A ternary herbicidal composition containing an als enzyme inhibitor and its use

Abstract

This invention provides a ternary herbicidal composition containing an ALS enzyme inhibitor and its application. The herbicide composition comprises three active ingredients: active ingredient A is pyrimisulfuron and its salt; active ingredient B is quinclorac acid and its salt; and active ingredient C is selected from one of clopyralid, triclopyralid, clopyralidic acid, fluorochloropyralidic acid and its salts and esters. The weight ratio of each active ingredient is 1:(1-50):(1-50), and the total weight percentage of the active ingredients in the herbicidal composition is 1-80%. This ternary herbicidal composition can be used to control various grass weeds, broadleaf weeds, and sedge weeds in warm-season lawns. It has a significant synergistic effect compared to single-component herbicides, improving control efficacy, especially against pyrimisulfuron-methyl weeds. Furthermore, it also has good control efficacy against older weeds, with a long-lasting effect and high safety.

Description

Technical Field

[0001] This invention belongs to the field of pesticides, specifically relating to a ternary herbicidal composition of pyrimisulfuron, quinclorac acid and clopyralid and its application. Background Technology

[0002] With the continuous acceleration of urbanization, warm-season turf is widely used in various fields due to its ability to beautify the environment and purify the air. It is not only widely used in urban green belts and park lawns, but also in various sports venues such as football fields and golf courses.

[0003] Weed control is a crucial aspect of lawn maintenance, and currently, selective herbicides are the most convenient and effective method. However, with the widespread use of herbicides, weed resistance has increased, leading to decreased control effectiveness. Furthermore, some older weeds are difficult to control. Effective control of these highly resistant and older weeds is necessary.

[0004] Currently, the main herbicide on the market for controlling warm-season lawn weeds is pyrimisulfuron, but it suffers from serious resistance and is largely ineffective against older weeds. Quinclorac is a hormone-type quinoline carboxylic acid herbicide used to control barnyard grass and other grassy weeds in lawns, but its effectiveness has significantly weakened in recent years due to increasing barnyard grass resistance. Clopyralid is a systemic hormone-type herbicide used to control broadleaf weeds in lawns, but it is ineffective against grassy and sedge weeds.

[0005] Patent EP3664609A4 discloses at least two hormone-based herbicides and at least one ALS-inhibiting herbicide. Fluroxypyr and quinclorac are mentioned only among the many hormone-based herbicides, and flazasulfuron is mentioned only among the many ALS-inhibiting herbicides. However, no data indicates a synergistic effect, and no specific application methods are provided.

[0006] Patent CN103281899A discloses that a combination of quinclorac acid and clopyralid has a synergistic effect on barnyard grass (Echinochloa crus-galli; ECHCG), leptospira chinensis (LEFCH), and brachiaria platyphylla (BRAPP) within a certain ratio range. This invention, based on quinclorac acid and clopyralid, adds the ALS enzyme inhibitor herbicide pyrimisulfuron. The synergistic effect, achieved through the cooperation of different mechanisms of action, is even more significant, and it also shows outstanding performance in controlling pyrimisulfuron-resistant weeds and older weeds.

[0007] To address the aforementioned technical problems, this invention provides a ternary herbicidal composition containing an ALS enzyme inhibitor. Through the combination of herbicides with different mechanisms of action, it exhibits significant synergistic effects against grassy weeds, broadleaf weeds, and sedges, with particularly good efficacy against weeds resistant to pyrimisulfuron. Furthermore, it also provides excellent control over older weeds, has a long residual effect, and high safety. Summary of the Invention

[0008] The purpose of this invention is to provide a ternary herbicidal composition containing an ALS enzyme inhibitor.

[0009] Another object of the present invention is to provide the weeding application of the weeding composition in warm-season lawns.

[0010] The herbicidal composition of the present invention has a synergistic effect, especially effective against weeds resistant to pyrimisulfuron; in addition, it also has a good control effect on older weeds, with a long-lasting effect and high safety.

[0011] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0012] This invention provides a ternary herbicidal composition containing an ALS enzyme inhibitor, comprising three active ingredients, wherein active ingredient A is pyrimisulfuron and its salt, active ingredient B is quinclorac acid and its salt, and active ingredient C is selected from one of clopyralid, triclopyralid, clopyralid, fluorochloropyralid, and their salts and esters. The weight ratio of active ingredients A, B and C is 1:(1-50):(1-50), and the total weight percentage of the active ingredients accounts for 1-80% of the total weight of the herbicidal composition.

[0013] In a further preferred embodiment, the weight ratio of active ingredients A, B and C is 1:(3-30):(3-30), and the total weight of the active ingredients accounts for 10-70% of the total weight of the herbicidal composition.

[0014] The active ingredients, compounds A, B, and C, in this invention can encompass any agriculturally acceptable salt, including sodium salts, potassium salts, ammonium salts, magnesium salts, calcium salts, monomethyl salts, dimethyl salts, triethyl salts, inorganic acid salts, organic acid salts, etc.

[0015] The esters covered by the active ingredient compound C in this invention can be any agriculturally acceptable ester, including methyl ester, ethyl ester, propyl ester, isooctyl ester, etc.

[0016] The present invention also provides the application of the herbicidal composition in controlling grass weeds, broadleaf weeds and / or sedge weeds.

[0017] Among them, the grassy weeds include barnyard grass (Echinochloa crus-galli), crabgrass (Digitaria sanguinalis), foxtail grass (Setaria viridis), goosegrass (Eleusine indica), wild oat (Alopecurus aequalis), Japanese wild oat (Alopecurus japonicus), wild oat (Avena fatua), etc.

[0018] The broadleaf weeds include Polygonum, Portulaca oleracea, Capsella bursa-pastoris, Abutilon theophrasti, Amaranthus spinosus, Amaranthus retroflexus, Chenopodium album, Rumexcrispus, Commelina communis, Xanthium strumarium, Solanum nigrum, Cassia tora, Stellaria media, Stellaria aguatica, Cerastium arvense, Galium aparine, and Veronica didyma, among others.

[0019] The sedges mentioned include Cyperus rotundus, Cyperus iria, and Cyperus difformis.

[0020] Furthermore, the present invention also provides the application of this herbicidal composition in controlling grassy weeds, broadleaf weeds, and / or sedge weeds in warm-season lawns. In particular, the herbicidal composition of the present invention is significantly effective in controlling resistant weeds and older weeds.

[0021] The resistance index (RI) of the resistant weeds is ≥10.

[0022] The term "old weeds" refers to weeds with 5 or more leaves and a plant height of 5 cm or more.

[0023] Among them, the warm-season turf varieties include Cynodon dactylon, Zoysia japonica Steud., and Eremochloa ophiuroides.

[0024] Furthermore, the herbicidal composition provided by the present invention can be applied to harmful plants, crops, plant seeds, or areas where plants grow.

[0025] The ternary herbicidal composition of the present invention can be formulated into solid formulations such as powders, wettable powders, water-dispersible granules, dry suspensions, or effervescent tablets; and liquid formulations such as suspensions and dispersible oil suspensions. The definitions, development methods, application technologies, quality indicators, and testing methods of the above formulations are referenced in Xu Yan, Liu Guangwen et al. ["Pesticide Liquid Formulations," (2018, Chemical Industry Press)], and Liu Guangwen et al. ["Pesticide Solid Formulations," (2018, Chemical Industry Press)].

[0026] The ternary herbicidal composition of the present invention also contains commonly used adjuvants required for the formulation of pesticide formulations, wherein the solid formulation includes dispersants, wetting agents, defoamers, complexing agents, pH adjusters and fillers, etc., and the liquid formulation includes dispersants, emulsifiers, wetting agents, stabilizers, thickeners, pH adjusters, defoamers and antifreeze agents, etc.

[0027] The wetting agent is selected from one or more of EO / PO block polyether, fatty alcohol polyoxyethylene ether, fatty alcohol ethoxy compound, tallow ethoxy ammonium salt, alkyl naphthalene sulfonate, fatty alcohol polyoxyethylene ether sulfate, and acyl glutamate.

[0028] The dispersant is selected from one or more of the following: EO / PO block polyether, condensed naphthalene sulfonate, sodium salt of phenol sulfonic acid condensate, sodium formaldehyde condensate of methyl naphthalene sulfonate, sodium lignin sulfonate, sodium methylene dinaphthalene sulfonate, sodium salt of acrylic acid homopolymer, high molecular weight polycarboxylate, sodium dioctyl sulfosuccinate, and sodium salt of maleic acid-acrylic acid copolymer.

[0029] The emulsifier is selected from one or more of alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, fatty amine polyoxyethylene ether, castor oil ethylene oxide adduct and its derivatives, alkyl sulfonates, alkyl biphenyl ether sulfonates, naphthalene sulfonic acid formaldehyde condensates, alkylphenol polyoxyethylene ether formaldehyde condensates, polyoxyethylene polyoxypropylene block copolymers, alkyl naphthalene sulfonic acid formaldehyde condensates, quaternary ammonium salts, tallow ethoxy ammonium salts, amino acids, amine oxides, betaine, and acylglutamates.

[0030] The application of these adjuvants aims to achieve the stability of the physical properties of the formulation and the desired field application effect. For the types, functions, and application techniques of adjuvants, please refer to Zhang Xiaojun, Liu Guangwen, et al. ["Pesticide Adjuvants", (2018, Chemical Industry Press).]

[0031] Those skilled in the art know that currently, the main herbicide on the market for controlling warm-season lawn weeds is pyrimisulfuron, but it suffers from serious resistance and is essentially ineffective against older weeds. Quinclorac, a hormone-type quinoline carboxylic acid herbicide, is commonly used to control barnyard grasses and other grassy weeds in lawns, but with increased use in recent years, barnyard grass resistance has continuously improved, significantly weakening its control effect. Clopyralid, a systemic hormone-type herbicide, is used to control broadleaf weeds in lawns, but it is ineffective against grassy and sedge weeds.

[0032] After extensive experimentation, the applicant unexpectedly discovered that when herbicides with different mechanisms of action are combined, particularly when the ALS enzyme inhibitor herbicide pyrimisulfuron is combined with the hormone herbicide quinclorac and the systemic hormone herbicide clopyralid, there is a significant synergistic effect on warm-season lawn weeds, further broadening the weed control spectrum and improving the control effect. In particular, it is remarkably effective against weeds resistant to pyrimisulfuron. Furthermore, the composition of this invention can achieve good control of grass weeds, broadleaf weeds, and sedge weeds, and also has a control effect on older weeds. It has significant control efficacy, long-lasting effect, high safety for lawns, and is not prone to resistance.

[0033] Compared with the prior art, the advantages of the present invention are as follows:

[0034] The ternary herbicidal composition provided by this invention consists of active ingredients with different mechanisms of action. Furthermore, the composition of this invention, when combined in a specific ratio, has good control effects on grass weeds, broadleaf weeds, and sedge weeds, and can effectively control weeds resistant to pyrimisulfuron, maintaining good weed control effect and exhibiting significant synergistic effects. It can significantly reduce the use of pesticides, has control effects on older weeds, and is highly safe for warm-season lawns.

[0035] The herbicidal composition provided by this invention can broaden the control spectrum, effectively delay the development of resistance, reduce the cost of use and reduce environmental pollution, and has great application value for controlling warm-season lawn weeds. Detailed Implementation

[0036] To better understand the essence of this invention, the following embodiments further illustrate the content of this invention, but these should not be considered as limitations on the invention. The content mentioned in the embodiments is not intended to limit the invention, and the selection of material formulations can be adapted to local conditions without substantially affecting the results. In these embodiments, unless otherwise stated, all percentages are weight percentages.

[0037] Example 1 of indoor activity assay:

[0038] The inventors conducted extensive target testing, using the toxicity test of fennel as an example, to demonstrate indoor activity determination.

[0039] The tests were conducted in accordance with the People's Republic of China Agricultural Industry Standard NY / T 1155.4-2006 "Guidelines for Indoor Bioassay of Pesticides - Herbicides Part 4: Activity Assay Test - Stem Spray Method" and the People's Republic of China Agricultural Industry Standard NY / T1155.7-2006 "Guidelines for Indoor Bioassay of Pesticides - Herbicides Part 7: Determination of Combined Effects of Mixtures".

[0040] 1. Experimental Objective

[0041] The fresh weight control efficacy of pyrimisulfuron, quinclorac acid, and clopyralid, as well as their different mixtures, against weeds was determined, and their combined effects were evaluated, providing a scientific basis for the formulation development of mixed pesticides and field efficacy trials for pesticide registration.

[0042] 2. Test conditions

[0043] 2.1 Test target: Anise

[0044] 2.2 Instruments and equipment: 3WPSH-500E bioassay spray tower, electronic balance (sensitivity 0.1mg), pots, beakers, pipettes.

[0045] 3. Experimental Design

[0046] 3.1 Test soil: The test used air-dried soil with organic matter content <3%, neutral pH, good permeability, and passed through sieve.

[0047] 3.2 Experimental Methods: Soil was quantitatively filled to 4 / 5 of the pot's capacity. Bottom irrigation was used to ensure complete soil moisture. Pretreated seeds of the target weed, *Hemiberlesia lataniae*, were evenly sown on the soil surface, covered with approximately 1.0 cm of soil, and then transplanted to a greenhouse for conventional cultivation. Water was added to the pots until saturation was achieved using bottom irrigation. After emergence, thinning was performed to ensure uniform weed density (120-150 plants per square meter). When the weeds had grown to 2-4 leaves, foliar spraying was performed using a 3WPSH-500E bioassay sprayer produced by the Nanjing Agricultural Machinery Research Institute. The spray volume was 20 mL, and the operating pressure was 0.15 MPa. Each treatment group was replicated three times, with a control group (no spray). The growth of the target weeds was observed regularly.

[0048] 4. Absolute value (numerical measurement) survey method

[0049] After treatment, the growth status of the tested weeds was observed and recorded regularly. Weed control activity was investigated and recorded 30 days after treatment using an absolute value (numerical measurement) method, and symptoms of damage were described. Main symptoms included: color changes (yellowing, etc.); morphological changes (curved new leaves, etc.); and growth changes (dehydration, wilting, dwarfing, tufting, etc.).

[0050] Based on the survey data, the fresh weight inhibition efficacy was calculated using the following formula, expressed as a percentage (%). The result was rounded to two decimal places. The fresh weight inhibition rate was calculated using the following formula based on the survey results:

[0051] Fresh weight inhibition rate (%) = (CK fresh weight - treatment fresh weight) / CK fresh weight × 100

[0052] The herbicidal activity of the mixed herbicides was tested using the Colby method, i.e., E0 = XYZ / 10000, where X is the weed survival rate of herbicide A at dosage P; Y is the weed survival rate of herbicide B at dosage Q; Z is the weed survival rate of herbicide C at dosage W; E0 is the theoretical weed survival rate of herbicides (A+B+C) at dosage (P+Q+W); and E is the actual weed survival rate of each treatment. According to the Colby method, when E0-E>10%, it indicates that the mixed herbicides have a synergistic effect; when E0-E<-10%, it indicates that the mixed herbicides have an antagonistic effect; and when the E0-E value is within ±10%, it indicates that the mixed herbicides have an additive effect.

[0053] 5. Experimental Results and Conclusions

[0054] Based on extensive compounding experiments of the present invention, the following ratios were used for toxicity testing and demonstration. The combined toxic effects of different ratios of pyrimisulfuron-methyl, quinclorac, and clopyralid on anise after preliminary testing are shown in Table 1:

[0055] Table 1: Combined toxicity of herbicidal compositions on fennel (spraying method)

[0056]

[0057] As shown in Table 1, when pyrimisulfuron and quinclorac were combined, the E0-E ratios were both within ±10% at 2:10 and 4:20, indicating an additive effect. At 1:0 and 2:40, the E0-E ratio was >10%, indicating a certain synergistic effect. When pyrimisulfuron and clopyralid were combined, the E0-E ratios were both within ±10% at 2:10 and 4:10, indicating an additive effect. At 1:20 and 2:20, the E0-E ratio was >10%, indicating a certain synergistic effect. When quinclorac and clopyralid were combined, the E0-E ratios were both within ±10% at 10:40 and 40:10, indicating an additive effect. At 20:10 and 10:10, the E0-E ratio was >10%, indicating a certain synergistic effect. When pyrimisulfuron, quinclorac, and clopyralid are combined, they exhibit excellent control efficacy against broadleaf weeds such as fennel compared to individual pesticide components used alone or in combination. At weight ratios of pyrimisulfuron, quinclorac, and clopyralid of 4:20:20, 2:20:40, 2:20:10, 2:40:40, 1:10:10, and 1:20:40, the E0-E ratio is greater than 10%. Specifically, at ratios of 4:20:20, 2:20:40, 2:20:10, 2:40:40, and 1:10:10, the E0-E ratio is greater than 15%. At ratios of 2:40:40 and 1:10:10, the E0-E ratio exceeds 20%. The theoretical survival rate of fennel is significantly higher than the actual survival rate, demonstrating a synergistic effect.

[0058] The herbicidal test results of the combination of the three components, pyrimisulfuron, quinclorac acid and clopyralid, showed that the activity of the ternary compound was significantly increased and was significantly better than that of the binary compound.

[0059] Example 2 of indoor resistant grass activity determination:

[0060] The inventors conducted extensive target testing, using the toxicity test of mature barnyard grass (Echinochloa crus-galli (L.) P. Beauv.) as an example to demonstrate indoor activity determination. Mature barnyard grass is obtained by indoor cultivation of barnyard grass seeds until the plant has more than 5 leaves and a height of more than 5 cm.

[0061] The tests were conducted in accordance with the People's Republic of China Agricultural Industry Standard NY / T 1155.4-2006 "Guidelines for Indoor Bioassay of Pesticides - Herbicides Part 4: Activity Assay Test - Stem Spray Method" and the People's Republic of China Agricultural Industry Standard NY / T1155.7-2006 "Guidelines for Indoor Bioassay of Pesticides - Herbicides Part 7: Determination of Combined Effects of Mixtures".

[0062] 1. Experimental Objective

[0063] The fresh weight control efficacy of pyrimisulfuron, quinclorac acid, and clopyralid, as well as their different mixtures, against weeds was determined, and their combined effects were evaluated, providing a scientific basis for the formulation development of mixed pesticides and field efficacy trials for pesticide registration.

[0064] 2. Test conditions

[0065] 2.1 Experimental Target: Old-growth barnyard grass

[0066] 2.2 Instruments and equipment: 3WPSH-500E bioassay spray tower, electronic balance (sensitivity 0.1mg), pots, beakers, pipettes.

[0067] 3. Experimental Design

[0068] 3.1 Test soil: The test used air-dried soil with organic matter content <3%, neutral pH, good permeability, and passed through sieve.

[0069] 3.2 Experimental Methods: Soil was quantitatively filled to 4 / 5 of the pots. Bottom irrigation was used to ensure complete soil moisture. Pretreated barnyardgrass resistant seeds were evenly sown on the soil surface, covered with approximately 1.0 cm of soil, and then transferred to a greenhouse for conventional cultivation. Water was added to the pots until saturated using bottom irrigation. After emergence, thinning was performed to ensure uniform weed density (120-150 plants per square meter). When the weeds had grown to 2-4 leaves, foliar spraying was performed using a 3WPSH-500E bioassay sprayer produced by the Nanjing Agricultural Machinery Research Institute. The spray volume was 20 mL, and the operating pressure was 0.15 MPa. Each treatment group was replicated three times, with a control group (no spray). The growth of the target weeds was observed regularly.

[0070] 4. Absolute value (numerical measurement) survey method

[0071] After treatment, the growth status of the tested weeds was observed and recorded regularly. Weed control activity was investigated and recorded 30 days after treatment using an absolute value (numerical measurement) method, and symptoms of damage were described. Main symptoms included: color changes (yellowing, etc.); morphological changes (curved new leaves, etc.); and growth changes (dehydration, wilting, dwarfing, tufting, etc.).

[0072] Based on the survey data, the fresh weight inhibition efficacy was calculated using the following formula, expressed as a percentage (%). The result was rounded to two decimal places. The fresh weight inhibition rate was calculated using the following formula based on the survey results:

[0073] Fresh weight inhibition rate (%) = (CK fresh weight - treatment fresh weight) / CK fresh weight × 100

[0074] The herbicidal activity of the mixed herbicides was tested using the Colby method, i.e., E0 = XYZ / 10000, where X is the weed survival rate of herbicide A at dosage P; Y is the weed survival rate of herbicide B at dosage Q; Z is the weed survival rate of herbicide C at dosage W; E0 is the theoretical weed survival rate of herbicides (A+B+C) at dosage (P+Q+W); and E is the actual weed survival rate of each treatment. According to the Colby method, when E0-E>10%, it indicates that the mixed herbicides have a synergistic effect; when E0-E<-10%, it indicates that the mixed herbicides have an antagonistic effect; and when the E0-E value is within ±10%, it indicates that the mixed herbicides have an additive effect.

[0075] 5. Experimental Results and Conclusions

[0076] Based on extensive mixing experiments of this invention, the following ratios were used for toxicity testing and demonstration. The combined toxicity effects of different ratios of pyrimisulfuron-methyl, quinclorac acid, and clopyralid on mature barnyardgrass after preliminary testing are shown in Table 2:

[0077] Table 2: Combined toxicity of herbicidal compositions against mature barnyardgrass (spraying method)

[0078]

[0079]

[0080] As shown in Table 2, when pyrimisulfuron and quinclorac were combined, the E0-E ratios were both within ±10% at 2:10 and 4:20, indicating an additive effect. At 1:10 and 2:40, the E0-E ratio was >10%, indicating a certain synergistic effect. When pyrimisulfuron and clopyralid were combined, the E0-E ratios were both within ±10% at 2:10 and 4:10, indicating an additive effect. At 1:20 and 2:20, the E0-E ratio was >10%, indicating a certain synergistic effect. When quinclorac and clopyralid were combined, the E0-E ratios were both within ±10% at 10:40 and 40:10, indicating an additive effect. At 20:10 and 10:10, the E0-E ratio was >10%, indicating a certain synergistic effect. When pyrimisulfuron, quinclorac, and clopyralid are combined, they exhibit excellent control efficacy against barnyardgrass and other grassy weeds compared to individual pesticide components used alone or in combination. At weight ratios of pyrimisulfuron, quinclorac, and clopyralid of 4:20:20, 2:20:40, 2:20:10, 2:40:40, 1:10:10, and 1:20:40, the effective rate (E0-E) is greater than 10%. Specifically, at ratios of 4:20:20, 2:20:40, 2:20:10, 2:40:40, and 1:10:10, the E0-E is greater than 15%. At ratios of 2:40:40 and 1:10:10, the E0-E exceeds 20%. The theoretical survival rate of barnyardgrass is significantly higher than the actual survival rate, demonstrating a synergistic effect.

[0081] The herbicidal test results of the combination of the three components, pyrimisulfuron, quinclorac acid and clopyralid, showed that the activity of the ternary compound was significantly increased and was significantly better than that of the binary compound.

[0082] Formulation Excipient Example 1: 34% pyrimisulfuron-dichloroquinoline acid-clopyralid water-dispersible granules (1:30:3)

[0083] The composition of 34% pyrimisulfuron-dichloroquinoline acid-clopyralid water-dispersible granules is shown in Table 3:

[0084] Table 3. Component details of 34% pyrimisulfuron-dichloroquinoline acid-clopyralid water-dispersible granules

[0085]

[0086] According to the component details in Table 3, active ingredient 1, active ingredient 2, active ingredient 3, dispersant, wetting agent, and carrier are added to a mixing tank and mixed for 10 minutes. The above materials are then subjected to air jet milling until D90 ≤ 25 μm. The milled materials are then mixed with water using a mixer (150-180 kg of deionized water per ton of material) to make the material plastic. The uniformly mixed material is then extruded into columnar particles with a diameter of 1.0 mm and dried with hot air at 80-90℃ until the moisture content is less than 3%, thus obtaining the 34% pyrimisulfuron-dichloroquinoline acid-clopyralid water-dispersible granules of the present invention. Testing shows that the 34% pyrimisulfuron-dichloroquinoline acid-clopyralid water-dispersible granules of the present invention meet all product standards and are qualified products.

[0087] Formulation Excipient Example 2: 34% pyrimisulfuron-dichloroquinoline-clopyralid water-dispersible granules (1:3:30)

[0088] The composition of 34% pyrimisulfuron-dichloroquinoline acid-clopyralid water-dispersible granules is shown in Table 4:

[0089] Table 4. Component details of 34% pyrimisulfuron-dichloroquinoline acid-clopyralid water-dispersible granules

[0090]

[0091] According to the component details in Table 4, active ingredient 1, active ingredient 2, active ingredient 3, dispersant, wetting agent, and carrier are added to a mixing tank and mixed for 10 minutes. The above materials are then subjected to air jet milling until D90 ≤ 25 μm. The milled materials are then mixed with water using a mixer (150-180 kg of deionized water per ton of material) to make the material plastic. The uniformly mixed material is then extruded into columnar particles with a diameter of 1.0 mm and dried with hot air at 80-90℃ until the moisture content is less than 3%, thus obtaining the 34% pyrimisulfuron-dichloroquinoline acid-clopyralid water-dispersible granules of the present invention. Testing shows that the 34% pyrimisulfuron-dichloroquinoline acid-clopyralid water-dispersible granules of the present invention meet all product standards and are qualified products.

[0092] Formulation Excipient Example 3: 11% pyrimisulfuron-dichloroquinoline-clopyralid suspension (1:5:5)

[0093] The composition of 11% pyrimisulfuron-dichloroquinoline-clopyralid suspension is shown in Table 5:

[0094] Table 5. Component Details of 11% Pyrimethanil·Quiloxane·Clonpyridoxine Suspension

[0095]

[0096] According to the component details in Table 5, weigh out the technical grade herbicide, dispersant, wetting agent, antifreeze, preservative, and a portion of thickener, defoamer, stabilizer, and water in proportion, mix thoroughly, and grind. Stop grinding when the particle size reaches 5 μm. Add the remaining thickener and defoamer and adjust until homogeneous to obtain the suspension product. Testing shows that the 11% pyrimisulfuron-dichloroquinoline-clopyralid suspension of this invention meets all product standards and is a qualified product.

[0097] Formulation Example 4: 21% pyrimisulfuron-dichloroquinoline-clopyralid water-dispersible granules (1:10:10)

[0098] The composition of 21% pyrimisulfuron-dichloroquinoline acid-clopyralid water-dispersible granules is shown in Table 6:

[0099] Table 6. Component Details of 21% Pyrimethanil·Quilochloric Acid·Clonpyridoxine Water Dispersible Granules

[0100]

[0101]

[0102] According to the component details in Table 6, active ingredient 1, active ingredient 2, active ingredient 3, dispersant, wetting agent, and carrier are added to a mixing tank and mixed for 10 minutes. The above materials are then subjected to air jet milling until D90 ≤ 25 μm. The milled materials are then mixed with water using a mixer (120-150 kg of deionized water per ton of material) to make the material plastic. The uniformly mixed material is then extruded into columnar particles with a diameter of 1.0 mm and dried with hot air at 80-90℃ until the moisture content is less than 3%, thus obtaining the 21% pyrimisulfuron-dichloroquinoline acid-clopyralid water-dispersible granules of the present invention. Testing shows that the 21% pyrimisulfuron-dichloroquinoline acid-clopyralid water-dispersible granules of the present invention meet all product standards and are qualified products.

[0103] Formulation Excipient Example 5: 32% pyrimisulfuron-dichloroquinoline-clopyralid wettable powder (1:10:5)

[0104] The composition of 32% pyrimisulfuron-dichloroquinoline acid-clopyralid wettable powder is shown in Table 7:

[0105] Table 7. Component Details of 32% Pyrimethanil·Quiloxane·Clonopyroxyacetic Acid Wettable Powder

[0106]

[0107] According to the component details in Table 7, active ingredient 1, active ingredient 2, active ingredient 3, dispersant, wetting agent, and carrier are added to a mixing vessel and mixed for 10 minutes. The above materials are then subjected to air jet milling until D90 ≤ 30 μm to obtain the 32% pyrimisulfuron-dichloroquinoline acid-clopyralid wettable powder of the present invention. Testing shows that the 32% pyrimisulfuron-dichloroquinoline acid-clopyralid wettable powder of the present invention meets all product standards and is a qualified product.

[0108] Formulation Excipient Example 6: 41% pyrimisulfuron-dichloroquinoline-clopyralid water-dispersible granules (1:20:20)

[0109] The composition of 41% pyrimisulfuron-dichloroquinoline acid-clopyralid water-dispersible granules is shown in Table 8:

[0110] Table 8. Component Details of 41% Pyrimethanil·Quilochloric Acid·Cloflupyroxyacetic Acid Water Dispersible Granules

[0111]

[0112] According to the component details in Table 8, active ingredient 1, active ingredient 2, active ingredient 3, dispersant, wetting agent, and carrier are added to a mixing tank and mixed for 10 minutes. The above materials are then subjected to air jet milling until D90 ≤ 25 μm. The milled materials are then mixed with water using a mixer (120-150 kg of deionized water per ton of material) to make the material plastic. The uniformly mixed material is then extruded into columnar particles with a diameter of 1.0 mm and dried with hot air at 80-90℃ until the moisture content is less than 3%, thus obtaining the 41% pyrimisulfuron-dichloroquinoline acid-clopyralid water-dispersible granules of the present invention. Testing shows that the 41% pyrimisulfuron-dichloroquinoline acid-clopyralid water-dispersible granules of the present invention meet all product standards and are qualified products.

[0113] Formulation Excipient Example 7: 31% pyrimisulfuron-methyl·sodium dichloroquinoline·clopyralid wettable powder (1:10:20)

[0114] The composition of 31% pyrimisulfuron-dichloroquinoline sodium-clopyralid wettable powder is shown in Table 9:

[0115] Table 9. Component Details of 31% Pyrimethanil·Sodium Dichloroquinoline·Clonpyridoxine Wettable Powder

[0116]

[0117] According to the component details in Table 9, active ingredient 1, active ingredient 2, active ingredient 3, dispersant, wetting agent, and carrier are added to a mixing vessel and mixed for 10 minutes. The above materials are then subjected to air jet milling until D90 ≤ 30 μm to obtain the 31% pyrimisulfuron-sodium dichloroquinoline-clopyralid wettable powder of the present invention. Testing shows that the 31% pyrimisulfuron-sodium dichloroquinoline-clopyralid wettable powder of the present invention meets all product standards and is a qualified product.

[0118] Formulation Excipient Example 8: 31% pyrimisulfuron-methyl·sodium dichloroquinoline·clopyralid wettable powder (1:20:10)

[0119] The composition of 31% pyrimisulfuron-dichloroquinoline sodium-clopyralid wettable powder is shown in Table 9:

[0120] Table 10 Component Details of 31% Pyrimethanil·Sodium Dichloroquinoline·Clonpyridoxine Wettable Powder

[0121]

[0122] According to the component details in Table 10, active ingredient 1, active ingredient 2, active ingredient 3, dispersant, wetting agent, and carrier are added to a mixing vessel and mixed for 10 minutes. The above materials are then subjected to air jet milling until D90 ≤ 30 μm to obtain the 31% pyrimisulfuron-dichloroquinoline sodium-clopyralid wettable powder of the present invention. Testing shows that the 31% pyrimisulfuron-dichloroquinoline sodium-clopyralid wettable powder of the present invention meets all product standards and is a qualified product.

[0123] Field efficacy methods for products:

[0124] According to the product formulation excipient examples, the present invention conducts field efficacy tests on the above formulations. The standard description is as follows:

[0125] Field efficacy example 1

[0126] Field trials of pyrimisulfuron, quinclorac, and clopyralid for weed control in warm-season bermudagrass lawns

[0127] The experiment was conducted in accordance with the People's Republic of China National Standard GB / T 17980.148-2004 "Guidelines for Field Efficacy Tests of Pesticides (II) Part 148: Herbicides for Controlling Weeds in Lawns":

[0128] 1. Experimental objective: To investigate the field control effects of different compound combinations on weeds in warm-season lawns.

[0129] 2. Target weeds: broadleaf weeds, grass weeds and sedge weeds.

[0130] 3. Test reagents: Product formulation excipients in Examples 3-7, 25% pyrimisulfuron WG (commercially available), 50% quinclorac WP (commercially available), and 20% clopyralid EC (commercially available).

[0131] 4. Application method: Regular foliar spray.

[0132] 5. Cell arrangement, area, and repetition:

[0133] Community area: 4-10 square meters 2 Leave a 1m protective row interval between each small space, and repeat 4 times.

[0134] 6. Experimental investigation and calculation methods:

[0135] 6.1 Weed survey: Record the weed population in the plot, including indicators such as the number of weeds, coverage or weight of weeds, which can be absolute numbers;

[0136] 6.2 Investigation period: Observe once a week after application of the medicine, record the rating, and investigate the results on the 30th day after 15 consecutive days;

[0137] 6.3 Survey Method: The total number of weeds or their fresh weight was investigated. Four points were randomly selected in each plot, each 1m wide. 2 Conduct a sampling survey;

[0138] 6.4 Method for Calculating Drug Efficacy

[0139] The efficacy of the drug is calculated using the formula: Prevention and control effect (%) = [1 - (CK - PT) / CK] × 100

[0140] In the formula: PT—the number or fresh weight of remaining grass in the treated area;

[0141] CK – Number of living grasses or fresh weight in the blank control area.

[0142] 6. Experimental Results and Conclusions

[0143] This experiment was conducted in Suqian City, Jiangsu Province, a region with flat terrain and normal management. The weed density and growth were relatively uniform across all experimental plots.

[0144] Based on the above conditions, this invention, according to Table 11 (A represents pyrimisulfuron, B represents quinclorac, and C represents clopyralid), designed a single spraying on April 26, 2023, followed by a final weed survey and statistical analysis on May 25, 2023. The experimental design is shown in Table 11:

[0145] Table 11 Field Trial Design

[0146]

[0147]

[0148] Based on the design in Table 11, on May 28, 2023, this invention identified and counted weeds according to the above-mentioned experimental survey results and calculation methods, and analyzed the control effect. The results are shown in Table 12:

[0149] Table 12 Results of field efficacy trials

[0150]

[0151] As shown in Table 12, formulations 3-7 have excellent control effects on broadleaf weeds, grass weeds, and sedges in warm-season lawns. After spraying once according to the dosage in Table 11, the control efficacy of the formulations against broadleaf weeds, grass weeds, and sedges in warm-season lawns reached over 90% after 30 days, which is significantly better than the control efficacy of each control agent. In particular, formulation 4, when the ratio of active ingredients is 1:10:10, can achieve a control efficacy of over 95%.

[0152] Field efficacy example 2

[0153] Field trials of pyrimisulfuron, quinclorac, and clopyralid for weed control in warm-season bermudagrass lawns

[0154] The experiment was conducted in accordance with the People's Republic of China National Standard GB / T 17980.148-2004 "Guidelines for Field Efficacy Tests of Pesticides (II) Part 148: Herbicides for Controlling Weeds in Lawns":

[0155] 1. Experimental objective: To investigate the field control effects of different compound combinations on weeds in warm-season lawns.

[0156] 2. Target weeds: broadleaf weeds, grass weeds and sedges.

[0157] 3. Test reagents: Product formulation excipients in Examples 3-7, 25% pyrimisulfuron WG (commercially available), 50% quinclorac WP (commercially available), and 20% clopyralid EC (commercially available).

[0158] 4. Application method: Regular foliar spray.

[0159] 5. Cell arrangement, area, and repetition:

[0160] Community area: 4-10 square meters 2 Leave a 1m protective row interval between each small space, and repeat 4 times.

[0161] 6. Experimental investigation and calculation methods:

[0162] 6.1 Weed survey: Record the weed population in the plot, including indicators such as the number of weeds, coverage or weight of weeds, which can be absolute numbers;

[0163] 6.2 Investigation period: Observe once a week after application of the medicine, record the rating, and investigate the results on the 30th day after 15 consecutive days;

[0164] 6.3 Survey Method: The total number of weeds or their fresh weight was investigated. Four points were randomly selected in each plot, each 1m wide. 2 Conduct a sampling survey;

[0165] 6.4 Method for Calculating Drug Efficacy

[0166] The efficacy of the drug is calculated using the formula: Prevention and control effect (%) = [1 - (CK - PT) / CK] × 100

[0167] In the formula: PT—the number or fresh weight of remaining grass in the treated area;

[0168] CK – Number of living grasses or fresh weight in the blank control area.

[0169] 6. Experimental Results and Conclusions

[0170] This experiment was conducted in Changzhou, Jiangsu Province, where warm-season turfgrass exhibits high resistance to pyrimisulfuron-methyl, the terrain is flat, and management is normal. The weed density and growth were relatively uniform in all experimental plots.

[0171] Based on the above conditions, according to Table 11 (A represents pyrimisulfuron, B represents quinclorac, and C represents clopyralid), the experiment was designed to be sprayed once on March 28, 2024, and a final weed survey and statistics were conducted on April 26, 2024. The experimental design is shown in Table 13:

[0172] Table 13 Field Trial Design

[0173]

[0174]

[0175] Based on the design in Table 13, on May 6, 2024, this invention identified and counted weeds according to the above-mentioned experimental survey results and calculation methods, and analyzed the control effect. The results are shown in Table 14:

[0176] Table 14 Results of Field Efficacy Trials

[0177]

[0178] Table 14 shows that the control efficacy of 25% pyrimisulfuron WG (commercially available) at 15g, ai / ha (active ingredient) was only about 20%, and at 45g, ai / ha (active ingredient) it was only about 40%, which is generally low, indicating that weeds in this area have high resistance to pyrimisulfuron. In contrast, formulations 3-7 showed excellent control effects on broadleaf weeds, grasses, and sedges in warm-season lawns. After one spraying at the dosages in Table 13, the control efficacy of these formulations reached over 75% after 30 days, significantly better than the control agents. Formulation 4, in particular, achieved a control efficacy of over 85% when the active ingredient ratio was 1:10:10.

[0179] In summary, this invention employs a ternary herbicidal composition for controlling various broadleaf weeds, grass weeds, and sedge weeds in warm-season lawns. The optimal ratio is between 1:(3-30):(3-30). Compared with existing formulations, it exhibits a significant synergistic effect, especially against weeds controlled by pyrimisulfuron. Furthermore, it also shows good control effects against older weeds, making it worthy of promotion and application in agricultural production.

[0180] The above description is only a preferred embodiment of the present invention and is not intended to limit 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 ternary herbicidal composition containing an ALS enzyme inhibitor, characterized in that, The herbicidal composition includes three active ingredients: active ingredient A is pyrimisulfuron and its salt, active ingredient B is quinclorac acid and its salt, and active ingredient C is selected from clopyralid. The weight ratio of active ingredients A, B and C is 1:(3~30):(3~30), and the total weight of the active ingredients accounts for 10~70% of the total weight of the herbicidal composition.

2. The application of the herbicidal composition according to claim 1 in controlling grass weeds, broadleaf weeds and / or sedge weeds.

3. The application according to claim 2, characterized in that, Application of the herbicidal composition in controlling grassy weeds, broadleaf weeds and / or sedge weeds in warm-season lawns.

4. The application according to claim 2, characterized in that, The grassy weeds are barnyard grass and crabgrass, the broadleaf weeds are shepherd's purse and fennel, and the sedge weeds are nutgrass.

5. The application according to claim 3, characterized in that, The warm-season turf is bermudagrass and / or zoysiagrass.

6. The application according to claim 2, characterized in that, The herbicidal composition acts on harmful plants, crops, plant seeds, or areas where plants grow.

7. The herbicidal composition according to claim 1, characterized in that, The herbicidal composition can be formulated into one of the following: wettable powder, granules, emulsifiable granules, water-dispersible granules, suspension concentrate, emulsion, dispersible oil suspension, and microcapsule suspension.

8. The herbicidal composition according to claim 7, characterized in that, The herbicidal composition also contains commonly used adjuvants required for the formulation of pesticide formulations. Commonly used adjuvants are one or more of the following: solvents, wetting agents, stabilizers, dispersants, thickeners, pH adjusters, defoamers, antifreeze agents, and fillers.

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