils, and microcapsule suspensions.

3. The herbicidal composition according to claim 2, characterized in that, The active ingredients A and B are present in the herbicidal composition at a weight percentage of 1% to 80%.

4. The herbicidal composition according to claim 3, characterized in that, When the herbicidal composition is a suspension emulsion, it comprises the following components in the indicated mass percentages: benzyl sulfide 1%–20%, sodium 2,4-D chlorpyrifos 3%–60%, tebuconazole 1%–20%, solvent 10%–50%, emulsifier 5%–8%, dispersant 0.1%–3%, thickener 0.1%–5%, pH adjuster 0.1%–5%, and water to make up the balance.

5. The herbicidal composition according to claim 3, characterized in that, When the herbicidal composition is an emulsion, it comprises the following components in the indicated mass percentages: benzyl sulfide 1%–20%, sodium 2,4-D chlorpyrifos 3%–60%, tebuconazole 1%–20%, solvent 10%–30%, emulsifier 8%–10%, dispersant 0.1%–8%, antifreeze 5%–10%, defoamer 0.1%–3%, preservative 0%–1%, thickener 0.1%–5%, density adjuster 0%–5%, pH adjuster 0.1%–5%, and water to make up the balance.

6. The herbicidal composition according to claim 3, characterized in that, When the herbicidal composition is a microemulsion, it comprises the following components in the indicated mass percentages: benzyl sulfide 1%–20%, sodium 2,4-D chlorpyrifos 3%–60%, tebuconazole 1%–20%, solvent 10%–30%, emulsifier 8%–10%, stabilizer 0.5%–3%, pH adjuster 0.1%–5%, antifreeze 2%–10%, and water to make up the balance.

7. The use of the herbicidal composition according to any one of claims 1 to 6 in the control of agricultural weeds.

8. The application according to claim 7, characterized in that, The herbicidal composition is used to control broadleaf weeds in wheat fields.

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