Weeding composition and application thereof

Abstract

The invention relates to the technical field of pesticides, and discloses a weeding composition and application thereof. The effective components of the weeding composition comprise mesosulfuron-methyl, isoproturon and metribuzin. The weeding composition can be applied to prevention and treatment of annual weeds in wheat crop fields. The invention provides a mesosulfuron, isoproturon and metribuzin ternary compound composition, a method for preparing the dispersible oil suspension and assistant optimization, the product stability is improved, the dispersible oil suspension can tolerate high and low temperature intervals, meanwhile, the dispersible oil suspension can tolerate different water qualities such as C water, D water and 3WHO water, the product suspension rate is high, and the dispersible oil suspension can be subsequently used in different countries and regions and has wide application prospects. And large-scale popularization and application are facilitated.

Description

Technical Field

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

[0002] Mesosulfuron-methyl is a sulfonylurea herbicide that is systemic and absorbed primarily through plant stems and leaves. It inhibits the activity of acetolactate synthase, leading to blockage of branched-chain amino acid synthesis, which in turn inhibits cell division and causes the death of sensitive plants. It has a broad control spectrum and is primarily used to control grass weeds and some broadleaf weeds in wheat fields.

[0003] Isoproturon is a substituted urea selective herbicide that achieves its control effect mainly by inhibiting weed photosynthesis. It is suitable for fields of wheat, barley and other cereal crops. It can effectively control annual broad-leaved weeds and some grass weeds, and has both soil sealing and early post-emergence weed control effects.

[0004] Methiazolin belongs to the triazobenzone class of herbicides and is suitable for use in crop fields such as soybeans, corn, potatoes, peanuts, and wheat. It can effectively control annual broadleaf weeds and some grass weeds and can be sprayed before sowing, before seedlings emerge, or before transplanting.

[0005] Herbicide varieties containing a single active ingredient often have varying degrees of deficiencies in agricultural weed control, such as a narrow herbicide spectrum, the tendency for weeds to develop resistance after continuous use, and increased environmental pollution with frequent use. Appropriate herbicide combinations offer strong complementarity, significant synergistic effects, a broadened control spectrum, and reduced application rates. However, if the active ingredients are inappropriately selected, compounding can easily lead to antagonism and poor formulation performance. Furthermore, the more active ingredients in a compound, the greater the difficulty in developing a formulation. Currently, most formulations on the market are single or binary combinations of related active ingredients, with ternary compound formulations being rare. Currently, there are no reports on ternary compound compositions of mesosulfuron, isoproturon, and metribuzin, and their formulations. Summary of the Invention

[0006] The purpose of the present invention is to overcome the problems existing in the prior art and provide a herbicidal composition and its application.

[0007] There are reports on two-way combinations of mesosulfuron + isoproturon and isoproturon + metribuzin, but no reports on mesosulfuron, isoproturon, and metribuzin. Regarding formulations, there are also no reports on ternary blends of dispersible oil suspension concentrates, water-dispersible granules, wettable powders, or dry suspension concentrates.

[0008] A first aspect of the present invention provides a herbicidal composition, wherein the active ingredients of the herbicidal composition include mesosulfuron-methyl, isoproturon and metribuzin.

[0009] In some embodiments of the present invention, the weight ratio of mesosulfuron, isoproturon, and metribuzin in the herbicidal composition is 1:50-150:5-20. Experiments have shown that within this weight ratio range, the combination of mesosulfuron, isoproturon, and metribuzin exhibits significant synergistic effects. Preferably, the synergistic effect is enhanced when the weight ratio of mesosulfuron, isoproturon, and metribuzin is 1:50-100:10-20. The optimal herbicidal effect is achieved when the weight ratio of mesosulfuron, isoproturon, and metribuzin is 1:100:14. In the present invention, the weight ratio can also be 1:50:5, or 1:50:20, or 1:150:5, or 1:150:20, or 1:150:10, or 1:120:15, or 1:60:8, or 1:55:8, or 1:70:5, and any value within the range of any two of the above values.

[0010] The herbicidal composition may further include a safener, and the safener is preferably mefenpyr-butyl. The mass content of the mefenpyr-butyl is preferably 2-5 times the mass content of mesosulfuron-methyl.

[0011] In some embodiments of the present invention, the weight percentage of the active ingredient in the herbicidal composition is 5-80%, or 10-38.4%, or 32.2%.

[0012] In some embodiments of the present invention, the herbicidal composition further comprises an adjuvant.

[0013] In some embodiments of the present invention, the auxiliary material is selected from at least one of an emulsifier, a dispersant, a thickener and a dispersion medium.

[0014] In some embodiments of the present invention, the herbicidal composition can be formulated into any of various agriculturally acceptable formulations, such as at least one of water-dispersible granules, wettable powders, dispersible oil suspensions, and dry suspension concentrates. Depending on the formulation, the selected excipients vary. Excipients can be selected from those reported in the prior art, but differences in excipients can result in differences in formulation performance and herbicidal efficacy.

[0015] Based on the above-mentioned active ingredients, the present inventors conducted further research and successfully developed a dispersible oil suspension concentrate (ODSC) formulation suitable for the ternary herbicidal components of mesosulfuron, isoproturon, and metribuzin. Furthermore, through extensive research and experimentation, the dispersant, emulsifier, thickener, and other auxiliary materials were selected, resulting in the DSC's excellent performance and herbicidal efficacy.

[0016] In some embodiments of the present invention, the dispersible oil suspension comprises the following components by weight: 10-60% active ingredient, 8-35% emulsifier, 1-5% dispersant, 1-6% thickener, and the dispersion medium makes up to 100%.

[0017] In some embodiments of the present invention, the active ingredient is 20-60%, or 25-60%, or 30-45%.

[0018] In some embodiments of the present invention, the emulsifier is 15-30%.

[0019] In some embodiments of the present invention, the dispersant is 2-5%.

[0020] In some embodiments of the present invention, the thickener is 2-5%.

[0021] In some embodiments of the present invention, the emulsifier is selected from at least one of calcium alkylbenzene sulfonate, polyoxyethylene fatty amine ether, polyoxyethylene castor oil ether, polyoxyethylene sorbitan monooleate, polyoxyethylene styrylphenol ether, and polyoxyethylene ether phosphate; or the emulsifier is calcium alkylbenzene sulfonate and polyoxyethylene sorbitan monooleate in a mass ratio of 1:2-4. The best performance is achieved when the emulsifier is a mixture of calcium alkylbenzene sulfonate and polyoxyethylene sorbitan monooleate in a mass ratio of 1:2-4.

[0022] In some embodiments of the present invention, the dispersant is at least one selected from the group consisting of alkylnaphthalene sulfonate formaldehyde condensate, polyoxyethylene-polyoxypropylene block copolymer, calcium lignin sulfonate and modified polyacrylic acid copolymer, preferably polyoxyethylene-polyoxypropylene block copolymer.

[0023] In some embodiments of the present invention, the thickener is selected from at least one of white carbon black, organic bentonite and urea; or, the thickener comprises white carbon black and organic bentonite in a weight ratio of 2:1.

[0024] In some embodiments of the present invention, the dispersion medium is selected from at least one of methyl oleate, castor oil, soybean oil, rapeseed oil methyl ester, and solvent naphtha. The dispersion medium used in the present invention is an environmentally friendly green solvent, which is more environmentally friendly and has good compatibility with the various ingredients, thereby improving product stability.

[0025] When the above auxiliary material components and contents are selected, a dispersible oil suspension formulation with good stability and excellent performance can be obtained, and the efficacy of mesosulfuron, isoproturon and metribuzin can be fully exerted.

[0026] In some embodiments of the present invention, the preparation method of the dispersible oil suspension can be prepared according to the preparation method disclosed in the prior art. In the present invention, the preparation method of the dispersible oil suspension is as follows: after the dispersion medium, thickener, emulsifier and dispersant are mixed for the first time, the active ingredient (and optional safener) are added for the second mixing, and finally the mixture is ground to a particle size D 90Less than 8 μm, to obtain the dispersible oil suspension.

[0027] In some embodiments of the invention, the second mixing is performed by shearing.

[0028] In some embodiments of the present invention, the shearing conditions include: a speed of 1000-10000 r / min and a time of 10-30 minutes. At this shearing speed, sufficient mixing and emulsification can be achieved quickly. The faster the shearing speed, the shorter the time. The shearing time is generally 10-30 minutes.

[0029] In the above preparation method, grinding can be carried out by any grinding method disclosed in the prior art, for example, grinding can be carried out under zirconia bead sand milling medium. After grinding, the particle size distribution is measured by a laser particle size analyzer until the particle size D 90 Less than 8µm.

[0030] The second aspect of the present invention provides the use of the herbicidal composition in controlling annual weeds in wheat crop fields.

[0031] In some embodiments of the present invention, the annual weeds are selected from at least one of Alopecurus mume (such as Alopecurus macrostachya), Aegilops tauschii, Avena striata, Artemisia sophora japonica, and Lolium.

[0032] Through the above technical solution, the beneficial technical effects achieved by the present invention are as follows: (1) The present invention compounds the three active ingredients of pesticides, namely, mesosulfuron, isoproturon and metribuzin. The three ingredients do not produce antagonism when mixed with each other, and the herbicidal spectrum is expanded, the herbicidal efficiency is improved, and a significant synergistic effect is exhibited. The invention can be used to control annual weeds in wheat crop fields.

[0033] (2) The ternary herbicide combination of mesosulfuron, isoproturon and metribuzin provided by the present invention has a good synergistic effect within a specific ratio, and the control effect is higher than that of single agents and binary mixtures. The dosage is small, the resistance of weeds is avoided, the drug lasting period is extended, and it is beneficial to environmental sustainable development.

[0034] (3) The herbicidal composition of the present invention can be prepared into a dispersible oil suspension concentrate. By selecting the auxiliary materials, a dispersible oil suspension concentrate with good stability and excellent performance can be obtained, and the efficacy of the active ingredients of the pesticide can be greatly promoted.

[0035] (4) The present invention improves product stability and can withstand high and low temperature ranges from -15°C to 65°C, effectively solving the impact of environmental changes on product quality during transportation. DETAILED DESCRIPTION

[0036] The following examples are further illustrations of the subject invention and are not intended to limit the scope of the invention, which should be determined by reference to the claims.

[0037] The following percentages are all by weight unless otherwise specified.

[0038] The following examples are further illustrations of the subject invention and are not intended to limit the scope of the invention, which should be determined by reference to the claims.

[0039] The following examples are further illustrations of the subject invention and are not intended to limit the scope of the invention, which should be determined by reference to the claims.

[0040] Example 1: Laboratory Toxicity Test The herbicidal synergistic effect of mesosulfuron-methyl, isoproturon and metamifop was determined by laboratory toxicity test. The laboratory toxicity test was performed according to the method of Sun Yunpei to determine the co-toxicity coefficient (CTC) of the mixed agents. CTC < 80 indicates antagonism, 80 ≤ CTC ≤ 120 indicates additivity, and CTC > 120 indicates synergism.

[0041] The test agents: mesosulfuron-methyl, isoproturon and metamifop were provided by Shandong Weifang Runfeng Chemical Co., Ltd.

[0042] Test design: After determining the effective inhibition concentration range of each agent by pre-test, a series of concentrations were set for each agent according to the active ingredient content, with water as the control. The test was performed according to the Guidelines for Laboratory Biological Test of Pesticides, and 21 days after the stem and leaf spray treatment, the aboveground parts of each treatment were cut and weighed to calculate the fresh weight inhibition rate. The fresh weight inhibition rate = (control group fresh weight - treatment group fresh weight) / control group fresh weight × 100%, and the dose value (ED 50 , in g ai / ha) at which the fresh weight inhibition reached 50% was calculated, and the co-toxicity coefficient was calculated by the method proposed by Sun Yunpei et al. (1960).

[0043] The calculation formula is as follows (taking mesosulfuron-methyl as the standard agent, with a toxicity index of 100): The toxicity index (TI) of isoproturon = ED 50 of mesosulfuron-methyl / ED 50 of isoproturon × 100.

[0044] The toxicity index (TI) of metamifop = ED 50 of mesosulfuron-methyl / ED 50 of metamifop × 100.

[0045] The actual toxicity index (ATI) of M = ED 50 of mesosulfuron-methyl / ED 50× 100.

[0046] Theoretical Toxicity Index (TTI) of M = TI of mesosulfuron + TI of isoproturon + TI of metamifop 甲基二磺隆 × P 异丙隆 × P 嗪草酮 .

[0047] Co-Toxicity Coefficient (CTC) of M = ATI of M / TTI of M × 100.

[0048] Wherein: M is a mixture of mesosulfuron, isoproturon and metamifop in different proportions; P 甲基二磺隆 is the proportion of mesosulfuron in the mixture; P 异丙隆 is the proportion of isoproturon in the mixture; P 嗪草酮 is the proportion of metamifop in the mixture.

[0049] The present application is a composition of three original drugs, and the toxicity index of the binary mixture + the toxicity index of another single agent can also be calculated: Theoretical Toxicity Index (TTI) of M = ATI of binary mixture + TI of another single agent × P 二元混剂 × P 另一单剂 (wherein the ATI of the binary mixture is the ATI of component A+B (or B+C or C+A) when used in combination (= the ED 50 of mesosulfuron / the ED 50 of component (A+B) (or B+C or C+A) × 100), P 二元混剂 is the proportion of component A+B (or B+C or C+A) in the mixture; the TI of another single agent is the TI of component C (or A or B), and P 另一单剂 is the proportion of component C (or A or B) in the mixture), to illustrate the synergistic effect of the ternary composition of the present application from multiple angles.

[0050] The test results are shown in Table 1: Table 1, Toxicity determination results of mesosulfuron, isoproturon and metamifop on Alopecurus pratensis ; Table 1 (continued) ; From Table 1, it can be seen that the ED 50The co-toxicity coefficients of the composite compositions were all greater than 120 when the weight ratios of mesosulfuron, isoproturon, and metribuzin were 1:50:5, 1:50:20, 1:150:5, 1:150:20, and 1:100:14, indicating a synergistic effect. However, when the weight ratio of mesosulfuron, isoproturon, and metribuzin was 1:40:25, the co-toxicity coefficient was only 113.47, indicating an additive effect.

[0051] Compared with the binary combination, the ternary combination of mesosulfuron, isoproturon and metribuzin can, on the one hand, solve the problem of annual weeds in wheat crop fields, and the weed control spectrum is wider than that of the binary combination; on the other hand, the ternary combination has a significant synergistic effect, which can solve the resistance problem of the binary combination, achieve the effect of reducing application and increasing efficiency, and also delay the development of weed resistance.

[0052] Example 2-12 Examples 2-12 provide a series of dispersible oil suspension concentrates, the specific formulations of which are shown in Table 2.

[0053] The preparation method of the dispersible oil suspension is as follows: Mix and disperse the dispersion medium, thickener, emulsifier and dispersant evenly, then add mesosulfuron, isoproturon and metribuzin and safener pyraclostrobin (1.0%), fully shear and mix evenly, and then grind the mixture to a particle size of D 90 Less than 8µm, and dispersible oil suspension concentrates of mesosulfuron, isoproturon and metribuzin were obtained.

[0054] The specific types of some materials are as follows: Castor oil polyoxyethylene ether: EL-40; Calcium alkylbenzene sulfonate: Nongru 500#; Fatty amine polyoxyethylene ether: Ethomeen C; Polyoxyethylene sorbitan monooleate: Tween-80; Styrene phenol polyoxyethylene ether: Nongru 600#; Polyoxyethylene ether phosphate: TRST; Alkylnaphthalenesulfonate formaldehyde condensate: NNO; Polyoxyethylene-polyoxypropylene block copolymer: DOWFAX-D800; Sodium ligninsulfonate: REAX85A.

[0055] Table 2. Dispersible oil suspension formulation (wt%) ; Table 2 ; Test Example 1: Physical and chemical indicators of preparation products The properties of the dispersible oil suspension products prepared in Examples 2-12 were tested, and the results are shown in Table 3 below.

[0056] Among them, the suspension rate is tested in accordance with GB / T 14825-2023, the method for determining the suspension rate of pesticides; the pourability (residue after pouring) is tested in accordance with GB / T 31737-2015, the method for determining the pourability of pesticides; the dispersion stability is tested in accordance with CIPAC MT 180, the method for determining the dispersion stability of suspoemulsions; the hot storage stability (performance before and after hot storage) is tested in accordance with GB / T 19136-2021, the method for determining the hot storage stability of pesticides; the cold storage stability is tested with reference to GB / T 19137-2003, the method for determining the low-temperature stability of pesticides, and the cold storage temperature is adjusted to -15°C for storage, and the appearance and dispersion stability are tested after the product is returned to room temperature for 1 day.

[0057] Table 3. Performance test results of dispersible oil suspension concentrate products ; As shown in Table 3, the finished dispersible oil suspension concentrates produced by the present invention all exhibit high suspension efficiency, low dumping residue, good dispersion stability, and excellent hot and cold storage stability. Example 12 exhibited poor quality both before and after hot storage. After 14 days of storage at 54°C and then transferred to room temperature, the sample's suspension efficiency decreased and the oil separation rate reached 18%. Examples 2-7 exhibited slightly poorer quality after hot storage, while Examples 8-11 exhibited excellent quality both before and after hot storage. Similar results were obtained for cold storage stability. The optimal choice of adjuvant plays a key role in product quality.

[0058] Test Example 2: Field test, efficacy test on annual weeds in wheat fields This experiment was conducted in a suburban farmland in Weicheng District, Weifang City, Shandong Province. The land was flat and level, with complete irrigation and drainage facilities, consistent field management, and uniform to moderate fertility. Wheat was cultivated using direct seeding. The main weeds in the experimental field were Alopecurus macrostachya, Aegilops tauschii, wild oats, Artemisia selengensis, and ryegrass.

[0059] The experiment set up 8 treatments (using Example 8, Example 12, 20% methyldisulfuron-methyl•isoproturon (19.6% isoproturon + 0.4% methyldisulfuron) dispersible oil suspension (commercially available), 45% methyldisulfuron-methyl•isoproturon•pizosulfuron dispersible oil suspension (Formulation Example 13 in CN105475324A), 36% methyldisulfuron-methyl•isoproturon•bifenazate dispersible oil suspension (Formulation Example 1 in CN111955472A), 36% methyldisulfuron-methyl•isoproturon•pyraclostrobin dispersible oil suspension (Formulation 1 in CN116869013A), 33% methyldisulfuron-methyl•isoproturon•pyraclostrobin suspoemulsion (Example 1 in CN119302308A), and clear water as a control). Each treatment was repeated 3 times, with a total of 24 plots, each with an area of ​​30m 2 The plots were arranged in randomized blocks. The water control was sprayed with water without pesticide. The remaining experimental plots were treated with pesticides. On March 1, 2024, during the wheat greening period, the pesticide was applied once using a Gongnong-16 backpack manual sprayer. 450 kg of the formulation was diluted with water per hectare, and the solution was evenly sprayed in the plot. During the experiment, the solution was prepared using 3WHO water prepared in the laboratory.

[0060] 30 days after application, investigate the fresh weight weed control efficacy of each treatment and its safety to wheat. 30 days after application, 4 points were randomly selected from each plot, with a depth of 0.25 m 2 , pull out annual weeds, classify them and weigh their fresh weight, and calculate the weed control effect by fresh weight.

[0061] ; The results of controlling annual weeds in wheat fields are shown in Table 4 below: Table 4. Field efficacy test results of each treatment agent for controlling annual weeds in wheat fields ; The test results in the table above demonstrate that the combination of mesosulfuron, isoproturon, and metribuzin demonstrates excellent control effectiveness against annual weeds in wheat fields. The present invention's ternary combination of mesosulfuron, isoproturon, and metribuzin significantly improves weed control efficacy and broad applicability compared to existing binary or similar ternary combinations. Furthermore, the choice of adjuvant in the present invention significantly influences the effectiveness of the active ingredients, demonstrating synergistic effects.

[0062] In addition, according to the full observation of the field test, within the test dosage range, the wheat fields grew well and no pesticide damage occurred, indicating that the compound agent has no pesticide damage to wheat.

[0063] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A herbicidal composition, characterized in that The effective ingredients of the herbicidal composition consist of mesosulfuron, isoproturon and metribuzin.

2. The herbicidal composition according to claim 1, characterized in that In the herbicidal composition, the weight ratio of mesosulfuron, isoproturon and metribuzin is 1:50-150:5-20.

3. The herbicidal composition according to claim 1 or 2, characterized in that The weight percentage of the active ingredient in the herbicidal composition is 5-80%.

4. The herbicidal composition according to claim 1 or 2, characterized in that The herbicidal composition further comprises an adjuvant; and / or, the auxiliary material is selected from at least one of an emulsifier, a dispersant, a thickener and a dispersion medium; And / or, the formulation of the herbicidal composition is at least one selected from water-dispersible granules, wettable powders, dispersible oil suspensions and dry suspensions.

5. The herbicidal composition according to claim 4, characterized in that The dispersible oil suspension comprises the following components by weight: 10-60% of active ingredient, 8-35% of emulsifier, 1-5% of dispersant, 1-6% of thickener, and the dispersion medium makes up to 100%.

6. The herbicidal composition according to claim 5, characterized in that The active ingredient is 20-60%; and / or, the emulsifier is 15-30%; and / or, the dispersant is 2-5%; And / or, the thickener is 2-5%.

7. The herbicidal composition according to claim 4, characterized in that The emulsifier is at least one selected from calcium alkylbenzene sulfonate, fatty amine polyoxyethylene ether, castor oil polyoxyethylene ether, polyoxyethylene sorbitan monooleate, styrylphenol polyoxyethylene ether and polyoxyethylene ether phosphate; and / or, the dispersant is selected from at least one of alkylnaphthalene sulfonate formaldehyde condensation products, polyoxyethylene-polyoxypropylene block copolymers, calcium lignin sulfonate and modified polyacrylic acid copolymers; and / or, the thickener is selected from at least one of white carbon black, organic bentonite and urea; And / or, the dispersion medium is selected from at least one of methyl oleate, castor oil, soybean oil, rapeseed oil methyl ester and solvent oil.

8. The herbicidal composition according to claim 4, characterized in that The preparation method of the dispersible oil suspension is as follows: the dispersion medium, thickener, emulsifier and dispersant are mixed for the first time, then the active ingredient is added for the second mixing, and finally the mixture is ground to a particle size of D 90 less than 8 μm, to obtain the dispersible oil suspension; and / or, the second mixing is performed by shearing; And / or, the shearing conditions include: a speed of 1000-10000 r / min; and a time of 10-30 min.

9. Use of the herbicidal composition according to any one of claims 1 to 8 for controlling annual weeds in wheat crop fields.

10. The use according to claim 9, characterized in that The annual weeds are selected from at least one of Alopecurus mume, Aegilops tauschii, Wild Oats, Artemisia selengensis, and Ryegrass.