A herbicidal composition of foramsulfuron and its use

Abstract

The present application relates to a kind of herbicidal composition of pyrimisulfan and its preparation method and application scheme, including active ingredient (A) pyrimisulfan or its salt, (B) quinclorac or its salt and (C) carfentrazone-ethyl or its salt, the weight ratio of each active ingredient is (1-24):48:(1-24), the total weight of active ingredient is 1% to 70% of the total weight percentage of herbicidal composition.Excellent activity is shown to a variety of grass weeds, broadleaf weeds and sedge weeds, such as barnyard grass, crabgrass, knotweed, pigweed, shepherd's purse, and cyperus rotundus, in warm-season turf, while the synergistic effect is significant, not only improves the effect of weeding, but also expands the control spectrum, while reducing the number of applications, reducing environmental pressure, reducing the use of pesticides and costs, and delaying the development of resistance.

Description

Technical Field

[0001] This invention belongs to the field of pesticide technology, specifically relating to a herbicidal composition of pyrimisulfuron and its application. Background Technology

[0002] Warm-season lawns are commonly found in sports fields, recreational areas, golf courses, and other green spaces. Weed infestation can negatively impact lawn quality, and the main challenge lies in effectively controlling weeds while ensuring the lawn's herbicide safety. Commonly used warm-season lawn herbicides include pyrimisulfuron, ammonium fluroxypyr, aminopyridine, and dichloropyridine. However, with continuous year-round use of these herbicides, weed resistance is increasing, leading to less than ideal control results.

[0003] Among existing methods, pyrimisulfuron is the most widely used herbicide, but it suffers from severe resistance and slow effectiveness, requiring 7-10 days to show results, and its effectiveness is significantly reduced below 20℃. Quinclorac can be used to control grassy weeds in lawns; different dosages show good control of barnyard grass at different leaf ages, but its effectiveness is not prominent at low temperatures. As a systemic herbicide, quinclorac has a rapid onset of action, with weeds typically showing symptoms of poisoning within 2-3 days. Azoxystrobin, as a contact herbicide, is fast-acting and cold-resistant, but because it does not damage roots, it often causes weeds to regrow, failing to eradicate diseases completely.

[0004] Existing technologies disclose binary compositions of pyrimisulfuron with quinclorac or carfentrazone-ethyl, but all suffer from low safety, slow effectiveness, and short-lasting effect. Patent CN103814926A discloses a composition of pyrimisulfuron and quinclorac for weed control in rice paddies. Patent CN105831142A discloses a binary herbicidal composition of pyrimisulfuron and carfentrazone-ethyl (flufentrazone-ethyl) and its application; this composition can control weeds such as bermudagrass, but has low safety for warm-season lawns. Patent CN104686545A discloses a binary herbicidal composition of pyrimisulfuron and carfentrazone-ethyl (flufentrazone-ethyl) for controlling grassy weeds, broadleaf weeds, and sedges in lawns, but the control effect is unsatisfactory, with slow effectiveness and a short-lasting effect, especially under low-temperature conditions (below 20°C).

[0005] To address the aforementioned technical problems, this invention creatively proposes a new warm-season herbicide solution. By combining three herbicides with different mechanisms of action, it can provide high safety for warm-season lawns while synergistically controlling grassy weeds, broadleaf weeds, and sedges. It also has both rapid and long-lasting effects, maintaining good weed control even at temperatures below 20°C. Summary of the Invention

[0006] The object of this invention is to provide a herbicidal composition of pyrimisulfuron.

[0007] Another object of the present invention is to provide the weeding application of the weeding composition in warm-season lawns.

[0008] The herbicidal composition of the present invention has a synergistic effect, which can broaden the spectrum of weed control, improve the control effect, extend the protection time, reduce the cost of use, and is safe for lawns and less likely to cause resistance.

[0009] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0010] The present invention provides a ternary herbicidal composition containing (A) pyrimisulfuron or its salt, (B) quinclorac or its salt and (C) cyclohexane or its salt, wherein the weight ratio of A, B and C is (1-24):48:(1-24), and the total weight percentage of the active ingredients is 1%-70% of the total weight of the herbicidal composition.

[0011] In a further preferred embodiment, the weight ratio of A, B and C is (2-16):48:(2-16), and the total weight of the active ingredients accounts for 3%-60% of the total weight of the herbicidal composition.

[0012] The salts covered by compounds A, B, and C can be any salt, as long as they are agriculturally acceptable. These include sodium salts, potassium salts, ammonium salts, magnesium salts, calcium salts, monomethyl salts, dimethyl salts, triethyl salts, inorganic acid salts, and organic acid salts.

[0013] The present invention also provides the application of the herbicidal composition in controlling grass weeds, broadleaf weeds and perennial weeds such as sedges in warm-season lawns.

[0014] Among them, the warm-season turf varieties include Cynodon dactylon, Zoysia japonica Steud., and Eremochloa ophiuroides.

[0015] As preferred options, warm-season lawns include bermudagrass and zoysia grass.

[0016] The grassy weeds mentioned 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), clover (Polypogon fugat), purslane (Beckmannia syzigachne), and annual bluegrass (Poa annua), etc.

[0017] The broadleaf weeds include Polygonum saffron, 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, Veronica didyma, Erigeron annuus, Vicia sativa, and Arabidopsis thaliana.

[0018] The sedges mentioned include Cyperus rotundus, Cyperus iria, and Cyperus difformis.

[0019] Furthermore, the herbicidal composition provided by the present invention can be applied to plants, plant parts, plant propagation materials and subsequently grown plant organs, soil or cultivation medium, materials or spaces.

[0020] Furthermore, the herbicidal composition provided by the present invention is typically applied by spraying, but may also be applied by other agricultural techniques as needed. It is typically applied to plants, plant propagation materials and subsequently growing plant organs, cultivation media, materials or spaces in an agronomically effective and substantially non-phytotoxic amount by methods such as seed treatment, foliar application, stem application, soaking, dripping, watering, spraying, misting, dusting, dispersing or fumigation, for example, applied to the leaves of the plant to be treated, i.e., applied to surfaces that are susceptible to or affected by weed infestation that is harmful to crop growth.

[0021] Furthermore, the herbicidal composition provided by this invention has a wider range of applicable ambient temperatures, specifically 3–45°C, preferably 5–35°C. For warm-season lawns, spring is the most crucial time for weed control, and frequent low temperatures can lead to decreased herbicide efficacy. This invention provides a herbicide composition with excellent efficacy at low temperatures.

[0022] 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)].

[0023] 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.

[0024] 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 glutamine salt.

[0025] 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.

[0026] 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.

[0027] 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).]

[0028] Those skilled in the art know that pyrimisulfuron is the most commonly used herbicide for controlling weeds in warm-season lawns, but it also suffers from severe resistance and slow onset of action, requiring 7-10 days to show results, and its effectiveness is significantly reduced below 20°C. Quinclorac can be used to control grassy weeds in lawns, and different dosages show good control efficacy against barnyard grass at different leaf ages, but its control effect is not prominent at low temperatures. As a systemic herbicide, quinclorac has a rapid onset of action, with weeds typically showing symptoms of poisoning within 2-3 days. Azoxystrobin, as a contact herbicide, is fast-acting and cold-resistant, but because it does not damage roots, it often causes weeds to regrow, failing to eradicate diseases completely.

[0029] The applicant unexpectedly discovered that when three herbicides with similar mechanisms of action—the ALS enzyme inhibitor pyrimisulfuron, the hormone-based herbicide quinclorac, and the protoporphyrinogen oxidase inhibitor oxychlorfenapyr—are combined, they can achieve a synergistic effect in controlling warm-season lawn weeds, further broadening the weed control spectrum and improving the control effect. This combination can effectively control grass weeds, broadleaf weeds, and sedge weeds, while also providing both rapid and sustained effects. It maintains good weed control even at low temperatures, thoroughly eliminates weeds without causing regrowth, significantly reduces usage costs, and is safe for lawns, making it less likely to develop resistance.

[0030] Compared with the prior art, the advantages of the present invention are as follows:

[0031] The weed control composition provided by this invention consists of effective ingredients with different mechanisms of action. When compounded in a specific ratio, it has good control effects on grass weeds, broadleaf weeds and sedge weeds. It can effectively overcome the influence of external environment such as low temperature, maintain good weed control effect, take effect quickly, kill weeds thoroughly, and has a significant synergistic effect. At the same time, it has high safety for warm-season lawns.

[0032] The herbicidal composition provided by this invention can broaden the spectrum of control, effectively delay the development of resistance, reduce pesticide usage, lower usage costs, and reduce environmental pollution. Detailed Implementation

[0033] 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.

[0034] Indoor activity assay method

[0035] The inventors conducted extensive target testing, using barnyard grass (Echinochloa crus-galli) as an example to demonstrate indoor activity determination.

[0036] 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".

[0037] 1. Experimental Objective

[0038] The fresh weight control efficacy of pyrimisulfuron, quinclorac acid, and oxychlorfenapyr and 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.

[0039] 2. Test conditions

[0040] 2.1 Experimental Target: Barnyard grass (Echinochloa crus-galli)

[0041] 2.2 Instruments and equipment: constant temperature light incubator, 3WPSH-500E bioassay spray tower, electronic balance (sensitivity 0.1mg), pots, beakers, pipettes.

[0042] 3. Experimental Design

[0043] 3.1 Test soil: The test used air-dried soil with organic matter content <3%, neutral pH, good permeability, and passed through sieve.

[0044] 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 barnyard grass 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 replenished to saturation using bottom irrigation. After emergence, thinning was performed to ensure uniform weed density (120-150 plants per square meter). When the weeds reached 5 cm in height, foliar spraying was performed using a 3WPSH-500E bioassay sprayer (Nanjing Agricultural Machinery Research Institute). The spray volume was 20 mL, and the working pressure was 0.15 MPa. Each treatment group was replicated three times, with a control group (no spray). After the weeds absorbed the spray from the leaves, they were transferred to a constant temperature and light incubator at 25±2℃. The growth of the target weeds was observed periodically.

[0045] 4. Absolute value (numerical measurement) survey method

[0046] After treatment, the growth status of the tested weeds was observed and recorded regularly. Herbicidal activity was investigated and recorded 21 days after treatment using an absolute value (numerical measurement) method, along with descriptions of damage symptoms. Main symptoms included: color changes (yellowing, etc.); morphological changes (curved new leaves, etc.); and growth changes (dehydration, wilting, dwarfing, clustering, etc.).

[0047] 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:

[0048] Fresh weight inhibition rate (%) = (CK fresh weight - treatment fresh weight) / CK fresh weight × 100

[0049] 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.

[0050] 5. Experimental Results and Conclusions

[0051] Based on extensive mixing experiments of this invention, this experiment was conducted in a constant temperature and light incubator at 25±2℃. The following ratios were used for toxicity testing and demonstration. The combined toxicity effects of different ratios of pyrimisulfuron, quinclorac, and oxychlorfenapyr on barnyardgrass after preliminary testing are shown in Table 1:

[0052] Table 1: Combined toxicity of herbicidal compositions against barnyardgrass (spraying method)

[0053]

[0054]

[0055] As shown in Table 1, when pyrimisulfuron and quinclorac were combined, the E0-E values ​​were all within ±10%, indicating an additive effect. When pyrimisulfuron and oxychloride were combined, the E0-E values ​​were within ±10% at ratios of 1:2 and 4:1, indicating an additive effect; at ratios of 2:1 and 2:2, the E0-E values ​​were >10%, indicating a certain synergistic effect. When quinclorac and oxychloride were combined, the E0-E values ​​were within ±10% at a ratio of 48:1, indicating an additive effect; at ratios of 12:2, 24:1, and 48:4, the E0-E values ​​were >10%, indicating a certain synergistic effect. Compared to individual pesticide components used alone or in combination, the combination of pyrimisulfuron, quinclorac, and oxychloride showed excellent control efficacy against barnyard grass and other gramineous weeds. When the weight ratio of pyrimisulfuron, quinclorac acid, and cyclohexane was 4:24:2, 2:12:4, 2:48:4, 4:12:1, and 1:24:4, E0-E > 10%, and further, E0-E > 18%. At 4:24:2, E0-E exceeded 20%, and the theoretical survival rate of barnyard grass was significantly higher than the actual survival rate, demonstrating a synergistic effect.

[0056] The herbicidal test results of the combination of the three components, pyrimisulfuron, quinclorac acid and oxychloride, showed that the activity of the ternary compound was significantly increased, which was significantly better than that of the binary compound.

[0057] Example 2 of indoor low-temperature activity determination:

[0058] The inventors conducted extensive target testing, using toxicity tests on barnyard grass (Echinochloa crus-galli) and sorrel (Polygonum) as examples to demonstrate indoor activity determination.

[0059] The experiment was conducted in accordance with the People's Republic of China Agricultural Industry Standard NY / T 1155.4-2006 "Guidelines for Indoor Bioassay Testing of Pesticides - Herbicides Part 4: Activity Assay Test - Stem Spray Method".

[0060] 1. Purpose of the experiment

[0061] The fresh weight control efficacy of pyrimisulfuron, quinclorac acid, and pyrazosulfuron and their different mixtures against weeds was determined at low temperature.

[0062] 2. Test conditions

[0063] 2.1 Experimental targets: Barnyard grass (Echinochloa crus-galli) and sorrel (Polygonum).

[0064] 2.2 Instruments and equipment: constant temperature light incubator, 3WPSH-500E bioassay spray tower, electronic balance (sensitivity 0.1mg), pots, beakers, pipettes.

[0065] 3. Experimental Design

[0066] 3.1 Test soil: The test used air-dried soil with organic matter content <3%, neutral pH, good permeability, and passed through sieve.

[0067] 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 barnyard grass 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 replenished to saturation using bottom irrigation. After emergence, thinning was performed to ensure uniform weed density (120-150 plants per square meter). When the weeds reached 5 cm in height, foliar spraying was performed using a 3WPSH-500E bioassay sprayer (Nanjing Agricultural Machinery Research Institute). The spray volume was 20 mL, and the working pressure was 0.15 MPa. Each treatment group was repeated three times, with a control group (no spray). After the weeds absorbed the spray from the leaves, they were transferred to a constant temperature and light incubator at 15±2℃. The growth of the target weeds was observed periodically.

[0068] 4. Investigation

[0069] After treatment, the growth status of the tested weeds was observed and recorded regularly. Weed control activity was visually assessed and recorded at 7 and 14 days post-treatment; at 21 days post-treatment, weed control activity was assessed using an absolute value (numerical) survey method, and symptoms of damage were described. The main symptoms included: color changes (yellowing, etc.); morphological changes (curved new leaves, etc.); and growth changes (dehydration, wilting, dwarfing, clustering, etc.).

[0070] 5. Data Statistics and Analysis

[0071] 5.1 Visual inspection method:

[0072] The herbicidal activity of the herbicide is evaluated based on the symptoms and severity of weed damage on the test target. The following standardized grading method can be used for the survey:

[0073] Level 1: All die;

[0074] Grade 2: Equivalent to 0-2.5% of the weeds in the blank control area;

[0075] Level 3: Equivalent to 2.6%–5% of the weeds in the blank control area;

[0076] Level 4: Equivalent to 5.1% to 10% of the weeds in the blank control area;

[0077] Level 5: Equivalent to 10.1%–15% of the weeds in the blank control area;

[0078] Level 6: Equivalent to 15.1%–25% of the weeds in the blank control area;

[0079] Level 7: Equivalent to 25.1%–35% of the weeds in the blank control area;

[0080] Level 8: Equivalent to 35.1%–67.5% of the weeds in the blank control area;

[0081] Level 9: Equivalent to 67.6% to 100% of the weeds in the blank control area.

[0082] 5.2 Absolute Value (Numerical Measurement) Survey Method

[0083] 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:

[0084] Fresh weight inhibition rate (%) = (CK fresh weight - treatment fresh weight) / CK fresh weight × 100

[0085] 6. Experimental Results and Conclusions

[0086] Based on extensive mixed-component experiments according to the present invention, this experiment was conducted in a constant temperature and light incubator at 15±2℃. The following ratios were used for toxicity testing and demonstration. The control efficacy of different ratios of pyrimisulfuron, quinclorac, and oxychlorpyrifos against barnyardgrass and sorrel after preliminary testing is shown in Table 2:

[0087] Table 2: Efficacy of herbicidal compositions against barnyard grass at low temperatures (spraying method)

[0088]

[0089]

[0090] As shown in Table 2, under low temperature conditions (15±2℃), the ternary herbicide composition of this invention has a good control effect on barnyard grass and sorrel. Seven days after application, the control efficacy against barnyard grass and sorrel reached level 4-5, demonstrating significant and rapid onset of action. Twenty-one days after application, the fresh weight control efficacy against barnyard grass and sorrel exceeded 93%. This is significantly superior to the control efficacy of pyrimisulfuron, quinclorac, oxadiazon, or binary combinations thereof.

[0091] Formulation Excipient Example 1: 17% pyrimisulfuron-methyl·quinclorac acid·azoxystrobin suspension (16:48:4)

[0092] The composition of 17% pyrimisulfuron-methyl·quinclorac acid·pyrazolium chloride suspension concentrate is shown in Table 3:

[0093] Table 3. Component details of 17% pyrimisulfuron-methyl·quinclorac acid·pyrazolium chloride suspension concentrate

[0094]

[0095] According to the component details in Table 3, weigh out the technical grade herbicide, wetting agent, dispersant, 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 17% pyrimisulfuron-methyl·quinclorac-methyl·azoxystrobin suspension of this invention meets all product standards and is a qualified product.

[0096] Formulation Example 2: 36% pyrimisulfuron-methyl·quinclorac acid·azoxystrobin water-dispersible granules (8:48:16)

[0097] The composition of 36% pyrimisulfuron-methyl·quinclorac acid·pyrazolium bromide water-dispersible granules is shown in Table 4:

[0098] Table 4. Component details of 36% pyrimisulfuron-methyl·quinclorac acid·pyrazolium bromide water-dispersible granules

[0099]

[0100] According to the component details in Table 4, active ingredient 3 is first mixed with silica in a high-speed mixing kettle for 5 minutes to prepare a uniform solid mixture of pyrazosulfuron and silica (hereinafter referred to as pyrazosulfuron masterbatch). Active ingredients 1, 2, pyrazosulfuron masterbatch, dispersant, wetting agent, and carrier are then added to the mixing kettle and mixed for 10 minutes. The above materials are then subjected to air jet milling until D90 ≤ 25 μm. The milled material is then mixed with water using a mixer (140-160 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 90°C until the moisture content is less than 3%, thus obtaining the 36% pyrazosulfuron-dichloroquinoline-pyrazosulfuron water-dispersible granules of the present invention. Testing shows that the 36% pyrazosulfuron-dichloroquinoline-pyrazosulfuron water-dispersible granules of the present invention meet all product standards and are qualified products.

[0101] Formulation Example 3: 30% pyrimisulfuron-methyl·quinclorac acid·azoxystrobin water-dispersible granules (8:48:4)

[0102] The composition of 30% pyrimisulfuron-methyl·quinclorac acid·pyrazolium bromide water-dispersible granules is shown in Table 5:

[0103] Table 5. Component details of 30% pyrimisulfuron-methyl·quinclorac acid·pyrazolium bromide water-dispersible granules

[0104]

[0105] According to the component details in Table 5, active ingredient 3 is first mixed with silica in a high-speed mixing kettle for 5 minutes to prepare a uniform solid mixture of pyrazosulfuron and silica (hereinafter referred to as pyrazosulfuron masterbatch). Active ingredients 1, 2, pyrazosulfuron masterbatch, dispersant, wetting agent, and carrier are then added to the mixing kettle and mixed for 10 minutes. The above materials are then subjected to air jet milling until D90 ≤ 25 μm. The milled material is then mixed with water using a mixer (160-180 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 90°C until the moisture content is less than 3%, thus obtaining the 30% pyrazosulfuron-dichloroquinoline acid-pyrazosulfuron water-dispersible granules of the present invention. Testing shows that the 30% pyrazosulfuron-dichloroquinoline acid-pyrazosulfuron water-dispersible granules of the present invention meet all product standards and are qualified products.

[0106] Formulation Excipient Example 4: 58% pyrimisulfuron-methyl·quinclorac acid·azoxystrobin wettable powder (2:48:8)

[0107] The composition of 58% pyrimisulfuron-methyl·quinclorac acid·pyrazolium bromide wettable powder is shown in Table 6:

[0108] Table 6. Component Details of 58% Pyrimisulfuron-Dichloroquinoline-Isopropyl Benzyl Alkyl Chloride Wettable Powder

[0109]

[0110] According to the component details in Table 6, active ingredient 3 is first mixed with silica in a high-speed mixing kettle for 5 minutes to prepare pyrazosulfuron-methyl masterbatch. Active ingredients 1, 2, pyrazosulfuron-methyl masterbatch, dispersant, wetting agent, and carrier are then added to the mixing kettle and mixed for 10 minutes. The above materials are then subjected to air jet milling until D90 ≤ 30 μm, thus obtaining the 58% pyrazosulfuron-methyl·quinclorac acid·pyrazosulfuron-methyl wettable powder of this invention. Testing shows that the 58% pyrazosulfuron-methyl·quinclorac acid·pyrazosulfuron-methyl wettable powder of this invention meets all product standards and is a qualified product.

[0111] Formulation Example 5: 27% pyrimisulfuron-methyl·quinclorac acid·azoxystrobin water-dispersible granules (2:48:4)

[0112] The composition of 27% pyrimisulfuron-methyl·quinclorac acid·pyrazolium bromide water-dispersible granules is shown in Table 7:

[0113] Table 7. Component Details of 27% Pyrimisulfuron-methyl·Quiloxane·Isobarbital Water Dispersible Granules

[0114]

[0115] According to the component details in Table 7, active ingredient 3 is first mixed with silica in a high-speed mixing kettle for 5 minutes to prepare a uniform solid mixture of pyrazosulfuron and silica (hereinafter referred to as pyrazosulfuron masterbatch). Active ingredients 1, 2, pyrazosulfuron masterbatch, dispersant, wetting agent, and carrier are then added to the mixing kettle and mixed for 10 minutes. The above materials are then subjected to air jet milling until D90 ≤ 25 μm. The milled material is then mixed with water using a mixer (160-180 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 90°C until the moisture content is less than 3%, thus obtaining the 27% pyrazosulfuron-dichloroquinoline acid-pyrazosulfuron water-dispersible granules of the present invention. Testing shows that the 27% pyrazosulfuron-dichloroquinoline acid-pyrazosulfuron water-dispersible granules of the present invention meet all product standards and are a qualified product.

[0116] Formulation Example 6: 50% pyrimisulfuron-methyl·quinclorac acid·azoxystrobin water-dispersible granules (1:48:1)

[0117] The composition of 50% pyrimisulfuron-methyl·quinclorac acid·pyrazolium bromide water-dispersible granules is shown in Table 8:

[0118] Table 8. Component Details of 50% Pyrimisulfuron-methyl·Quilamine dichlorophenate·Isobutanil Water Dispersible Granules

[0119]

[0120] According to the component details in Table 8, active ingredient 3 is first mixed with silica in a high-speed mixing kettle for 5 minutes to prepare a uniform solid mixture of pyrazosulfuron and silica (hereinafter referred to as pyrazosulfuron masterbatch). Active ingredients 1, 2, pyrazosulfuron masterbatch, dispersant, wetting agent, and carrier are then added to the mixing kettle and mixed for 10 minutes. The above materials are then subjected to air jet milling until D90 ≤ 25 μm. The milled material is then mixed with water using a mixer (140-150 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 90°C until the moisture content is less than 3%, thus obtaining the 50% pyrazosulfuron-dichloroquinoline acid-pyrazosulfuron water-dispersible granules of the present invention. Testing shows that the 50% pyrazosulfuron-dichloroquinoline acid-pyrazosulfuron water-dispersible granules of the present invention meet all product standards and are a qualified product.

[0121] Formulation Excipient Example 7: 30% pyrimisulfuron-methyl·quinclorac sodium·pyrazosulfuron wettable powder (20:48:24)

[0122] The composition of 30% pyrimisulfuron-methyl·sodium quinclorac·pyrazol wettable powder is shown in Table 9:

[0123] Table 9. Component Details of 30% Pyrimisulfuron-methyl·Sodium dichloroquinoline·Isotrione Wettable Powder

[0124]

[0125]

[0126] According to the component details in Table 9, active ingredient 3 is first mixed with silica in a high-speed mixing kettle for 5 minutes to prepare pyrazosulfuron-methyl masterbatch. Active ingredients 1, 2, pyrazosulfuron-methyl masterbatch, dispersant, wetting agent, and carrier are then added to the mixing kettle and mixed for 10 minutes. The above materials are then subjected to air jet milling until D90 ≤ 30 μm, thus obtaining the 30% pyrazosulfuron-methyl·sodium quinclorac·pyrazosulfuron-methyl wettable powder of this invention. Testing shows that the 30% pyrazosulfuron-methyl·sodium quinclorac-methyl·pyrazosulfuron-methyl wettable powder of this invention meets all product standards and is a qualified product.

[0127] Formulation Excipient Example 8: 10% pyrimisulfuron-methyl·sodium dichloroquinoline·azolidinium suspension (4:48:12)

[0128] The composition of 10% pyrimisulfuron-methyl·sodium dichloroquinoline·pyrazolium chloride suspension concentrate is shown in Table 10:

[0129] Table 10 Component Details of 10% Pyrimisulfuron-methyl·Sodium quinclorac·Isobarbital Suspension Concentrate

[0130]

[0131] According to the component details in Table 10, weigh the technical grade herbicide, wetting agent, dispersant, antifreeze, preservative, and a portion of the thickener, defoamer, stabilizer, and water according to the specified proportions, mix them evenly, and grind them. When the particle size reaches 5 μm, stop grinding, add the remaining thickener and defoamer, and adjust evenly to obtain the suspension product. Testing showed that the 10% pyrimisulfuron-methyl·quinclorac sodium·pyrazosulfuron suspension of this invention meets all product standards and is a qualified product.

[0132] Methods for assessing the efficacy of the product in the field:

[0133] According to the product formulation excipient examples, the present invention conducts field efficacy tests on the above formulations. The present invention uses barnyard grass (Echinochloa crus-galli), crabgrass (Digitaria sanguinalis), sorrel (Polygonum), and purslane (Portulaca oleracea) as examples to conduct field efficacy tests on the products, and their standard descriptions are as follows:

[0134] Field efficacy example 1: Field trial of pyrimisulfuron, quinclorac, and oxychlorfenapyr for controlling weeds in warm-season bermudagrass lawns.

[0135] 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":

[0136] 1. Experimental objective: To investigate the field control effects of different compound combinations on weeds in warm-season lawns.

[0137] 2. Target plants for control: barnyard grass (Echinochloa crus-galli), crabgrass (Digitaria sanguinalis), sorrel (Polygonum), and purslane (Portulaca oleracea).

[0138] 3. Test reagents: Product formulation excipients in Examples 1-5, 25% pyrimisulfuron WG (commercially available), 50% quinclorac WP (commercially available), and 10% cyclohexane WP (commercially available).

[0139] 4. Application method: Regular foliar spray.

[0140] 5. Cell arrangement, area, and repetition:

[0141] Community area: 4-10 square meters 2 Leave a 1m protective row interval between each small space, and repeat 4 times.

[0142] 6. Experimental investigation and calculation methods:

[0143] 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;

[0144] 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;

[0145] 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;

[0146] 6.4 Method for Calculating Drug Efficacy

[0147] The efficacy of the drug is calculated using the formula: Prevention and control effect (%) = [1 - (CK - PT) / CK] × 100

[0148] In the formula: PT — number or fresh weight of remaining grass in the treated area;

[0149] CK – Blank control area: number of living grasses or fresh weight.

[0150] 6. Experimental Results and Conclusions

[0151] This experiment was conducted in Lu'an City, Anhui Province. During this period, the average high temperature in the region was 30℃, the average low temperature was 21℃, the terrain was flat, and management was normal. The weed density and growth were relatively uniform in all experimental plots.

[0152] Based on the above conditions, according to Table 11 (A represents pyrimisulfuron, B represents quinclorac, and C represents cyclohexane), the experiment was designed to be sprayed once on May 10, 2022, and a final weed survey and statistics were conducted on June 9, 2022. The experimental design is shown in Table 11:

[0153] Table 11 Field Trial Design

[0154]

[0155] Based on the design in Table 11, on June 15, 2022, 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:

[0156] Table 12 Results of field efficacy trials

[0157]

[0158] As shown in Table 12, the formulations in Examples 1-5 have excellent control effects on barnyard grass, crabgrass, sorrel, and purslane in warm-season lawns. When the formulations are sprayed once according to the dosage in Table 11, the control efficacy against barnyard grass, crabgrass, sorrel, and purslane in warm-season lawns reaches over 92% 30 days after application, which is significantly better than the control efficacy of each control agent. Especially at the ratio of 8:48:4, the control efficacy can reach over 95%.

[0159] Field efficacy example 2: Herbicidal activity of a ternary herbicidal composition of pyrimisulfuron, quinclorac acid, and oxychlorfenapyr at low temperatures

[0160] 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":

[0161] 1. Experimental objective: To determine the rapid efficacy and fresh weight control efficacy of pyrimisulfuron and the ternary herbicide combination under low temperature conditions.

[0162] 2. Target plants for control: barnyard grass (Echinochloa crus-galli), crabgrass (Digitaria sanguinalis), sorrel (Polygonum), and purslane (Portulaca oleracea).

[0163] 3. Test reagents: Product formulation excipients in Examples 1-5, 25% pyrimisulfuron WG (commercially available), 50% quinclorac WP (commercially available), and 10% cyclohexane WP (commercially available).

[0164] 4. Application method: Regular foliar spray.

[0165] 5. Cell arrangement, area, and repetition:

[0166] Community area: 4m² 2 ~10m 2 Leave a 1m protective row interval between each small space, and repeat 4 times.

[0167] 6. Experimental investigation and calculation methods:

[0168] 6.1 Weed survey: Record the weed population in the plot, including indicators such as weed number, coverage or weed weight. Weed control activity was recorded by estimation method 7 days and 14 days after treatment; weed control activity was recorded by absolute value (numerical measurement) survey method 21 days after treatment.

[0169] 7. Data Statistics and Analysis

[0170] 7.1 Valuation Method:

[0171] The herbicidal activity of the herbicide is evaluated based on the symptoms and severity of weed damage on the test target. The following standardized grading method can be used for the survey:

[0172] Level 1: All die;

[0173] Grade 2: Equivalent to 0-2.5% of the weeds in the blank control area;

[0174] Level 3: Equivalent to 2.6%–5% of the weeds in the blank control area;

[0175] Level 4: Equivalent to 5.1% to 10% of the weeds in the blank control area;

[0176] Level 5: Equivalent to 10.1%–15% of the weeds in the blank control area;

[0177] Level 6: Equivalent to 15.1%–25% of the weeds in the blank control area;

[0178] Level 7: Equivalent to 25.1%–35% of the weeds in the blank control area;

[0179] Level 8: Equivalent to 35.1%–67.5% of the weeds in the blank control area;

[0180] Level 9: Equivalent to 67.6% to 100% of the weeds in the blank control area.

[0181] 7.2 Absolute Value (Numerical Measurement) Survey Method

[0182] 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:

[0183] The efficacy of the drug is calculated using the formula: Prevention and control effect (%) = [1 - (CK - PT) / CK] × 100

[0184] In the formula: PT — number or fresh weight of remaining grass in the treated area;

[0185] CK – Blank control area: number of living grasses or fresh weight.

[0186] 8. Experimental Results and Conclusions

[0187] This experiment was conducted on March 4, 2022, in Zhengzhou, Henan Province. The average high temperature in that region that month was 17℃ and the average low temperature was 7℃. The terrain was flat and the site was well-managed. The weed density and growth were relatively uniform in all experimental plots.

[0188] Based on the above conditions, according to Table 13 (A represents pyrimisulfuron, B represents quinclorac, and C represents cyclohexane), the present invention designed a single spraying on March 4, 2022, followed by three weed surveys on March 11, 2022, March 18, 2022, and March 25, 2022. The efficacy was evaluated using the estimation method for the first two surveys, and the efficacy by fresh weight was calculated for the last survey. The experimental design is shown in Table 13.

[0189] Table 13 Field Low Temperature Experiment Design

[0190]

[0191] Based on the design in Table 13, on March 28, 2022, this invention identified and counted weeds using the above-mentioned experimental survey and calculation methods, and analyzed the control effect. The results are shown in Table 14:

[0192] Table 14 Results of field low-temperature efficacy tests

[0193]

[0194]

[0195] As shown in Table 14, at temperatures between 7 and 17°C, formulations 1, 3, and 4 exhibited excellent control effects against barnyard grass, crabgrass, sorrel, and purslane in warm-season lawns. When the formulations were sprayed once according to the dosages in Table 13, 25% pyrimisulfuron WG showed only a level 9 control efficacy against barnyard grass and sorrel at 7 and 14 days, indicating very low efficacy and slow onset of action. A binary mixture of 25% pyrimisulfuron WG, 50% quinclorac WP, 10% cyclohexane WP, or a mixture thereof showed a level 7-8 control efficacy at 7 days. In contrast, the ternary herbicide composition of this invention achieved a level 4-5 control efficacy at 7 days, demonstrating significant efficacy and rapid onset of action.

[0196] The control efficacy of 25% pyrimisulfuron WG against barnyard grass and sorrel knotweed was only about 20% after 21 days; the control efficacy against barnyard grass and sorrel knotweed after 21 days was 55-75% when 25% pyrimisulfuron WG, 50% quinclorac WP, 10% cyclohexane WP or a combination thereof was 55-75% when 21 days; while the ternary herbicide composition of the present invention had a control efficacy of more than 93% against fresh weight of barnyard grass and sorrel knotweed after 21 days.

[0197] In conclusion, under low-temperature conditions, the ternary herbicidal composition has a rapid onset of action and significant control effect, which corresponds to the results of laboratory tests.

[0198] Example 3: Safety Test of Product Field Efficacy

[0199] The experiment was conducted in Taizhou City, Zhejiang Province. Three experimental sites were selected in this region: a warm-season turfgrass (Bermudagrass), a warm-season turfgrass (Zoysia japonica), and a paddy field. The experimental design is shown in Table 15.

[0200] Based on the above conditions, according to Table 15, the present invention was designed to be sprayed once on June 17, 2022.

[0201] Table 15 Field Safety Trial Design

[0202]

[0203] Based on the design in Table 15, on July 24, 2022, the safety of this invention was analyzed based on the above-mentioned experimental investigation and calculations, and the results are shown in Table 16:

[0204] Table 16 Results of Field Safety Trials

[0205]

[0206] Table 16 shows that Bermuda grass and Zoysia japonica grew well without any pesticide spots, indicating that all pesticides are safe for warm-season turfgrass. In rice plots treated with pyrimisulfuron, rice growth was significantly inhibited, with some leaves withering and plants becoming stunted. In rice plots treated with quinclorac and oxychloride, rice grew well without obvious pesticide spots, indicating that quinclorac and oxychloride are safe for rice.

[0207] In field efficacy examples 1 and 2, warm-season turfgrass grew well in all treatment plots without any pesticide spots, indicating that the formulations of pyrimisulfuron, quinclorac acid, and oxychlorfenapyr at different ratios were all safe for warm-season turfgrass.

[0208] Based on the results of field efficacy trials 1, 2 and 3, it was found that single-agent formulations of pyrimisulfuron, quinclorac, and oxychlorfenapyr, as well as compound formulations of ternary herbicides, are safe for warm-season turfgrasses, regardless of whether they are used at normal or high doses.

[0209] In summary, this invention employs a ternary herbicidal composition for controlling various grass weeds, broadleaf weeds, and sedge weeds in warm-season lawns. The optimal ratio is between (2-16):48:(2-16). Compared with existing formulations, it not only has a significant synergistic effect but also exhibits good control efficacy and high safety for warm-season lawns, making it worthy of promotion and application in agricultural production.

[0210] 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 herbicidal composition containing pyrimisulfuron, characterized in that, The active ingredients of the herbicidal composition include (A) pyrimisulfuron or its salt, (B) quinclorac or its salt and (C) cyclohexane or its salt, wherein the weight ratio of A, B and C is (2~16):48:(2~16), and the total weight of the active ingredients accounts for 3%~60% of the total weight of the herbicidal composition.

2. The application of the herbicidal composition according to claim 1 in controlling grassy weeds, broadleaf weeds and / or sedge weeds in warm-season lawns.

3. The application according to claim 2, characterized in that, The warm-season lawns are bermudagrass lawns and zoysia grass lawns.

4. The application according to claim 2, characterized in that, The grassy weeds are barnyard grass or crabgrass, the broadleaf weeds are sorrel or purslane, and the sedges are nutgrass.

5. The application according to claim 2, characterized in that, The ambient temperature is 3~45℃.

6. The application according to claim 2, characterized in that, The ambient temperature is 5~35℃.

7. The application according to claim 2, characterized in that, The herbicidal composition acts on plants or cultivation media.

8. The application according to claim 2, characterized in that, The herbicidal composition is applied to plants or their cultivation media in an agronomically effective and substantially non-phytotoxic amount by means of seed treatment, foliar application, stem application, soaking, dripping, watering, spraying, dusting or fumigation.

9. The herbicidal composition according to claim 1, characterized in that, The herbicidal composition can be formulated into one of the following: powder, wettable powder, granules, emulsifiable granules, water-dispersible granules, tablets, suspensions, emulsions, dispersible oil suspensions, and microcapsule suspensions.

10. The herbicidal composition according to claim 9, characterized in that, The herbicidal composition also contains commonly used adjuvants required for the formulation of pesticide formulations. Commonly used adjuvants are one or a mixture of several of the following: solvents, wetting agents, stabilizers, dispersants, thickeners, pH adjusters, defoamers, antifreeze agents, and fillers.

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