Herbicidal compositions, formulations and their applications

Abstract

The present invention relates to the field of agrochemical technology, specifically to herbicidal compositions, formulations and their applications. A herbicidal composition, comprising pyriminobac and glyphosate, the weight ratio of pyriminobac to glyphosate being 1:(10-100). The present invention also includes a dispersible oil suspension of the above herbicidal composition, and by screening and optimizing the type and content of emulsifier, dispersant, synergist, viscosity modifier and dispersion medium, the dispersible suspension obtained has stable quality and excellent performance, which is more conducive to efficacy. At the same time, it has excellent low-temperature fluidity, dispersion stability, high-temperature storage stability, etc., easy availability of raw materials, simple manufacturing process, and easy realization of industrialized production. Suitable for controlling non-arable weeds.

Description

[Technical field]

[0001] The present invention relates to the field of agrochemical technology, specifically to herbicidal compositions, formulations and their applications. [Background technology]

[0002] The chemical name of Pyriminobac is 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, which is composed of uracil and isoxazole bonded together. It has a unique structure and has a higher herbicidal effect than saflufenacil, and can effectively control annual and perennial weeds in gardens and non-cultivated areas, but is more expensive. Currently, varieties of herbicides containing a single active ingredient have the defects that they are prone to drug resistance with continuous use, have a narrow herbicidal spectrum, and can only control monocotyledonous or dicotyledonous weeds, or germinated or ungerminated weeds, but cannot control both at the same time. However, by combining two or more active ingredients, the control effect can be improved, the amount of active ingredients used can be reduced, control costs can be saved, the development of drug resistance in weeds can be delayed, the service life of the drug can be extended, and environmental pollution can be reduced.

[0003] Dispersible oil suspensions are oil-phase suspension systems in non-aqueous media that are highly dispersible and stable within a certain period of time, consisting of drug substances and auxiliary agents (emulsifiers, dispersants and viscosity modifiers, etc.) with an oil phase as a carrier, and at least one component is unnecessary for non-aqueous media, and are used by diluting with water. Compared with other dosage forms, dispersible oil suspensions are safe, environmentally friendly, highly effective, have no dust pollution in the manufacturing process, do not use flammable and explosive organic solvents, are safer for workers and users, are convenient and safe to store and transport, and are relatively safe for the environment, so they are widely used internationally. Due to the physical and chemical properties of some drug substances, or the lack of synergistic effects between drug substances and auxiliary agents, for example, some drug substances with low lipophilicity cannot penetrate through the epidermis of agricultural crops into the interior of the plant, making it difficult to exert the absorption effect in the tissue, and have low penetration and adhesion, making it difficult to exert efficacy, so that dispersible oil suspensions can achieve synergistic effects for drug substances with poor lipophilicity, especially herbicides that are not soluble in the oil phase. Due to the large differences in the physical and chemical properties of different pesticide active ingredients, the performance, interaction of the active ingredients, and the effect on the active ingredients of the various screened auxiliary agents are very different. At present, dispersible oil suspension agents have problems such as low-temperature fluidity, poor dispersion stability and high-temperature storage stability (oil separation, decomposition, discoloration, adhesion, and crystallization occur after high-temperature storage), and the nozzles and filters are easily clogged during use, which directly affects the quality and use effect of dispersible oil suspension agents. Summary of the Invention [Problem to be solved by the invention]

[0004] In view of the above technical problems, the present invention provides a herbicidal composition containing pyriminobac and a dispersible oil suspending agent prepared therefrom, and solves the stability problems existing in the current dispersible oil suspending agents by selecting an adjuvant. [Means for solving the problem]

[0005] In order to solve the above technical problems, a first aspect of the present invention provides a herbicidal composition, comprising pyriminobac and glyphosate, and the weight ratio of the pyriminobac to glyphosate is 1:(10-100).

[0006] A first aspect of the present invention provides a herbicidal composition formulation comprising the herbicidal composition described above and an agriculturally acceptable adjuvant.

[0007] As a preferred technical solution of the present invention, the formulation of said herbicidal composition is one selected from the following: soluble concentrate, microemulsion, dispersible oil suspension, hydrate, water-dispersible granule.

[0008] As a preferred technical solution of the present invention, the weight ratio of said herbicidal composition in said herbicidal composition formulation is 5%-90%.

[0009] As a preferred technical solution of the present invention, the formulation of the herbicidal composition is a dispersible oil suspension, and the agriculturally acceptable adjuvants include at least one of emulsifiers, wetting agents, dispersants, stabilizers, defoamers, viscosity modifiers, and base oils.

[0010] As a preferred technical solution of the present invention, the emulsifier is at least one selected from castor oil polyoxyethylene ether, calcium dodecylbenzene sulfonate, fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, alkylphenol formaldehyde resin polyoxyethylene ether, sorbitan monostearate, sorbitan monostearate polyoxyethylene ether, phenethylphenol polyoxyethylene ether, phenethylphenol polyoxyethylene polyoxypropylene ether, alkoxypolyoxyethylene ether sulfonate, fatty alcohol sulfate, alkyl phosphate, fatty alcohol polyoxyethylene ether sulfate, EO-PO block copolymer and phenethylphenol polyoxyethylene ether sulfonate.

[0011] As a preferred technical solution of the present invention, said emulsifier is a combination of castor oil polyoxyethylene ether and phenethylphenol polyoxyethylene ether sulfonate, and the weight ratio thereof is 1:(0.1-0.5).

[0012] As a preferred technical solution of the present invention, the dispersant is at least one selected from polycarboxylates, lignosulfonates, EO-PO block copolymers, phosphates and their salts, sulfonates, alkylnaphthalenesulfonates, alkylphenol ethoxylates and aliphatic alcohol polyoxyethylene ethers.

[0013] As a preferred technical solution of the present invention, said viscosity modifier is a combination of organic bentonite and magnesium aluminum silicate, and the weight ratio thereof is 1:(0.5-2).

[0014] A third aspect of the present invention provides the application of a herbicidal composition for controlling weeds in non-cultivated land. Effect of the Invention

[0015] The present invention provides a herbicidal composition and a dispersible oil suspension containing the herbicidal composition, the beneficial effects of which are as follows:

[0016] 1. By combining pyriminovac and glyphosate, the unique mechanism of action has no cross-resistance, a synergistic effect is achieved, the herbicidal spectrum is broadened, the control effect is improved, and the shortcomings of the low control effect of single-use agents against major weeds are compensated for. At the same time, it improves the sustained effect of each component of the composition, delays the occurrence of weed resistance, reduces the repeated use of pesticides, and reduces the amount and cost of use. It can be mainly used to control non-arable weeds, especially glyphosate-resistant weeds such as burdock and cowrie.

[0017] 2. Through screening and optimization of the types and contents of emulsifiers, dispersants, synergists, viscosity modifiers and dispersion media, the resulting dispersing suspension has stable quality and excellent performance, which is more conducive to efficacy. At the same time, it has excellent low-temperature fluidity, dispersion stability, high-temperature storage stability, etc., and is easy to obtain raw materials, has a simple manufacturing process, and is easy to realize industrialized production. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The contents of the present invention can be more easily understood by referring to the following detailed description of the preferred embodiment of the present invention and the included examples. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention belongs. In case of conflict, the definitions in this specification shall prevail.

[0019] As used herein, the term "prepared from" is synonymous with "comprising." As used herein, the terms "comprise," "include," "have," "contain," or forms thereof are intended to cover a non-exclusive inclusion. For example, a composition, step, method, product, or apparatus that includes recited elements is not limited to those elements and may include other elements not expressly recited or other elements inherent to such composition, step, method, product, or apparatus.

[0020] The conjunction "consisting of" excludes any element, step, or ingredient not specified. When used in a claim, this conjunction limits the scope of the claim to include no materials other than those recited, except for common impurities associated therewith. When the conjunction "consisting of" appears in a subsection of a claim rather than immediately following the subject matter, it limits the claim to only the elements recited in that subsection and does not exclude other elements from the claim.

[0021] When an equivalent amount, concentration, or other value or parameter is expressed as a range, a preferred range, or a range limited by a series of upper and lower preferred values, this should be understood to specifically disclose all ranges formed by any combination of the upper or preferred value of the range with the lower or preferred value of the range, whether or not the ranges are disclosed individually. For example, if a range of "1 to 5" is disclosed, the range described should be understood to include ranges such as "1 to 4," "1 to 3," "1 to 2," "1 to 2 and 4 to 5," "1 to 3 and 5," etc. When a range of numerical values ​​is described herein, unless otherwise stated, the range is intended to include the endpoints and all integers and fractions within the range.

[0022] The singular forms include plural referents unless the context clearly dictates otherwise. "Any" or "any one" means that the subsequently described item or event may or may not occur and that the description includes circumstances in which the event may or may not occur.

[0023] Approximate terms used in the specification and claims modify a quantity and indicate that the invention is not limited to a specific number, but includes close and permissible modifications of this number that do not change the basic function involved. Thus, modifying a numerical value by "approximately," "about," etc. means that the invention is not limited to this exact numerical value. In some cases, the approximation term may correspond to the precision of an instrument for measuring the numerical value. In the specification and claims, ranges can be defined by combinations and / or interchanges. Unless otherwise specified, these ranges include all subranges contained therein.

[0024] In order to solve the above technical problems, a first aspect of the present invention provides a herbicidal composition, the composition comprising pyriminobac and glyphosate, and the weight ratio of the pyriminobac to glyphosate is 1:(10-100).

[0025] In a preferred embodiment, the weight ratio of pyriminobac to glyphosate is 1:(20-60).

[0026] In a more preferred embodiment, the weight ratio of pyriminobac to glyphosate is 1:40.

[0027] The inventors have discovered that by combining pyriminobac and glyphosate, the unique mechanism of action of the two active ingredients eliminates cross-resistance, achieves a synergistic effect, broadens the herbicidal spectrum, and improves the control effect, compensating for the shortcomings of low control effect of single-use agents against major weeds. At the same time, it improves the sustained effect of each component of the composition, delays the development of weed resistance, reduces repeated use of pesticides, and reduces the amount of use and costs. It can be mainly used to control non-arable weeds, especially glyphosate-resistant weeds such as burdock and cowrie.

[0028] A second aspect of the present invention provides a herbicidal composition formulation comprising the herbicidal composition described above and a pesticidally acceptable adjuvant.

[0029] In a preferred embodiment, the formulation of the herbicidal composition is one selected from the group consisting of a soluble concentrate, a microemulsion, a dispersible oil suspension, a hydrate, and a water-dispersible granule.

[0030] In a preferred embodiment, the weight ratio of the herbicidal composition in the herbicidal composition formulation is 5%-90%.

[0031] In a preferred embodiment, the herbicidal composition formulation is a dispersible oil suspension, and the pesticidally acceptable adjuvants include at least one of an emulsifier, a wetting agent, a dispersant, a stabilizer, an antifoaming agent, a viscosity modifier, and a base oil.

[0032] Oil dispersion agent In the present invention, the raw material for preparing the dispersible suspension of the herbicide contains, by weight percentage, at least 5-50% of the herbicidal composition, 5-20% of the emulsifying agent, 0-5% of the wetting agent, 1-5% of the dispersing agent, 0-5% of the defoaming agent, 2-10% of the viscosity modifier, and a base oil to make up the remaining amount to 100%.

[0033] emulsifier An emulsifier is a compound that allows a liquid mixture of two or more mutually insoluble components to form a stable emulsion. Its mechanism of action is that during the emulsification period, the dispersed phase is dispersed in the continuous phase in the form of droplets (micron scale), and the emulsifier reduces the interfacial tension of each component in the mixed system and forms a stronger film on the surface of the droplets, or forms an electric double layer on the surface of the droplets due to the charge of the emulsifier, preventing the droplets from coagulating with each other and maintaining the emulsion in a uniform state. From the perspective of phase, the emulsion is still heterogeneous. The dispersed phase in the emulsion can be an aqueous phase or an oil phase, most of which is an oil phase. The continuous phase can be an oil phase or an aqueous phase, most of which is an aqueous phase. An emulsifier is a surfactant that has a hydrophilic group and a lipophilic group in the molecule. To express the hydrophilicity or lipophilicity of an emulsifier, the "hydrophilic-lipophilic balance value (HLB value)" is usually used, and the lower the HLB value, the higher the lipophilicity, and conversely, the higher the HLB value, the better the hydrophilicity. Different types of emulsifiers have different HLB values, and it is necessary to select an appropriate emulsifier to obtain a stable emulsion.

[0034] In the present invention, the emulsifier is at least one selected from castor oil polyoxyethylene ether, calcium dodecylbenzenesulfonate, aliphatic alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, alkylphenol formaldehyde resin polyoxyethylene ether, sorbitan monostearate, sorbitan monostearate polyoxyethylene ether, phenethylphenol polyoxyethylene ether, phenethylphenol polyoxyethylene polyoxypropylene ether, alkoxypolyoxyethylene ether sulfonate, fatty alcohol sulfate, alkyl phosphate, aliphatic alcohol polyoxyethylene ether sulfate, and EO-PO block copolymer phenethylphenol polyoxyethylene ether sulfonate.

[0035] In a preferred embodiment, the emulsifier is a combination of castor oil polyoxyethylene ether and phenethylphenol polyoxyethylene ether sulfonate, the weight ratio of which is 1:(0.1-0.5).

[0036] In a more preferred embodiment, the weight ratio of the castor oil polyoxyethylene ether to the phenethylphenol polyoxyethylene ether sulfonate is 1:0.35.

[0037] Castor Oil Polyoxyethylene Ether

[0038] In the present invention, the HLB value of the castor oil polyoxyethylene ether is 9-14.

[0039] In a preferred embodiment, the castor oil polyoxyethylene ether has an HLB value of 11-13.

[0040] In a preferred embodiment, the castor oil polyoxyethylene ether has a saponification value of 30-100 mg KOH / g.

[0041] In a more preferred embodiment, the castor oil polyoxyethylene ether has a saponification value of 50-70 mg KOH / g.

[0042] In the present invention, the source of the castor oil polyoxyethylene ether is not particularly limited, and may be Jiangsu Haian Petrochemical Plant, etc., with model numbers such as EL20, HEL20, EL30, HEL30, EL40, HEL40, etc.

[0043] Phenethylphenol polyoxyethylene ether sulfonate

[0044] In the present invention, the source of the phenethylphenol polyoxyethylene ether sulfonate is not particularly limited, and may be Shandong Tiandao Bioengineering Co., Ltd., model number #602.

[0045] The inventor found that by blending castor oil polyoxyethylene ether and phenethylphenol polyoxyethylene ether sulfonate in this system, it is possible to effectively prevent the aggregation of drug substance particles, and improve the suspension stability and storage stability of the dispersible oil suspension. The inventor believes that this is because the blending of castor oil polyoxyethylene ether and phenethylphenol polyoxyethylene ether sulfonate greatly reduces the surface free energy of drug substance ions, and castor oil polyoxyethylene ether can adsorb particles to form a thick adsorption layer, while phenethylphenol polyoxyethylene ether sulfonate generates a diffuse electric double layer on the surface of the particles, which generates repulsion between drug substance ions, and at the same time increases the steric hindrance of the bond between particles, which can further improve the stability of the system.

[0046] In particular, when the weight ratio of the castor oil polyoxyethylene ether and the phenethylphenol polyoxyethylene ether sulfonate is 1:(0.1-0.5), the suspension stability of the obtained dispersible oil suspension is the highest, and no particle precipitation occurs even after long-term storage. The inventor found in the course of research that the dispersion performance of the dispersible oil suspension dissolved in water can also be improved by adding an emulsifier. The inventor believes that the emulsion has many interfaces and is a thermodynamically unstable system, which has the tendency of auto-combination, stratification, sedimentation, etc. to reduce the interfaces, but the emulsifier used in this system can produce a synergistic effect, effectively reducing the tension of the oil-water interface, and the drug substance particles also have the ability to maintain dispersion in water, which is the cause of promoting emulsification and helping to improve the stability of the emulsion.

[0047] Wetting Agent Also known as a wetting agent. It is a type of pesticide adjuvant. It is a substance that can make water-insoluble or water-wettable solid pesticides wettable with water. Its main role is to reduce the surface tension or interfacial tension of water, making the solid surface wettable with water. By mixing water-insoluble pesticides with water to prepare a suspension and using it, the pest control effect can be improved and the occurrence of chemical damage can be reduced by wetting and spreading the liquid over the surfaces of crops, insects, and bacteria.

[0048] In the present invention, the wetting agent is not particularly limited and is well known to those skilled in the art.

[0049] In a preferred embodiment, in order to further improve the ability of the drug substance particles to remain dispersed into fine individual particles in water and to improve the dispersibility of the drug substance particles in water, the wetting agent is at least one selected from alkylphenol polyoxyethylene ether formaldehyde condensation sulfates, alkylphenol polyoxyethylene ether phosphates, phenethylphenol polyoxyethylene ether phosphates, alkyl sulfates, alkyl sulfonic acids, and naphthalene sulfonates.

[0050] In the present invention, the weight ratio of the emulsifier to the wetting agent is 1:(0.05-0.5).

[0051] In a preferred embodiment, the weight ratio of the emulsifier to the wetting agent is 1:0.2.

[0052] Dispersants A dispersant is a surfactant that has two opposing properties in its molecule: lipophilicity and hydrophilicity.

[0053] In the present invention, the dispersant is at least one selected from the group consisting of polycarboxylates, lignosulfonates, EO-PO block copolymers, phosphates and their salts, sulfonates, alkylnaphthalenesulfonates, alkylphenol ethoxylates, and aliphatic alcohol polyoxyethylene ethers.

[0054] In a preferred embodiment, the dispersant is a combination of sulfonate and phosphate, the weight ratio of which is 1:(0.1-1.5).

[0055] In a more preferred embodiment, the weight ratio of the sulfonate to the phosphate is 1:0.85.

[0056] Sulfonates

[0057] In the present invention, the sulfonate is at least one selected from the group consisting of naphthalenesulfonic acid formaldehyde condensates, alkylnaphthalenesulfonic acid formaldehyde condensates, lignosulfonates, and sulfamic acid.

[0058] In a preferred embodiment, the sulfonate is most preferably a compound having an aryl group in its molecular structure, and is preferably selected from naphthalenesulfonic acid formaldehyde condensates and alkylnaphthalenesulfonic acid formaldehyde condensates.

[0059] In the present invention, the source of the naphthalenesulfonic acid formaldehyde condensate and alkylnaphthalenesulfonic acid formaldehyde condensate is not particularly limited, and may be Jinan Hongboli Chemical Co., Ltd.

[0060] Phosphates

[0061] In the present invention, the phosphate preferably employs a compound having an amino group or an amide group in its molecular structure.

[0062] In a preferred embodiment, the phosphate is an alkylamido polyoxyethylene ether phosphate.

[0063] In the present invention, the source of the alkylamide polyoxyethylene ether phosphate is not particularly limited, and may be Guangzhou Bifeng Trading Co., Ltd.

[0064] In the present invention, the weight ratio of the emulsifier to the dispersant is 1:(0.1-0.5).

[0065] In a preferred embodiment, the weight ratio of the emulsifier to the dispersant is 1:0.4.

[0066] The inventors found that the adoption of sulfonate dispersants with aryl groups in their structures and phosphate ester surfactants with amino or amide groups in their structures in this system can effectively improve the stability of dispersible oil suspensions after high / low temperature storage. The inventors believe that this is because the surface of the drug substance particles has a relatively hydrophobic structure, especially pyriminovac, which has a low melting point and is prone to aggregation, and the dispersant molecules adopted in the present invention achieve a synergistic effect with van der Waals attraction, hydrogen bonding force, electrostatic repulsion and spatial steric hindrance force on the surface of the pesticide, so that the drug substance particles can be better dispersed without being affected by temperature. However, when the amount of dispersant used is less than 1%, the dispersant does not reach a saturated adsorption state on the surface of the drug substance particles, and the pesticide particles cannot be completely covered with the dispersant molecules, so that under the action of van der Waals force and gravitational field, the particles will coalesce and settle, and the viscosity of the formulation will increase. If the amount of dispersant used exceeds 10%, the excess dispersant molecules in the system will be entangled with the coating layer on the surface of the active ingredient particles, causing bridges between the particles, resulting in aggregation, increasing the viscosity of the formulation, reducing the fluidity of the formulation, and even affecting the appearance of the formulation.

[0067] Viscosity modifier Viscosity modifiers are used to adjust the viscosity and consistency of a product. There are two general types: viscosity reducers and viscosity increasers.

[0068] In the present invention, the viscosity modifier is not particularly limited and is well known to those skilled in the art.

[0069] In a preferred embodiment, in order to further improve the suspension stability of the system and inhibit the sedimentation of the drug substance particles, it is necessary to maintain the fluidity of the system while ensuring that stratification and austenite ripening do not occur during high-temperature storage. The viscosity modifier includes gum arabic, xanthan gum, polyvinylpyrrolidone, organic bentonite, hydroxymethylcellulose, polyvinyl alcohol, silicon dioxide, magnesium aluminum silicate, etc.

[0070] In a more preferred embodiment, the viscosity modifier is a combination of organobentonite and magnesium aluminum silicate, the weight ratio being 1:(0.5-2).

[0071] In a more preferred embodiment, the weight ratio of the organobentonite to magnesium aluminum silicate is 1:0.76.

[0072] The inventors believe that by combining organic bentonite with magnesium aluminum silicate, the system will swell in water to form a hydrogel network structure, while at the same time allowing the polymer chains to extend through covalent bonds and hydrogen bonds or through the repulsive forces between ions to form a two-dimensional structure, and further providing the system with thixotropy, thereby increasing the structural strength of the suspension.

[0073] Base Oil

[0074] In the present invention, the base oil is not particularly limited and may be any oil well known to those skilled in the art, such as vegetable oil, vegetable oil ester compound, mineral oil, etc.

[0075] In a preferred embodiment, the base oil is at least one selected from soybean oil, corn oil, rapeseed oil, cottonseed oil, castor oil, turpentine oil, palm oil, coconut oil, sunflower oil, methyl oleate, diesel oil, machine oil, and mineral oil.

[0076] In a more preferred embodiment, the base oil includes at least methyl oleate.

[0077] In a more preferred implementation, the base oil is a combination of castor oil and methyl oleate in a weight ratio of 1:(0.1-10).

[0078] The inventors have discovered that by blending castor oil and methyl oleate, this system can increase the dispersion stability of the emulsifier and dispersant in the base oil, improving the suspension stability of the system and its dispersibility in water, while also reducing the oil separation rate of the system during storage at room temperature and at high temperatures, and further improving the suspension rate.

[0079] The inventor believes that the organic bentonite and magnesium aluminum silicate absorb and swell with oil, forming a mesh gel structure in methyl oleate, encapsulating a large amount of oil-based medium molecules in the gaps of the mesh, and the overlapping of the organic carbon chains of the organic bentonite increases the opportunities for covering, increasing the structural destructive force, increasing the yield value of the system, decreasing the oil separation rate of the system, and increasing the suspension rate.

[0080] In the present invention, the method for preparing the dispersible oil suspension is to mix the herbicide composition, the emulsifier, the wetting agent, the dispersant, the defoamer, the viscosity modifier and the base oil, disperse the mixture by high speed shearing for 10-60 minutes, and grind the mixture until the D97 is 1-10 μm.

[0081] In a more preferred embodiment, the D97 is 3±1 μm.

[0082] D97 refers to the particle size value when the cumulative distribution rate from small to large in the particle size distribution reaches 97%. In other words, in a powder, particles with a particle size smaller than D97 account for 97% of the total number of particles. It is usually an index that represents the particle size on the coarse side of a powder, and is an important index in the production and application of powders.

[0083] The inventors have discovered that controlling the D97 of the system to 1-10 μm can significantly improve the dispersibility and storage stability of the system.

[0084] A third aspect of the present invention provides the application of said herbicidal composition for controlling weeds in non-cultivated land.

[0085] In a preferred embodiment, the non-cultivated land includes forest land, lawns, roads, railways, warehouses, fields, drainage ditches, forest fire prevention roads, and the like.

[0086] The present invention will be described in detail below through examples. Hereinafter, it should be understood that the following examples are only used to further illustrate the present invention, and do not limit the protection scope of the present invention. Those skilled in the art will recognize that non-essential improvements and adjustments made based on the content of the present invention are still within the protection scope of the present invention. EXAMPLES

[0087] Example 1

[0088] Example 1 provides a herbicide dispersible oil clouding agent, which includes at least the following components by weight: herbicide composition 30%, emulsifier 10%, wetting agent 2%, dispersant 4%, viscosity modifier 6%, and base oil to make up the remaining amount to 100%. The herbicide composition is a combination of pyriminovac and glyphosate, with a weight ratio of 1:40. The emulsifier is a combination of castor oil polyoxyethylene ether and phenethylphenol polyoxyethylene ether sulfonate, with a weight ratio of 1:0.35. The castor oil polyoxyethylene ether is purchased from Jiangsu Haian Petrochemical Plant, with the model number EL30. The phenethylphenol polyoxyethylene ether sulfonate is purchased from Shandong Tiandao Bioengineering Co., Ltd., with the model number #602. The wetting agent is alkylphenol polyoxyethylene ether formaldehyde condensed sulfate, purchased from Jiangsu Haian Petrochemical Plant. The dispersant is a combination of alkylnaphthalene sulfonic acid formaldehyde condensate and alkylamide polyoxyethylene ether phosphate, with a weight ratio of 1:0.85. The alkylnaphthalene sulfonic acid formaldehyde condensate is purchased from Jinan Hongboli Chemical Co., Ltd. The alkylamide polyoxyethylene ether phosphate is purchased from Guangzhou Bifeng Trading Co., Ltd. The viscosity modifier is a combination of organic bentonite and magnesium aluminum silicate, with a weight ratio of 1:0.76. The organic bentonite is purchased from Tuoyi New Material (Guangzhou) Co., Ltd. The base oil is a combination of castor oil and methyl oleate, with a weight ratio of 1:0.8.

[0089] The dispersible oil suspension is prepared as follows: the herbicidal composition, emulsifier, wetting agent, dispersant, defoamer, viscosity modifier and base oil are mixed, dispersed by high speed shear for 30 minutes, and further ground until D97 is 5 μm. Example 2

[0090] Example 2 provides a herbicide dispersible oil clouding agent, which contains at least the following components by weight: herbicide composition 30%, emulsifier 5%, dispersant 1%, viscosity modifier 2%, and base oil to make up the remaining amount to 100%. The herbicide composition is a combination of pyriminovac and glyphosate, with a weight ratio of 1:40. The emulsifier is a combination of castor oil polyoxyethylene ether and phenethylphenol polyoxyethylene ether sulfonate, with a weight ratio of 1:0.1. The castor oil polyoxyethylene ether is purchased from Jiangsu Haian Petrochemical Plant, with the model number EL30. The phenethylphenol polyoxyethylene ether sulfonate is purchased from Shandong Tiandao Bioengineering Co., Ltd., with the model number #602. The wetting agent is alkylphenol polyoxyethylene ether formaldehyde condensed sulfate, purchased from Jiangsu Haian Petrochemical Plant. The dispersant is a combination of alkylnaphthalene sulfonic acid formaldehyde condensate and alkylamide polyoxyethylene ether phosphate, and the weight ratio is 1:0.1. The alkylnaphthalene sulfonic acid formaldehyde condensate is purchased from Jinan Hongboli Chemical Co., Ltd. The alkylamide polyoxyethylene ether phosphate is purchased from Guangzhou Bifeng Trading Co., Ltd. The viscosity modifier is a combination of organic bentonite and magnesium aluminum silicate, and the weight ratio is 1:0.5. The organic bentonite is purchased from Tuoyi New Material (Guangzhou) Co., Ltd. The base oil is a combination of castor oil and methyl oleate, and the weight ratio is 1:0.1.

[0091] The dispersible oil suspension is prepared as follows: the herbicidal composition, emulsifier, wetting agent, dispersant, defoamer, viscosity modifier and base oil are mixed, dispersed by high speed shear for 30 minutes, and further ground until D97 is 5 μm. Example 3

[0092] Example 3 provides a herbicide dispersible oil clouding agent, which includes at least the following components by weight: herbicide composition 50%, emulsifier 20%, wetting agent 5%, dispersant 5%, viscosity modifier 10%, and base oil to make up the remaining amount to 100%. The herbicide composition is a combination of pyriminovac and glyphosate, with a weight ratio of 1:40. The emulsifier is a combination of castor oil polyoxyethylene ether and phenethylphenol polyoxyethylene ether sulfonate, with a weight ratio of 1:0.5. The castor oil polyoxyethylene ether is purchased from Jiangsu Haian Petrochemical Plant, with the model number EL30. The phenethylphenol polyoxyethylene ether sulfonate is purchased from Shandong Tiandao Bioengineering Co., Ltd., with the model number #602. The wetting agent is alkylphenol polyoxyethylene ether formaldehyde condensed sulfate, purchased from Jiangsu Haian Petrochemical Plant. The dispersant is a combination of alkylnaphthalene sulfonic acid formaldehyde condensate and alkylamide polyoxyethylene ether phosphate, with a weight ratio of 1:1.5. The alkylnaphthalene sulfonic acid formaldehyde condensate is purchased from Jinan Hongboli Chemical Co., Ltd. The alkylamide polyoxyethylene ether phosphate is purchased from Guangzhou Bifeng Trading Co., Ltd. The viscosity modifier is a combination of organic bentonite and magnesium aluminum silicate, with a weight ratio of 1:2. The organic bentonite is purchased from Tuoyi New Material (Guangzhou) Co., Ltd. The base oil is a combination of castor oil and methyl oleate, with a weight ratio of 1:10.

[0093] The dispersible oil suspension is prepared as follows: the herbicidal composition, emulsifier, wetting agent, dispersant, defoamer, viscosity modifier and base oil are mixed, dispersed by high speed shear for 30 minutes, and then ground until the D97 is 1-10 μm. Example 4

[0094] The difference between Example 4 and Example 1 is that the emulsifier does not contain castor oil polyoxyethylene ether. Example 5

[0095] The difference between Example 5 and Example 1 is that the emulsifier does not contain phenethylphenol polyoxyethylene ether sulfonate. Example 6

[0096] The difference between Example 6 and Example 1 is that an alkylphenol ethoxylate is used in place of the phenethylphenol polyoxyethylene ether sulfonate in the emulsifier. Example 7

[0097] The difference between Example 7 and Example 1 is that the dispersant does not contain an alkylnaphthalenesulfonic acid formaldehyde condensate. Example 8

[0098] The difference between Example 8 and Example 1 is that the dispersant does not contain an alkylamido polyoxyethylene ether phosphate. Example 9

[0099] The difference between Example 9 and Example 1 is that sodium lignosulfonate is used in place of alkylnaphthalenesulfonic acid formaldehyde condensate in the dispersant. Example 10

[0100] The difference between Example 10 and Example 1 is the use of alkylphenol polyoxyethylene ether phosphate in place of alkylamido polyoxyethylene ether phosphate in the dispersant. Example 11

[0101] The difference between Example 10 and Example 1 is that the viscosity modifier does not contain magnesium aluminum silicate. Example 12

[0102] The difference between Example 11 and Example 1 is that the base oil does not contain methyl oleate. Example 13

[0103] The difference between Example 13 and Example 1 is that the herbicidal composition is a combination of pyriminobac and glyphosate, and the weight ratio is 1:30. (Performance test)

[0104] 1.High temperature storage stability: Take about 10g of oil suspension sample with a pipette, pour it into a clean ampoule, seal it at high temperature, put it in a thermostatic box at constant temperature (54±2℃), and store it for 14 days, then take it out and measure the suspension rate and viscosity of the dispersible oil suspension. If each index before and after high temperature storage meets the national standard, it is considered to have passed the high temperature storage test, and if the sample can be stored at room temperature for 2 years, it is considered to have passed. If it passes, it is indicated with "√", and if it fails, it is indicated with "×".

[0105] 2.Low temperature storage stability: Take about 80mL of oil suspension sample with a pipette, pour it into a 100mL beaker, place it in a refrigerator at (0±2℃) for 1 hour, stir once every 15 minutes, stir for 15s each time, observe the change in appearance, and then place the beaker in the refrigerator for 7 days. After 7 days, take it out and leave it until it reaches room temperature, and measure the suspension rate and viscosity of the oil suspension. If each index before and after low-temperature storage meets the national standard, it is considered to have passed the high-temperature storage test, and if the sample can be stored at room temperature for 2 years, it is considered to have passed. If it passes, it is indicated with "√", and if it fails, it is indicated with "×".

[0106] 3. Viscosity: At room temperature, measure the viscosity of the dispersible oil suspension with a NDJ-1 rotational viscometer, measuring three times for each sample, and taking the average value.

[0107] 4. Suspension rate: Measured in accordance with HG / T 2467.5-2003. The measurement results are shown in Table 1.

[0108] [Table 1]

[0109] 5. Control test: Sample: Pyriminovac, glyphosate. Target specimens: Conyza canadensis (L.) Cronq., which is resistant to glyphosate, is collected from Baihe Mountain in Changde City, Hunan Province. Eleusine indica (L.) Gaertn., which is resistant to glyphosate, is collected from Ma'an Town, Huizhou City, Guangdong Province. Test Method: In-house cultivation of target specimens Seeds of burdock and burdock mixed with soil were sown in trays, and transplanted after they had germinated to about 10 cm. One seed per paper cup was placed in a normal cultivation greenhouse, and the stems and leaves were sprayed 15 days after transplanting. Processing method: The plants were sprayed using a crawler-type crop sprayer (designed and manufactured by Engineer Research Ltd., UK) at a spray pressure of 1.95 kg / cm according to the doses designed in the study. 2 , spray amount 500L / hm 2 The test was repeated three times. After treatment, the samples were placed in the work area, and after the solution had dried naturally, they were placed in a greenhouse and managed in the usual way, and the reaction of the test weeds to the chemicals was observed and recorded. After treatment, the control effect of the test chemicals on the weeds was periodically investigated by visual inspection or by fresh weight. Test result statistics and analysis: ED of the test drug 50 / ED 90 Calculating values Calculate with DPS statistical analysis software Calculation of cotoxicity factor: JPEG0007618826000002.jpg24140Here, P A is the proportion of drug A in the active ingredients of the mixed drug, and P B is the ratio of drug B in the active ingredients of the mixed drug. If the cotoxicity coefficient is less than 80, there is an antagonistic effect, if the cotoxicity coefficient is more than 120, there is a synergistic effect, and if the cotoxicity coefficient is between 80 and 120, there is an additive effect. The results are shown in Tables 2 and 3, where A is pyriminobac and B is glyphosate.

[0110] [Table 2]

[0111] [Table 3]

[0112] 6.Tabata Efficacy Test: Test Drugs: Herbicide Dispersible Oil Suspension of Example 13 Control Formulation: 10% Pyriminovac aqueous emulsion (Nantong Jiangshan Pesticides & Chemicals Co., Ltd.), 30% glyphosate solution (Product name: Nongda) Test location: Yangtze River embankment in Chizhou Target for control: The dominant weeds are cowrie and burdock, which grow vigorously and densely, with an average height of 10 to 30 cm after treatment. Other weeds include annual burdock, golden cabbage, horsetail, Chinese larkspur, litchikusa, Japanese laurel wort and Japanese laurel. Test Method: Area division: Each treatment was repeated three times, randomly arranged, each area 20m 2 . Usage: May 23, 2020, spray on stems and leaves. The sprayer is a 3WBD-20L electric sprayer, the nozzle is a fan nozzle, the working pressure is 0.2-0.4Mpa, the spray amount is 45kg / mu, and the spray is evenly distributed. (Normally, embankment weeding is required 2-3 times. The pesticides used are mainly a mixture of glyphosate, dimethyl tetrachloride, and dicamba, to which the weeds are relatively resistant.) Survey, recording and measurement methods Weather data: The weather on the day of spraying was fine, with an average temperature of 20.4°C, a maximum temperature of 25.3°C, and a light breeze. There were many rainy days during the test period, but the environment was not harsh. Weed survey: Visually observe the symptoms and speed of weed death on the 3rd, 6th, 9th, 12th, and 16th days after application of the test chemical. On the 16th day, take samples from three locations in each area, survey the number of weeds remaining in each 0.25 m2 area, and calculate the number of weeds controlled. Control effect of borer (16 days after treatment): JPEG0007618826000005.jpg85149

[0113] The above examples are merely illustrative of some features of the methods described herein. The appended claims are intended to claim the broadest possible scope, and the examples set forth herein are intended to describe embodiments selected according to all possible example combinations. It is therefore the applicant's intention that the appended claims not be limited by the selection of examples that illustrate features of the invention. Any numerical ranges used in the claims include subranges contained therein, and variations within these ranges, where possible, are to be construed as being within the scope of the appended claims.

Claims

1. A herbicidal composition formulation comprising a herbicidal composition and a pesticidally acceptable adjuvant, The herbicidal composition comprises pyriminobac and glyphosate, and the weight ratio of the pyriminobac to the glyphosate is 1:(10-100); The formulation of the herbicidal composition is a dispersible oil suspension, and the agriculturally acceptable adjuvants include at least one of an emulsifier, a wetting agent, a dispersant, a stabilizer, a defoamer, a viscosity modifier, and a base oil; The emulsifier is a combination of castor oil polyoxyethylene ether and phenethylphenol polyoxyethylene ether sulfonate, and the weight ratio thereof is 1:(0.1-0.5); The dispersant is a combination of sulfonate and phosphate, the weight ratio of which is 1:(0.1-1.5); The sulfonate is at least one selected from the group consisting of naphthalenesulfonic acid formaldehyde condensates, alkylnaphthalenesulfonic acid formaldehyde condensates, lignosulfonates, and sulfamic acid, and the phosphate ester contains a compound having an amino group or an amide group in its molecular structure.

2. The herbicidal composition formulation according to claim 1, characterized in that the weight percentage of the herbicidal composition in the herbicidal composition formulation is 5-90%.

3. The herbicidal composition formulation according to claim 1, wherein the viscosity modifier is a combination of organic bentonite and magnesium aluminum silicate, and the weight ratio thereof is 1:(0.5-2).

4. The application of the herbicidal composition formulation according to claim 1, characterized in that it is used for controlling weeds in non-cultivated areas.

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