A herbicidal composition containing saflufenacil and its application

By combining Tolpyralate and pyrolysulamide in the herbicide and adjusting its mass ratio and dosage form, the problem of poor compounding effect of existing herbicides is solved, and effective prevention and elimination of weeds in corn, wheat and barley fields is achieved.

CN116172005BActive Publication Date: 2025-04-25JIANGSU REPONT PESTICIDE FACTORY
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Patent Information

Application Number
CN202211630881.6
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2022-12-19
Publication Date
2025-04-25
Estimated Expiration
2042-12-19

AI Technical Summary

Technical Problem

Existing herbicides often show additive or antagonistic effects after compounding, making it difficult to achieve a synergistic effect, and have poor control of broad-leaved weeds and grass family weeds in corn fields, wheat fields and barley fields.

Method used

The herbicidal composition containing Tolpyralate and phenylamin is used to achieve synergistic effects by adjusting the mass ratio of the two (1 to 10:1, preferably 2 to 8:1, further preferably 2 to 4:1 or 3:1) and dosage forms (suspended agent, water dispersed granules, wettable powder, granules, dispersible oil suspension agent).

Benefits of technology

The herbicidal composition has a significant synergistic effect on broad-leaved weeds and grass family weeds in corn fields, wheat fields and barley fields, and has enhanced prevention and efficacy, reduced the dosage, delayed the generation of weed resistance, and was safe for corn, wheat, barley and the next crops.

✦ Generated by Eureka AI based on patent content.

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Abstract

The invention discloses a herbicidal composition containing tolpyralate and an application thereof, wherein the active ingredients are tolpyralate and saflufenacil. The herbicidal composition of the invention has a good control effect on broadleaf weeds and grass weeds in corn fields, wheat fields and barley fields, effectively controls some difficult-to-control weeds and malignant weeds, and is safe for corn, wheat, barley and the next crop.
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Description

Technical Field

[0001] The invention relates to the technical field of pesticides, and in particular to a herbicidal composition containing saflufenacil and application thereof. Background Art

[0002] Chemical weed control is one of the main means of controlling weeds in agriculture. In recent years, due to the large-scale use of some herbicide varieties alone, many weeds have developed resistance. At the same time, due to the complex weed phase when weeds occur, multiple types of weeds such as grass weeds, broadleaf weeds, and sedges are mixed together. A single variety of herbicide cannot solve the weeds in farmland, and will show defects and limitations in some aspects.

[0003] Tolpyralate belongs to the benzoylpyrazole selective herbicide and is an HPPD inhibitor. Its chemical name is 1-(1-ethyl-4-(3-(2-methoxyethoxy)-2-methyl-4-(methylsulfonyl)benzoyl)-1H-pyrazol-5-yloxy)ethyl methyl carbonate. Its CAS registration number is 1101132-67-5. Its chemical structure is:

[0004]

[0005] Tolpyralate is a new type of post-emergence herbicide for corn fields discovered by Ishihara Industries of Japan, with the development code SL-573. Tolpyralate can effectively control most broadleaf and grass weeds in corn fields and is safe for corn. The results of herbicidal activity tests showed that tolpyralate has excellent herbicidal activity against zinnia, velvetleaf, foxtail grass and barnyard grass, but has unsatisfactory control effect on some broadleaf weeds and is ineffective against sedge weeds.

[0006] Saflufenacil, English common name: Saflufenacil, chemical name: N′-{2-chloro-4-fluoro-5-[1,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]benzoyl}-N-isopropyl-N-methanesulfonamide. Saflufenacil's CAS registration number is 372137-35-4, and its chemical structure is:

[0007]

[0008] Safensulfuron is a protoporphyrinogen oxidase (PPO) inhibitor, which can inhibit the activity of PPO in plants, causing cell membrane damage, leading to cell leakage, tissue necrosis, and ultimately plant death. Safensulfuron has good weed control effects, fast action, and long residual period on more than 90 broadleaf weeds (including some weeds resistant to atrazine, glyphosate, and acetolactate synthase (ALS) inhibitors), and can effectively control small-seeded broadleaf weeds such as quinoa and large-seeded weeds that are difficult to control (such as morning glory).

[0009] In the field of herbicides, two or more herbicides are usually compounded to expand the weed control spectrum. Compounding different types of herbicides has the advantages of broad weed control spectrum, improved actual effect, delayed weed resistance, and time and labor saving. Through pesticide formulation screening, the actual prevention and control effect can be effectively improved, the amount of medicine used can be reduced, the cost can be reduced, and the occurrence of resistance to diseases, insects, and weeds can be delayed. It is an important means of comprehensive agricultural management.

[0010] However, many herbicides will show additive or even antagonistic effects after compounding, and only a very few will show synergistic effects.

[0011] Regarding the compound herbicidal composition of Tolpyralate, Chinese patent document CN 113873887 A (application number 202080038848.7) discloses a herbicidal composition containing TOLPYRALATE and fluazifop-butyl as active ingredients. Chinese patent document CN 113950245 A (application number 202080038843.4) discloses a herbicidal composition containing (a) TOLPYRALATE and (b) foramsulfuron as active ingredients. Summary of the invention

[0012] The technical problem to be solved by the present invention is to provide a herbicidal composition containing tolpyralate and saflufenacil which has good control effect on broadleaf weeds and gramineous weeds in corn fields, wheat fields and barley fields and its application.

[0013] The technical solution for achieving the first object of the present invention is a herbicidal composition containing saflufenacil, wherein the active ingredients are tolpyralate and saflufenacil.

[0014] The mass ratio of tolpyralate to saflufenacil is 1 to 10:1.

[0015] Preferably, the mass ratio of tolpyralate to saflufenacil is 2 to 8:1.

[0016] More preferably, the mass ratio of tolpyralate to saflufenacil is 2 to 4:1.

[0017] More preferably, the mass ratio of tolpyralate to saflufenacil is 3:1.

[0018] The active ingredient accounts for 0.1 wt% to 90 wt% of the total weight of the herbicidal composition.

[0019] Preferably, the active ingredient accounts for 6 wt% to 80 wt% of the total weight of the herbicidal composition.

[0020] The dosage form of the herbicidal composition is a suspension, a water-dispersible granule, a wettable powder, a granule, and a dispersible oil suspension.

[0021] The technical solution for achieving the second object of the present invention is to use the herbicidal composition as described above to control weeds in corn fields, wheat fields, and barley fields.

[0022] The weeds are grass weeds and broadleaf weeds in corn fields, wheat fields and barley fields.

[0023] The present invention has positive effects:

[0024] (1) The herbicidal composition of the present invention has a good control effect on broad-leaved weeds and grass weeds in corn fields, wheat fields and barley fields, effectively controls some difficult-to-control weeds and malignant weeds, and is safe for corn, wheat, barley and subsequent crops.

[0025] (2) The herbicidal composition of the present invention not only has complementary herbicidal spectrum advantages, but also has an additive and synergistic interaction after tolpyralate and saflufenacil are compounded, and the prevention effect is enhanced. The application effect is significantly better than the sum of the theoretical effects of a single agent, and can better control the damage caused by dominant weeds.

[0026] Specifically, the use of low-dose saflufenacil makes up for the deficiency of high dosage of tolpyralate. When used in combination with tolpyralate, it has good synergy, enhancement, reduction in dosage, good selectivity, outstanding control effect on resistant weeds, and crop safety. The actual weed control effect is significantly better than the theoretical sum of the separate uses, and it has very practical and broad application prospects in production.

[0027] (3) The rapid effect and long-lasting effect of the herbicidal composition of the present invention complement each other effectively, avoiding the problem of rapid development of weed resistance caused by the use of a single herbicide, and delaying the occurrence of weed resistance; in addition, the amount of medicine used is reduced, the safety to crops is improved, and the cost of use is reduced, which is of great significance to the protection of the ecological environment. DETAILED DESCRIPTION

[0028] (Example 1, 40% suspension)

[0029] 40% tolpyralate·safensulfuron suspension: tolpyralate 30%, safensulfuron 10%, wetting agent phenethylphenol polyoxyethylene ether 5%, dispersant polycarboxylate 3%, antifreeze agent propylene glycol 5%, rheological agent magnesium aluminum silicate 1%, thickener xanthan gum 0.3%, fungicide sodium benzoate 0.3%, water to 100% (the above contents are all mass percentages, the same below).

[0030] The mass ratio of tolpyralate to saflufenacil is 1 to 10:1; in this embodiment, the mass ratio of tolpyralate to saflufenacil is 3:1.

[0031] Preparation method: put the active ingredient, wetting agent, dispersant, antifreeze agent, rheological agent and water into a stirring tank. After sufficient stirring, the material is pumped into a sand mill for sufficient grinding. After grinding, it is pumped into a high-speed shearing machine, and after adding a thickener, high-speed shearing is performed. After shearing, the suspension is obtained and then filled.

[0032] (Example 2, 60% water dispersible granules)

[0033] 60% tolpyralate·safensulfuron water dispersible granules: tolpyralate 45%, safensulfuron 15%, polycarboxylate dispersant 3%, sodium lauryl sulfate 3%, dispersant sodium lignin sulfonate 6%, disintegrant ammonium sulfate 4%, filler kaolin to make up to 100%.

[0034] The mass ratio of tolpyralate to saflufenacil is 1 to 10:1; in this embodiment, the mass ratio of tolpyralate to saflufenacil is 3:1.

[0035] Preparation method: After the above materials weighed according to the formula are mixed evenly, they are crushed by a jet mill and mixed evenly again. Then, a certain amount of water is added to knead the mixture, extruded into granules, and dried and sieved to obtain water-dispersible granules.

[0036] (Example 3, 80% wettable powder)

[0037] 80% tolpyralate·safensulfuron wettable powder: tolpyralate 60%, safensulfuron 20%, wetting agent sodium lauryl sulfate 4%, dispersant sodium naphthalenesulfonate formaldehyde condensate 6%, filler diatomaceous earth to make up to 100%.

[0038] The mass ratio of tolpyralate to saflufenacil is 1 to 10:1; in this embodiment, the mass ratio of tolpyralate to saflufenacil is 3:1.

[0039] Preparation method: The active ingredient and the auxiliary agents are mixed evenly, put into a mechanical crusher for initial crushing, then crushed by a jet mill, and then mixed evenly to obtain a wettable powder.

[0040] (Example 4, 6% granules)

[0041] 6% tolpyralate·safensulfuron granules: tolpyralate 4.5%, safensulfuron 1.5%, wetting agent alkyl succinate sulfonate 0.6%, dispersant alkylphenol polyoxyethylene ether formaldehyde condensate sulfonate 1.0%, colorant basic green (malachite green) 0.2%, filler bentonite to make up to 100%.

[0042] The mass ratio of tolpyralate to saflufenacil is 1 to 10:1; in this embodiment, the mass ratio of tolpyralate to saflufenacil is 3:1.

[0043] Preparation method: After the active ingredient and various auxiliary agents are evenly mixed, a certain amount of water is added to knead the mixture, extrusion granulation is performed, and granules are obtained after drying and sieving.

[0044] (Example 5, 20% dispersible oil suspension)

[0045] 20% tolpyralate·safensulfuron dispersible oil suspension: tolpyralate 15%, safensulfuron 5%, emulsifier alkyl aryl polyoxypropylene polyoxyethylene ether 5%, emulsifier sodium sulfonated dioctyl succinate 8%, dispersant sodium p-methoxy fatty amide benzene sulfonate 3%, thickener organic bentonite 0.8%, and the dispersion medium decolorized soybean oil is supplemented to 100%.

[0046] The mass ratio of tolpyralate to saflufenacil is 1 to 10:1; in this embodiment, the mass ratio of tolpyralate to saflufenacil is 3:1.

[0047] Preparation method: put the active ingredient, emulsifier, dispersant and dispersion medium into a stirring kettle, stir thoroughly, pump into a high-speed shearing machine for high-speed shearing, and then pump into a sand mill for thorough sand grinding. After qualified sand grinding, add a thickener and stir evenly to obtain a dispersible oil suspension.

[0048] (Example 6, 40% suspension)

[0049] 40% tolpyralate·safensulfuron suspension: tolpyralate 26.66%, safensulfuron 13.33%, wetting agent phenethylphenol polyoxyethylene ether 5%, dispersant polycarboxylate 3%, antifreeze agent propylene glycol 5%, rheological agent magnesium aluminum silicate 1%, thickener xanthan gum 0.3%, fungicide sodium benzoate 0.3%, water is supplemented to 100%. In this embodiment, the mass ratio of tolpyralate to safensulfuron is 2:1.

[0050] (Example 7, 60% water dispersible granules)

[0051] 60% tolpyralate·safensulfuron water dispersible granules: tolpyralate 40%, safensulfuron 20%, polycarboxylate dispersant 3%, sodium lauryl sulfate 3%, dispersant sodium lignin sulfonate 6%, disintegrant ammonium sulfate 4%, filler kaolin is supplemented to 100%. In this embodiment, the mass ratio of tolpyralate to safensulfuron is 2:1.

[0052] (Example 8, 80% wettable powder)

[0053] 80% tolpyralate·safensulfuron wettable powder: tolpyralate 64%, safensulfuron 16%, wetting agent sodium lauryl sulfate 4%, dispersant sodium naphthalenesulfonate formaldehyde condensate 6%, filler diatomaceous earth supplemented to 100%. In this embodiment, the mass ratio of tolpyralate to safensulfuron is 4:1.

[0054] (Example 9, 6% granules)

[0055] 6% tolpyralate·safensulfuron granules: tolpyralate 4.8%, safensulfuron 1.2%, wetting agent alkyl succinate sulfonate 0.6%, dispersant alkylphenol polyoxyethylene ether formaldehyde condensate sulfonate 1.0%, colorant basic green (malachite green) 0.2%, filler bentonite is supplemented to 100%. In this embodiment, the mass ratio of tolpyralate to safensulfuron is 4:1.

[0056] (Example 10, 20% dispersible oil suspension)

[0057] 20% tolpyralate·safensulfuron dispersible oil suspension: tolpyralate 16%, safensulfuron 4%, emulsifier alkyl aryl polyoxypropylene polyoxyethylene ether 5%, emulsifier dioctyl sulfonated succinate sodium salt 8%, dispersant sodium p-methoxy fatty amide benzene sulfonate 3%, thickener organic bentonite 0.8%, dispersing medium decolorized soybean oil supplemented to 100%. In this embodiment, the mass ratio of tolpyralate to safensulfuron is 4:1.

[0058] (Test Example 1, Indoor Biological Activity Test)

[0059] Test agents: tolpyralate technical and saflufenacil technical.

[0060] Test targets: Several representative weeds from the grass family and broadleaf weeds, including Setaria viridis, Echinochloa crusgalli, Abutilon, Amaranthus chinensis, Pharbitis chinensis, Chenopodium album, and Channa chustenii, were selected as test weeds. These weeds are annual weeds, and their seeds were collected from the field for reproduction.

[0061] Design of drug configuration: saflufenacil is configured into 0.2 gram of active ingredient per mu of solution for standby use; tolpyralate is configured into 0.1, 0.2, 0.4, 0.6, 0.8, 1.2, 1.6, 2, and 2.4 gram of active ingredient per mu of solution for standby use; saflufenacil and tolpyralate are configured into 0.2+0.1, 0.2+0.2, 0.2+0.4, 0.2+0.6, 0.2+0.8, 0.2+1.2, 0.2+1.6, 0.2+2, and 0.2+2.4 gram of active ingredient per mu of solution for standby use (the ratios are 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:6, 1:8, 1:10, and 1:12 respectively), and the water consumption is 30 liters per mu.

[0062] Test method: A plastic frame with a height of 10 cm, a length of 25 cm, and a width of 18 cm was filled with a certain amount of soil. 50 target weed seeds were sown in the plastic pot, covered with 0.5-1 cm thick fine soil, and then placed in a greenhouse for cultivation. When the weeds grew to the 3-5 leaf stage, the stems and leaves were sprayed. Each frame was sprayed with about 2 mL of the liquid. Each treatment was repeated 4 times, and a treatment without spraying the agent was set as a control. After treatment, the test materials were placed in a greenhouse for cultivation, and the growth of the target weeds was observed regularly. After 20 days, the target damage symptoms and growth inhibition were visually observed, and the fresh weight of the part above the soil was weighed. The toxicity of the agent on the target weeds was evaluated by the target fresh weight inhibition rate.

[0063] Investigation method: 20 days after the experimental treatment, the target damage symptoms and growth inhibition were visually observed, the fresh weight of the above-ground part was measured, and the fresh weight inhibition rate (%) was calculated.

[0064] Evaluation method of combined action: The combination of herbicides was evaluated according to the Gowing method (NY / T 1155.7-2006), and the formula is as follows:

[0065] E0﹦X﹢Y–XY / 100.

[0066] Wherein, X is the fresh weight inhibition rate of target weeds when tolpyralate is used alone at a certain dose; Y is the fresh weight inhibition rate of target weeds when saflufenacil is used alone at a certain dose; E0 is the theoretical value of the fresh weight inhibition rate of target weeds when tolpyralate and saflufenacil are mixed; E is the measured value of the fresh weight inhibition rate of target weeds when tolpyralate and saflufenacil are mixed.

[0067] Evaluation criteria: When E–E0>10%, it indicates a synergistic effect; when –10%≤E–E0≤10%, it indicates an additive effect; when E–E0<–10%, it indicates an antagonistic effect.

[0068] The test results are shown in Tables 1 to 5:

[0069] Table 1. The combined effect of saflufenacil and tolpyralate on Setaria viridis

[0070]

[0071]

[0072] It can be seen from Table 1 that the combination of saflufenacil + tolpyralate has a synergistic effect on Setaria viridis in a weight ratio of 1:1 to 10, among which the synergistic effect of the weight ratio of 1:3 is the most obvious.

[0073] Table 2. The combined effects of saflufenacil and tolpyralate on barnyard grass

[0074]

[0075]

[0076] It can be seen from Table 2 that the combination of saflufenacil + tolpyralate has a synergistic effect on barnyard grass in the weight ratio range of 1:1 to 10, among which the synergistic effect of the weight ratio of 1:3 is the most obvious.

[0077] Table 3. The combined effect of saflufenacil and tolpyralate on ramie

[0078]

[0079] As can be seen from Table 3, the combination of saflufenacil + tolpyralate has a synergistic effect on ramie in a weight ratio range of 1:1 to 10, among which the synergistic effect of the weight ratio of 1:3 is the most obvious.

[0080] Table 4. The combined effect of saflufenacil and tolpyralate on Amaranthus tricolor

[0081]

[0082]

[0083] It can be seen from Table 4 that the combination of saflufenacil + tolpyralate has a synergistic effect on Amaranthus tricolor in the weight ratio range of 1:1 to 10, among which the synergistic effect of the weight ratio of 1:3 is the most obvious.

[0084] Table 5. The combined effect of saflufenacil and tolpyralate on Pharbitis rapa

[0085]

[0086]

[0087] It can be seen from Table 5 that the combination of saflufenacil + tolpyralate has a synergistic effect on morning glory in the weight ratio range of 1:1 to 10, among which the synergistic effect of the weight ratio of 1:3 is the most obvious.

[0088] Table 6. Combined effects of saflufenacil and tolpyralate on Chenopodium album

[0089]

[0090]

[0091] It can be seen from Table 6 that the combination of saflufenacil + tolpyralate has a synergistic effect on Chenopodium album in the weight ratio range of 1:1 to 10, among which the synergistic effect of the weight ratio of 1:3 is the most obvious.

[0092] Table 7. Combined effects of saflufenacil and tolpyralate on snakehead intestine

[0093]

[0094] It can be seen from Table 7 that the combination of saflufenacil + tolpyralate has a synergistic effect on snakehead intestine in the weight ratio range of 1:1 to 10, among which the synergistic effect of the weight ratio of 1:3 is the most obvious.

[0095] In summary, the combination of saflufenacil and tolpyralate has a significant synergistic effect on the control of weeds such as Setaria, Echinochloa crusgalli, Ramie, Amaranthus tricolor, Pharbitis chinensis, Chenopodium album, and Channa chussima within a weight ratio range of 1:1 to 10, among which the most significant synergistic effect is achieved at a weight ratio of 1:3.

[0096] (Test Example 2, Field Efficacy Test)

[0097] Test agents: 10 binary compound agents in Examples 1 to 10.

[0098] Control agents: tolpyralate technical, 70% saflufenacil water dispersible granules.

[0099] Test crops: summer corn; the corn grew well, the plants were strong, without other diseases and pests, and were in the 3-5 leaf stage.

[0100] Targets for control: Annual broad-leaved and grass weeds such as morning glory, ramie, quinoa, polygonum, amaranth, Xanthium sibiricum, sonchus endive, Channa natans, Setaria viridis, crabgrass, barnyard grass, etc. Broad-leaved weeds are in the 2-6 leaf stage, and grass weeds are in the 3-5 leaf stage.

[0101] Test method: According to the area of ​​the test plot, accurately weigh various agents, dilute with water, and use a backpack sprayer to spray evenly. Use a fan-shaped nozzle dedicated to herbicides. When spraying, pay attention to spraying the liquid medicine evenly into the test plot to prevent over-spraying and missed spraying. Implementation 4 and Example 9 are granules, and the poisoned soil method is used for application. 20 kg of fine soil is mixed per mu for broadcasting.

[0102] Observe the growth of crops within 1-15 days after application of the pesticide to determine whether the pesticide has any harm to the crops.

[0103] The death of weeds was observed 20 days and 40 days after application, and the number of weeds or fresh weight was counted to compare the herbicidal activity of each agent.

[0104] After sowing the next crop, observe the impact on the next crop.

[0105] The herbicidal effects of the application examples of the present invention are shown in Table 8 (20 days after application) and Table 9 (40 days after application).

[0106] Table 8. Field efficacy test results (20 days after application)

[0107]

[0108]

[0109] Table 9. Field efficacy test results (40 days after application)

[0110]

[0111] As can be seen from Tables 8 and 9, the field test results show that the compound formulations of Examples 1-5, with a mass ratio of tolpyralat and saflufenacil of 3:1 (i.e. saflufenacil: tolpyralat=1:3), all have the effect of significantly expanding the weed control spectrum, improving the weed control activity, and enhancing the weed control effect, and have a significant synergistic effect.

[0112] The herbicidal effects of Examples 8-10 in which tolpyralat and saflufenacil were prepared in a mass ratio of 4:1 were slightly better than those of Examples 6 and 7 in which the mass ratio was 2:1, and the synergistic effect was slightly better; the herbicidal effects were slightly worse than those of Examples 1-5 in which the mass ratio was 3:1, and the synergistic effect was slightly inferior.

[0113] Observation was performed 3, 7, and 15 days after application. No obvious adverse phenomena such as yellowing leaves, whitening, distortion, stagnant growth, and dead seedlings were observed in the corn in the areas treated with the embodiments and the control agent. The growth was normal, which was consistent with the growth of corn in the blank control area, with no significant difference, indicating that the compound agents in the embodiments are safe for corn growth at this dosage.

[0114] It was observed that the compound formulations of each embodiment had no obvious adverse effect on the growth of the next crop, wheat.

Claims

1. A herbicidal composition containing saflufenacil, characterized in that: The active ingredients are tolpyralate and saflufenacil; the mass ratio of tolpyralate to saflufenacil is 1-10:

1.

2. The herbicidal composition containing saflufenacil according to claim 1, characterized in that: The mass ratio of tolpyralate to saflufenacil is 2 to 8:

1.

3. The herbicidal composition containing saflufenacil according to claim 2, characterized in that: The mass ratio of tolpyralate to saflufenacil is 2-4:

1.

4. The herbicidal composition containing saflufenacil according to claim 3, characterized in that: The mass ratio of tolpyralate to saflufenacil is 3:

1.

5. The herbicidal composition containing saflufenacil according to claim 1, characterized in that: The active ingredient accounts for 0.1 wt% to 90 wt% of the total weight of the herbicidal composition.

6. The herbicidal composition containing saflufenacil according to claim 5, characterized in that: The active ingredient accounts for 6 wt% to 80 wt% of the total weight of the herbicidal composition.

7. The herbicidal composition containing saflufenacil according to claim 1, characterized in that: The dosage form of the herbicidal composition is a suspension, a water-dispersible granule, a wettable powder, a granule, and a dispersible oil suspension.

8. Use of the herbicidal composition according to claim 1 for controlling weeds in corn fields, wheat fields and barley fields.

9. Use of the herbicidal composition according to claim 8 for controlling weeds in corn fields, wheat fields, and barley fields, characterized in that: The weeds are grass weeds and broadleaf weeds in corn fields, wheat fields and barley fields.

Citation Information

Patent Citations

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    CN113873887A

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    CN113950245A

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    CN102245029A