Liquid herbicides

Abstract

This invention provides a stable emulsifiable concentrate comprising cyhalofop-butyl, and chlorpyrifos or its salts or esters. This invention also provides a method for controlling undesirable weeds using such a composition.

Description

Technical Field

[0001] This invention provides a stable liquid herbicidal composition comprising cyhalofop-butyl, and chlorpyrifos or their salts or esters. More particularly, this invention provides an emulsifiable concentrate of herbicidal cyhalofop-butyl and chlorpyrifos or their salts or esters. Background Technology

[0002] Effective herbicide resistance management programs include crop rotation and tillage, as well as herbicide rotation or the use of combinations of herbicides with different modes of action or sites of action. These practices help control the development of resistance.

[0003] To effectively utilize herbicides with different weed spectra and modes of action, these herbicides should be formulated in a highly effective manner as co-formulations. For example, the formulation should contain the active ingredient in an effective amount at the desired weight ratios and should be easily accessible to the end user for efficient application. Simultaneously, the formulation must have a shelf life of at least two years.

[0004] Aryloxyphenoxypropionates are herbicides with strong weeding activity against many grass species. Because the weeding activity of such herbicides is largely limited to grasses, it is strongly recommended to combine them with a secondary herbicide (such as a pyridine carboxylic acid herbicide) with strong broadleaf weeding activity to produce a highly effective product.

[0005] Cyhalofop-butyl (an aryloxyphenoxypropionate) is a fatty acid synthesis inhibitor that works by inhibiting acetyl-CoA carboxylase (ACCase). Rice's tolerance to cyhalofop-butyl is due to its rapid metabolism into a dicarboxylic acid with no herbicidal activity, while susceptible grasses metabolize cyhalofop-butyl into a monocarboxylic acid with herbicidal activity. Cyhalofop-butyl is a post-emergence herbicide that is absorbed only by the leaves and has no soil activity. It is a systemic herbicide that is readily absorbed by plant tissues, moderately moves through the phloem, and accumulates in the meristematic region. Grass weeds stop growing immediately after treatment and develop yellow patches within 2 to 3 days to a week, leading to necrosis and death of the entire plant within 2 to 3 weeks. Cyhalofop-butyl has been widely used for post-emergence control of grass weeds in rice.

[0006] Trilopyr butotyl (a pyridinecarboxylic acid) is a selective systemic herbicide that is rapidly absorbed by leaves and roots and moves throughout the plant, accumulating in meristematic tissues. It induces an auxin-type response in susceptible species, primarily broadleaf and grass weeds unaffected by normal application rates. Trilopyr has been used to control woody plants and many broadleaf weeds (e.g., nettle, sorrel, creeping berries, vitex, datura) in grasslands, uncultivated lands, industrial areas, coniferous forests, planted crops, and paddy fields.

[0007] Many such herbicides are most conveniently formulated as water-soluble salts in aqueous solutions. Combinations of these herbicides can also be formulated as dry microparticles, such as granular products; however, for many agricultural purposes, liquid concentrate formulations are preferred.

[0008] WO 2001010210 discloses a microemulsion composition comprising a water-soluble herbicide and an oil-soluble cyclohexenone or aryloxyphenoxypropionate herbicide.

[0009] Emulsifiable concentrates (ECs) are among the most common formulation types in agrochemicals. Formulators prefer to prepare ECs for active ingredients with low water solubility. ECs are prepared by dissolving the active ingredient in an organic solvent along with a sufficient amount of emulsifier. The advantages of ECs include better penetration and slow evaporation from the plant surface. Such formulations are easy to handle and easy to measure and transport. However, preparing stable formulations presents many challenges because precipitation and separation of components from the EC can occur frequently. The instability of ECs can be caused by a variety of factors, such as chemical instability, physical instability due to phase separation, and climatic factors (e.g., temperature and humidity). Crystallization, sedimentation, and emulsification are some of the factors that should be carefully considered when developing ECs. These factors can be exacerbated if the formulation contains multiple active ingredients with different physical and chemical properties. Stable formulations are required to achieve optimal range, potency, and delivery efficiency. Therefore, new product methods and processes that can effectively eliminate the shortcomings of existing products are essential.

[0010] These and other challenges have now been unexpectedly solved by the invention described below.

[0011] The inventors of this invention have observed that a stable and effective composition of cyhalofop-butyl as well as chlorpyrifos salt and ester (especially chlorpyrifos ester) can be formulated into an emulsifiable concentrate using a mixture of nonionic and anionic surfactants.

[0012] Purpose of the invention

[0013] One object of the present invention is to provide a stable composition of cyhalofop-butyl and chlorpyrifos or their salts and esters.

[0014] One object of the present invention is to provide stable emulsifiable oil compositions of cyhalofop-butyl, chlorpyrifos or its salts and esters (especially chlorpyrifos ester).

[0015] Another object of the present invention is to provide an emulsifiable concentrate composition comprising cyhalofop-butyl; and chlorpyrifos and / or its salts and esters, particularly chlorpyrifos; and a mixture of nonionic and anionic surfactants.

[0016] Another object of the present invention is to provide a method for controlling unwanted weeds using a composition comprising cyhalofop-butyl, and chlorpyrifos and / or their salts and esters. The composition may be an emulsifiable concentrate. In particular, an object of the present invention is to provide a method for controlling unwanted weeds using a composition comprising cyhalofop-butyl and chlorpyrifos. Summary of the Invention

[0017] One aspect of the present invention provides a composition comprising:

[0018] Cyhalofop-butyl;

[0019] Green chlorpyrifos or its salts or esters; and

[0020] A mixture containing nonionic surfactants and anionic surfactants.

[0021] One aspect of the present invention provides an emulsifiable concentrate composition comprising:

[0022] Cyhalofop-butyl;

[0023] Green chlorpyrifos or its salts or esters; and

[0024] A mixture containing nonionic surfactants and anionic surfactants.

[0025] One aspect of the present invention provides a composition comprising:

[0026] Cyhalofop-butyl;

[0027] Green chlorpyrifos; and

[0028] A mixture containing nonionic surfactants and anionic surfactants.

[0029] One aspect of the present invention provides a composition comprising:

[0030] Cyhalofop-butyl;

[0031] Green chlorpyrifos or its salts or esters; and

[0032] A mixture comprising a nonionic surfactant and anionic surfactant, wherein the ratio of the nonionic surfactant to the anionic surfactant is from about 10:1 to about 1:10.

[0033] One aspect of the present invention provides an emulsifiable concentrate composition comprising:

[0034] Cyhalofop-butyl;

[0035] Green chlorpyrifos; and

[0036] A mixture comprising a nonionic surfactant and anionic surfactant, wherein the ratio of the nonionic surfactant to the anionic surfactant is from about 10:1 to about 1:10.

[0037] According to one aspect of the invention, a method for preparing the inventive composition according to the invention is provided, the method comprising dissolving cyhalofop-butyl, and chlorpyrifos or its salts or esters (especially chlorpyrifos ester) in an organic solvent, then adding a mixture comprising a nonionic surfactant and an anionic surfactant, and homogenizing the resulting mixture to obtain the composition.

[0038] According to one aspect of the invention, the use of an emulsifiable concentrate composition as a herbicide is provided, said emulsifiable concentrate composition comprising cyhalofop-butyl; and chlorpyrifos or its salts or esters, particularly chlorpyrifos ester; and a mixture comprising a nonionic surfactant and anionic surfactant.

[0039] According to one aspect of the invention, a method for controlling unwanted weeds is provided, the method comprising applying a herbicidal amount of the composition according to the invention to the weed or its location. Detailed Implementation

[0040] This invention provides stable emulsifiable concentrate compositions comprising cyhalofop-butyl; chlorpyrifos or its salts or esters, particularly chlorpyrifos ester; and a mixture comprising a nonionic surfactant and anionic surfactant. Surprisingly, the desired enhanced physical stability was achieved through specific proportions and / or concentrations of the mixture comprising nonionic and anionic surfactants. Furthermore, the inventors have noted that the inventive compositions exhibit no crystallization, deposition, or emulsification and remain stable during storage. Even more surprisingly, the compositions have been observed to be effective for the desired weed control.

[0041] In accordance with this invention, the proportion or concentration of the mixture comprising nonionic and anionic surfactants is sufficient to provide acceptable physical stability of the emulsifiable concentrate. The physical stability of the emulsifiable concentrate is acceptable if no significant phase separation, crystallization, deposition, or emulsification occurs after storage. In accordance with this invention, the term "stable emulsifiable concentrate" refers to an emulsifiable concentrate formulation that remains stable at 54°C for at least two weeks and exhibits no crystallization, precipitation, or emulsification during its storage.

[0042] In one embodiment, the invention includes a composition comprising...

[0043] Aryloxyphenoxypropionic acid herbicides;

[0044] Pyridine herbicides; and

[0045] One or more agriculturally acceptable components.

[0046] In a preferred embodiment, the aryloxyphenoxypropionic acid herbicide is cyhalofop-butyl.

[0047] In a preferred embodiment, the pyridine herbicide is chlorpyrifos, its salt, or its ester.

[0048] In another preferred embodiment, the pyridine herbicide is chlorpyrifos.

[0049] In one embodiment, the agrochemically acceptable component may be any one or a combination of the following: adjuvants, solubilizers, surfactants, colorants, emulsifiers, thickeners, antifreeze agents, biocides, defoamers, stabilizers, wetting agents, or mixtures thereof, said components may optionally be added to the compositions of the present invention.

[0050] In another embodiment, the composition can be formulated as a solution, emulsion, suspension, powder, granule, paste, granule, compressed form, capsule, and mixtures thereof. Examples of composition types include suspensions (e.g., SC, OD, FS), emulsifiable concentrates (e.g., EC), emulsions (e.g., EW, EO, ES, ME), capsules (e.g., CS, ZC), pastes, tablets, wettable powders or powders (e.g., WP, SP, WS, DP, DS), compressed forms (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticides (e.g., LN), and gel formulations (e.g., GF) for treating plant reproductive material (e.g., seeds).

[0051] In a preferred embodiment, the composition is an emulsifiable concentrate.

[0052] In one embodiment, the present invention provides a composition comprising:

[0053] Cyhalofop-butyl;

[0054] Green chlorpyrifos or its salts or esters; and

[0055] A mixture containing nonionic surfactants and anionic surfactants.

[0056] In a preferred embodiment, chlorpyrifos is present in the composition in the form of its ester, more preferably chlorpyrifos ester.

[0057] In one embodiment, the present invention provides an emulsifiable concentrate composition comprising:

[0058] Cyhalofop-butyl;

[0059] Green chlorpyrifos or its salts or esters; and

[0060] A mixture containing nonionic surfactants and anionic surfactants.

[0061] In a preferred embodiment, chlorpyrifos is present in the composition in the form of its ester, more preferably chlorpyrifos ester.

[0062] In another embodiment, the present invention provides an emulsifiable concentrate composition comprising:

[0063] Cyhalofop-butyl;

[0064] Green chlorpyrifos or its salts or esters; and

[0065] A mixture comprising a nonionic surfactant and anionic surfactant, wherein the ratio of the nonionic surfactant to the anionic surfactant is from about 10:1 to about 1:10.

[0066] In a preferred embodiment, chlorpyrifos is present in the composition in the form of its ester, more preferably chlorpyrifos ester.

[0067] In one embodiment, cyhalofop-butyl may be present in an amount of about 1% to about 60% by weight of the formulation.

[0068] In a preferred embodiment, the composition of the present invention may contain about 5% to about 40% by weight of cyhalofop-butyl.

[0069] In one embodiment, chlorpyrifos or its salts or esters may be present in an amount of about 5% by weight to about 80% by weight of the formulation.

[0070] In a preferred embodiment, the composition of the present invention may contain about 10% to about 50% by weight of chlorpyrifos or its salts or esters.

[0071] In one embodiment, chlorpyrifos may be present in an amount of about 5% to about 80% by weight of the formulation.

[0072] In a preferred embodiment, the composition of the present invention may contain about 10% to about 50% by weight of chlorpyrifos.

[0073] In one embodiment, the emulsifiable concentrate composition comprises a mixture of a nonionic surfactant and anionic surfactant.

[0074] In one embodiment, the nonionic surfactant is selected from fatty alcohol alkoxylates, alkylphenol alkoxylates, fatty acid alkoxylates, and EO / PO copolymers.

[0075] In another embodiment, the nonionic surfactant is selected from ethoxylated fatty acids and alkoxylated fatty acids, ethoxylated amines, ethoxylated alcohols, alkylphenol ethoxylates and nonylphenol ethoxylates, ethoxylated sorbitol esters, castor oil ethoxylates, and EO / PO copolymers.

[0076] Exemplary nonionic surfactants include ethoxylated alcohols and alkylphenol ethoxylates and nonylphenol ethoxylates (Tween 80, Soprophor BSU, Emulsogen EP4901, Emulsogen EL 360, Imbentin AG / 124S / 070 90%, Emulsogen 3510, Atlox 3484, Tween 85).

[0077] In one embodiment, the anionic surfactant is selected from linear or branched alkylbenzene sulfonates, alcohol ether sulfates, secondary alkyl sulfonates, and alcohol sulfates.

[0078] In another embodiment, the anionic surfactant is selected from alkyl sulfates, alkali metal or alkaline earth metal salts and amides of alkyl sulfonic acids, alkali metal or alkaline earth metal salts or sulfonates of dialkyl succinates, sulfonates of alkylphenol polyoxyethylene formaldehyde condensation products, sodium polyoxyethylene ether salts of fatty alcohol alkyl polyoxyethylene ether sulfates, alkyl naphthalene sulfonates, fatty acid or fatty acid ester sulfates.

[0079] Exemplary anionic surfactants include, but are not limited to, alkyl sulfates, alkyl sulfonates (alkali metal or alkaline earth metal salts and amides), and dialkyl succinates (alkali metal or alkaline earth metal salts or sulfonates) (Rhodacal 60 / BE, Nansa EVM 40 / 2ND, Aerosol OT-A ND, Atlox 4838B).

[0080] In one embodiment, the composition according to the invention comprises a mixture of a nonionic surfactant and anionic surfactant.

[0081] In one embodiment, the composition according to the invention comprises a mixture of a nonionic surfactant and anionic surfactant, wherein the ratio of the nonionic surfactant to the anionic surfactant is from about 10:1 to about 1:10.

[0082] In one embodiment, the ratio of nonionic surfactant to anionic surfactant is about 5:1 to about 1:5.

[0083] In one embodiment, the composition of the present invention may further comprise an antifoaming agent selected from polydimethoxysiloxane, polydimethylsiloxane, alkyl polyacrylate, castor oil, fatty acids, fatty acid esters, fatty acid sulfates, fatty alcohols, fatty alcohol esters, fatty alcohol sulfates, olive oil, monoglycerides and diglycerides, paraffin oil, paraffin wax, polypropylene glycol, silicone oil, vegetable and animal fats, vegetable and animal fat sulfates, vegetable and animal oils, vegetable and animal oil sulfates, vegetable and animal waxes, and vegetable and animal wax sulfates.

[0084] In one embodiment, the composition of the present invention may further comprise a solvent, such as water, toluene, xylene, solvent naphtha, dioxane, dimethyl sulfoxide, N,N-dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, or an alcohol.

[0085] The present invention also provides an emulsifiable concentrate composition comprising:

[0086] Cyhalofop-butyl;

[0087] Green chlorpyrifos or its salts or esters; and

[0088] The composition comprises a mixture of nonionic and anionic surfactants in an amount of about 1% to about 80% by weight.

[0089] In a preferred embodiment, chlorpyrifos is present in the composition in the form of its ester, more preferably chlorpyrifos ester.

[0090] The present invention also provides an emulsifiable concentrate composition comprising:

[0091] Cyhalofop-butyl;

[0092] Green chlorpyrifos or its salts or esters; and

[0093] c) A mixture comprising about 1% to 50% by weight of a nonionic surfactant and about 1% to 30% by weight of an anionic surfactant in the composition.

[0094] In a preferred embodiment, chlorpyrifos is present in the composition in the form of its ester, more preferably chlorpyrifos ester.

[0095] In one embodiment, the composition according to the invention comprises a nonionic surfactant in an amount of about 1% to 50% by weight of the composition.

[0096] In one embodiment, the composition according to the invention comprises a nonionic surfactant in an amount of about 3% to 30% by weight of the composition.

[0097] In one embodiment, the composition according to the invention comprises an anionic surfactant in an amount of about 1% to 30% by weight of the composition.

[0098] In one embodiment, the composition according to the invention comprises an anionic surfactant in an amount of about 3% to 20% by weight of the composition.

[0099] In one embodiment, the present invention provides an emulsifiable concentrate composition comprising 5% to 40% cyhalofop-butyl, 10% to 40% chlorpyrifos or its salts or esters, and a mixture comprising a nonionic surfactant and an anionic surfactant, wherein the ratio of the nonionic surfactant to the anionic surfactant is from about 10:1 to about 1:10.

[0100] In one embodiment, the present invention provides an emulsifiable concentrate composition comprising 10% to 20% cyhalofop-butyl, 15% to 30% chlorpyrifos or its salts or esters, and a mixture comprising a nonionic surfactant and anionic surfactant, wherein the ratio of the nonionic surfactant to the anionic surfactant is from about 10:1 to about 1:10.

[0101] In one embodiment, the present invention provides an emulsifiable concentrate composition comprising 5% to 40% cyhalofop-butyl, 10% to 40% chlorpyrifos or its salts or esters, and a mixture comprising a nonionic surfactant and anionic surfactant in an amount of about 1% to 80% by weight of the composition.

[0102] In one embodiment, the present invention provides an emulsifiable concentrate composition comprising 5% to 40% cyhalofop-butyl, 10% to 40% chlorpyrifos or its salts or esters, and a mixture comprising about 1% to 50% by weight of a nonionic surfactant and about 1% to 30% by weight of an anionic surfactant in the composition.

[0103] In one embodiment, the present invention provides an emulsifiable concentrate composition comprising 10% to 20% cyhalofop-butyl, 15% to 30% chlorpyrifos or its salt or ester, and a mixture comprising about 3% to 30% by weight of a nonionic surfactant and about 1% to 15% by weight of an anionic surfactant in the composition.

[0104] In one embodiment, the present invention provides an emulsifiable concentrate composition comprising 10% cyhalofop-butyl, 18% chlorpyrifos or its salt or ester, and a mixture comprising a nonionic surfactant and an anionic surfactant, wherein the nonionic surfactant is selected from ethoxylated tristyrylphenol, C9 to C11 alcohol ethoxylates (Neodol 91-6, Synperonic 91 / 6, Impentin-C / 91 / 080), and the anionic surfactant is selected from calcium dodecylbenzenesulfonate (Rhodacal 60 / BE, Nansa EVM 40 / 2ND, Calsogen 4818), wherein the ratio of the nonionic surfactant to the anionic surfactant is from about 10:1 to about 1:10.

[0105] In any of the above embodiments, chlorpyrifos may be present in the composition in the form of its ester, more preferably chlorpyrifos ester.

[0106] In one implementation, it may be expected to include at least two nonionic surfactants.

[0107] The compositions of the present invention may optionally contain other desired agriculturally acceptable ingredients, including surfactants of a variety other than those defined above.

[0108] Other optional components of the compositions of the present invention include agents for altering color, viscosity, gelling properties, freezing point, dissolution rate, dispersibility, or other formulation properties.

[0109] In one embodiment, the composition according to the invention further comprises an organic solvent.

[0110] In one embodiment, the organic solvent is selected from aromatic solvents, amides, esters, or alcohols.

[0111] In one embodiment, the organic solvent is selected from γ-butyrolactone, esters of vegetable oils, methyl octanoate, dimethyl glutarate, dimethyl succinate, dimethyl adipate, benzyl alcohol, methyl benzoate, dimethyldecylamide, esters derived from L-lactic acid and D-lactic acid (such as 2-ethylhexyl-1-lactic acid ester), ethylene glycol ethers, diethylene glycol monoethyl ether dimethyl sulfoxide, etc.

[0112] In one embodiment, the composition according to the invention contains an organic solvent in an amount of about 10% to 80% by weight of the composition.

[0113] The compositions of the present invention may optionally contain one or more additional herbicides. These additional herbicides may be selected from the class comprising aryloxyphenoxypropionates, anilines, sulfonylureas, triazolinones, pyridinecarboxylic acids, quinolinecarboxylic acids, and pyrimidinoxybenzoic acids.

[0114] The present invention also provides a method for preparing the inventive composition according to the invention, the method comprising dissolving cyhalofop-butyl and chlorpyrifos or their salts or esters in an organic solvent, then adding a mixture comprising a nonionic surfactant and an anionic surfactant, and homogenizing the resulting mixture to obtain the composition.

[0115] In one embodiment, the present invention provides a method for preparing a composition comprising:

[0116] Cyhalofop-butyl;

[0117] Green chlorpyrifos or its salts or esters; and

[0118] A mixture containing nonionic and anionic surfactants;

[0119] In one embodiment, the present invention provides a method for preparing an emulsifiable concentrate composition comprising:

[0120] Cyhalofop-butyl;

[0121] Green chlorpyrifos or its salts or esters; and

[0122] A mixture containing nonionic and anionic surfactants;

[0123] The method includes dissolving cyhalofop-butyl, chlorpyrifos, or their salts or esters in an organic solvent, then adding a mixture comprising a nonionic surfactant and an anionic surfactant, and homogenizing the resulting mixture to obtain a composition.

[0124] In one embodiment, the present invention provides a method for preparing an emulsifiable concentrate composition comprising:

[0125] Cyhalofop-butyl;

[0126] Green chlorpyrifos or its salts or esters; and

[0127] A mixture containing nonionic and anionic surfactants;

[0128] The method includes dissolving cyhalofop-butyl and chlorpyrifos or their salts or esters in an organic solvent, then adding a mixture comprising a nonionic surfactant and anionic surfactant (wherein the ratio of nonionic surfactant to anionic surfactant is about 10:1 to about 1:10), and homogenizing the resulting mixture to obtain a composition.

[0129] In one embodiment, the present invention provides a method for preparing an emulsifiable concentrate composition comprising:

[0130] Cyhalofop-butyl;

[0131] Green chlorpyrifos or its salts or esters; and

[0132] A mixture containing nonionic and anionic surfactants;

[0133] The method comprises dissolving cyhalofop-butyl and chlorpyrifos or their salts or esters in an organic solvent, then adding a mixture comprising a nonionic surfactant and anionic surfactant in an amount of about 1% to about 80% by weight of the composition, and homogenizing the resulting mixture to obtain the composition.

[0134] In one embodiment, the present invention provides a method for preparing an emulsifiable concentrate composition comprising:

[0135] Cyhalofop-butyl;

[0136] Green chlorpyrifos or its salts or esters; and

[0137] A mixture containing nonionic and anionic surfactants;

[0138] The method comprises dissolving cyhalofop-butyl and chlorpyrifos or their salts or esters in an organic solvent, then adding a mixture comprising about 1% to 50% by weight of a nonionic surfactant and about 1% to 30% by weight of an anionic surfactant in the composition, and homogenizing the resulting mixture to obtain the composition.

[0139] In addition to those outlined above, methods involving the order of addition are also possible.

[0140] In any of the above methods, chlorpyrifos can exist in the form of its ester, particularly chlorpyrifos ester.

[0141] The present invention provides the use of compositions comprising cyhalofop-butyl, chlorpyrifos or their salts or esters, and a mixture comprising nonionic and anionic surfactants as herbicides.

[0142] The present invention also provides a method for controlling unwanted weeds, comprising applying a herbicidal amount of the composition according to the invention to the weeds or their location.

[0143] In one embodiment, the present invention provides a method for controlling unwanted weeds, comprising applying a herbicidally effective amount of a composition comprising:

[0144] Cyhalofop-butyl;

[0145] Green chlorpyrifos or its salts or esters; and

[0146] A mixture containing nonionic surfactants and anionic surfactants.

[0147] In one embodiment, the present invention provides a method for controlling unwanted weeds, comprising applying a herbicidally effective amount of a composition comprising:

[0148] Cyhalofop-butyl;

[0149] Green chlorpyrifos or its salts or esters; and

[0150] A mixture comprising a nonionic surfactant and anionic surfactant, wherein the ratio of the nonionic surfactant to the anionic surfactant is from about 10:1 to about 1:10.

[0151] The method of the present invention, comprising compositions of cyhalofop-butyl, chlorpyrifos, or their salts or esters, is applicable to any and all plant species for which cyhalofop-butyl, chlorpyrifos, or their salts or esters are bioactive herbicides. This covers a very wide variety of plant species worldwide.

[0152] In one embodiment, the weed species suitable for the composition according to the invention comprising cyhalofop-butyl, chlorpyrifos, or their salts or esters are selected from Eleusine indica, Pennisetum purpureum, Klinga punula, Cyperus esculantus, Setaria barbata, Mimosa invisa, Panicum laxum, Synedrella nodiflora, Euphorbia Hétérophyla, and Ageratum. ), Stachytarpheta angustifolia, Emilia coccinea, Commelina bengalensis, Ergieron floribundus, Hydrolia glabra, Phyllanthus savantus, Ischaemum rugosum, Echinochloa colona, ​​Cyperus iria, C. dffirmis Scirpus jacobii, Fimbristylis litorqlis, Alternanthera sessilis, Physalis angulata, Ludwigia abyssinica, Phyllanthus emorlts, Corchorus The genera *Ipomoea* include *Ipomoea olitorius*, *Melochia corchorifolia*, *Ipomoea aquatica*, *Eclipta prostrata*, *Ludwigia adscendens*, *Kyllinga sp.*, *Sesbania sp.*, *Paspalum scrobiculatum*, *Sphenocileazeyl anica*, and *Fimbristylis ferruginea*.

[0153] In one embodiment, the present invention provides a method for post-emergence control of grassy weeds in rice.

[0154] In another embodiment, the present invention provides a method for post-emergence control of broadleaf weeds in rice.

[0155] To provide the desired level of herbicidal activity, the selection of the amount of application of the composition comprising cyhalofop-butyl, chlorpyrifos or its salts or esters, and a mixture comprising nonionic and anionic surfactants, is within the technical skill of an average agricultural technician.

[0156] According to one embodiment of the present invention, a kit is provided. The kit comprises a plurality of components, each of which may contain at least one or more of the components of the storage-stable insecticidal composition of the present invention.

[0157] In accordance with the above objectives, the present invention provides a medicine box comprising:

[0158] (a) The first component containing cyhalofop-butyl;

[0159] (b) A second component comprising chlorpyrifos or its salt or its ester; and

[0160] (c) A mixture containing nonionic surfactants and anionic surfactants.

[0161] The first, second, and third components are instructed to be mixed before being applied to the site.

[0162] According to one embodiment of the invention, the various components of the storage-stable insecticidal composition can be used individually or have been partially or completely mixed with each other to prepare the composition according to the invention. They can also be packaged and further used as combined compositions, such as kits.

[0163] In one embodiment of the invention, the kit may contain one or more (including all) components that can be used to prepare a storage-stable insecticide composition. For example, the kit may contain an active ingredient and / or a mixture of nonionic and anionic surfactants. One or more components may have been combined together or pre-formulated. In those embodiments where the kit provides more than two components, the components may have been combined together and packaged as is in a single container, such as a vial, bottle, box, bag, pouch, or can.

[0164] In other embodiments, the two or more components of the kit may be packaged separately, i.e., not pre-formulated. Therefore, the kit may include one or more individual containers, such as vials, boxes, bottles, bags, pouches, or jars, each containing a separate component for storing a stable insecticidal composition.

[0165] In both forms, the components of the medicament can be applied separately or together with other components, or as components of a combined composition according to the invention for preparing a storage-stable insecticidal composition according to the invention.

[0166] In a preferred embodiment of the invention, the insecticidal composition comprising (a) cyhalofop-butyl; (b) chlorpyrifos or its salt or ester; and (c) a mixture of nonionic and anionic surfactants is in the form of a kit having single or multiple packages.

[0167] The invention is explained in more detail through the following embodiments. However, it should be understood that the scope of the invention is not limited in any way to these embodiments. Any person skilled in the art will understand that the invention includes the foregoing examples, and further modifications and changes can be made within the technical scope of the invention.

[0168] Example:

[0169] Example 1: An emulsifiable concentrate composition comprising cyhalofop-butyl and chlorpyrifos was prepared according to the present invention as follows:

[0170] Element Quantity (% weight / weight) Cyhalofop-butyl 19.23 Green chlorpyrifos 34.61 Calcium dodecylbenzenesulfonate 3.69 Ethoxylated tristyrylphenol 7.60 silicone defoamer 0.00 Aromatic solvents 34.87

[0171] method:

[0172] Add the required amount of solvent to the mixing container. Add the required amounts of cyhalofop-butyl and chlorpyrifos, and stir until completely dissolved. Add the anionic and nonionic surfactants and mix for 30 minutes. Then filter the product through a 50 μm filter and package it.

[0173] Example 2: The emulsifiable concentrate composition comprising cyhalofop-butyl and chlorpyrifos according to the present invention was prepared as follows:

[0174] Element Quantity (% weight / weight) Cyhalofop-butyl 17.85 Green chlorpyrifos 32.11 Calcium dodecylbenzenesulfonate 7.27 EO / PO copolymer 3.12 silicone defoamer 0.00 Methyl benzoate 39.65

[0175] The composition was prepared according to the method of Example 1.

[0176] Example 3: The emulsifiable concentrate composition comprising cyhalofop-butyl and chlorpyrifos according to the present invention was prepared as follows:

[0177] Element Quantity (% weight / weight) Cyhalofop-butyl 10.34 Green chlorpyrifos 18.56 Calcium dodecylbenzenesulfonate 4.81 Ethoxylated tristyrylphenol 3.21 <![CDATA[C9 to C 11 alcohol ethoxylate]]> 15.06 silicone defoamer 0.004 Aromatic solvents 48.02

[0178] The composition was prepared according to the method of Example 1.

[0179] Example 4 (Comparative Example): An emulsifiable concentrate composition of cyhalofop-butyl and chlorpyrifos was prepared as follows:

[0180] Element Quantity (% weight / weight) Cyhalofop-butyl 17.85 Green chlorpyrifos 32.03 Calcium dodecylbenzenesulfonate 0.0 Ethoxylated tristyrylphenol 10.40 silicone defoamer 0.00 Methyl benzoate 39.72

[0181] Example 5 (Comparative Example): An emulsifiable concentrate composition of cyhalofop-butyl and chlorpyrifos was prepared as follows:

[0182]

[0183]

[0184] Example 6 (Comparative Example): An emulsifiable concentrate composition of cyhalofop-butyl and chlorpyrifos was prepared as follows:

[0185] Element Quantity (% weight / weight) Cyhalofop-butyl 17.91 Green chlorpyrifos 32.28 Calcium dodecylbenzenesulfonate 10.45 Nonionic surfactants 0 silicone defoamer 0.00 Methyl benzoate 39.36

[0186] Testing of storage stability and emulsion stability

[0187] The storage stability and emulsion stability of the emulsifiable concentrate compositions according to the invention were tested at different temperatures (according to CIPAC MT 39.3). Observations of samples after 14 days at 25°C, 0°C, and 54°C are summarized in the following tables (Tables 1 and 2).

[0188] Table 1: Storage stability of the composition

[0189]

[0190] Table 2: Storage stability and real-time data of emulsifiable concentrate compositions of cyhalofop-butyl and chlorpyrifos (Example 3)

[0191]

[0192]

[0193] Table 3: Emulsion Stability

[0194] According to CIPAC MT 36.1, the emulsion stability of the compositions according to the invention was tested 24 hours after dilution, and the results are summarized in Table 3 below.

[0195]

[0196] The formulation stability of samples prepared according to the present invention (Examples 1 to 3) was tested after 14 days at different temperatures of 25°C, 0°C, and 54°C. All these formulations were found to produce stable emulsions. After 14 days, all samples yielded clear and stable EC formulations at all temperatures without any phase separation. This indicates that the combined surfactants according to the present invention impart excellent stability to the emulsions. This is further demonstrated by the stability of sample (Example 3) after a 12-month storage period. However, samples 4 and 5 exhibited sedimentation and emulsification at the bottom of the container, indicating that the lack of the surfactant combination of the present invention resulted in unstable products.

[0197] In addition, the emulsion stability of the samples was tested. It was found that the compositions prepared according to the present invention were stable after 24 hours of observation, without any deposition or layer separation (results summarized in Table 3).

[0198] The stability of Examples 4 and 5, prepared in the absence of anionic surfactants, and Example 6, prepared in the absence of nonionic surfactants, was also tested. Deposition was observed in these samples during storage, confirming their unsuitability for commercialization.

[0199] Stability of active ingredients:

[0200] The degradation of the active ingredient in the compositions prepared according to the present invention was investigated. The stability of samples prepared according to Examples 1 to 3 was observed by holding them at 54 ± 2 °C for up to 14 days (AHS according to CIPAC MT 46.3), and Sample 3 was further tested at 40 °C for 8 weeks and at 25 °C for 24 months. The results are summarized in Table 4.

[0201] Table 4: Stability of Active Ingredients

[0202]

[0203] As is evident from Table 4, no degradation of cyhalofop-butyl or chlorpyrifos was observed after holding at 54±2°C for 14 days. This was further confirmed by extended studies of one of the samples, holding it at 40°C for 8 weeks and at 25°C for 24 months. No change in the pH of the emulsifiable concentrate composition was also observed during these time periods. The adjuvant combination according to the invention produces a stable formulation that does not undergo any chemical or physical changes when stored at low temperatures and is suitable for its intended use.

Claims

1. A composition, which is an emulsifiable concentrate, and has the following composition: Cyhalofop-butyl is present in an amount of 1% to 60% by weight of the composition; The herbicide, or its salt or ester, is present in an amount from 5% to 80% by weight of the composition; A mixture comprising a nonionic surfactant present in an amount of 1% to 50% by weight of the composition and an anionic surfactant present in an amount of 1% to 30% by weight of the composition; and Organic solvents, The ratio of the nonionic surfactant to the anionic surfactant is 10:1 to 1:

10. The nonionic surfactant is selected from fatty alcohol alkoxylates, alkylphenol alkoxylates, fatty acid alkoxylates and EO / PO copolymers, and mixtures thereof. The anionic surfactant is selected from linear or branched alkylbenzene sulfonates, alcohol ether sulfates, secondary alkyl sulfonates, and alcohol sulfates.

2. The emulsifiable concentrate composition according to claim 1, wherein the ratio of the nonionic surfactant to the anionic surfactant is 5:1 to 1:

5.

3. The composition according to claim 1, wherein the organic solvent is selected from aromatic solvents, amides, esters or alcohols.

4. The composition according to claim 3, wherein the organic solvent is present in an amount of 10% to 80% by weight of the composition.

5. The composition according to claim 1, wherein chlorpyrifos is present in the composition in the form of chlorpyrifos ester.

6. A method for preparing a composition according to any one of claims 1-5, comprising dissolving cyhalofop-butyl, and chlorpyrifos or their salts or esters in an organic solvent, then adding a mixture comprising a nonionic surfactant and an anionic surfactant, and homogenizing the resulting mixture to obtain the composition.

7. A method for controlling unwanted weeds, comprising applying a herbicidal amount of the composition according to any one of claims 1-5 to the weed or its location, wherein the method is used for post-emergence control of grassy weeds in rice.

8. The method for controlling unwanted weeds according to claim 7, wherein the method is used for post-emergence control of broadleaf weeds in rice.

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