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    • 专利摘要:
    The present invention relates to a herbicidal composition comprising an aqueous suspension of microcapsules, the microcapsules having a wall composed of a porous polymeric condensate and containing a solution of clomazone in a solvent system comprising one or more inedible oils. The invention also relates to a process for the preparation of this composition, comprising obtaining a water immiscible phase comprising clomazone, an isocyanate and optionally an ACD crosslinking agent, dissolved in a solvent system comprising an oil. inedible ; obtaining an aqueous phase comprising one or more surfactants; combining the water immiscible phase and the aqueous phase to form a dispersion of the water immiscible phase in the aqueous phase; forming in this manner polyurea microcapsules containing droplets of the immiscible phase with water; and curing the microcapsules.
    公开号:FR3018998A1
    申请号:FR1552157
    申请日:2015-03-17
    公开日:2015-10-02
    发明作者:James Timothy Bristow；Yifan Wu
    申请人:Rotam Agrochem International Co Ltd；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a herbicidal composition comprising clomazone as an active ingredient. The invention further relates to the preparation of the formulation and its use.
    [0002] Clomazone formulations are known and are commercially available. A commercial formulation of clomazone is an emulsifiable concentrate (EC) based on a solvent. The formulation is usually prepared by dissolving the active ingredient clomazone in an inert liquid organic solvent together with a suitable emulsifying system. The mixture of the resulting combination with water spontaneously forms an oil-in-water emulsion of the clomazone / solvent solution. Modern agricultural practice needs better control over the application of biologically active components to target plants. This better control in turn provides a number of benefits. First, the better control of the active ingredient makes it possible to use compounds with better stability for extended periods of time. In addition, the better control reduces the risk to the environment presented by the herbicide composition. In addition, better control makes it possible to reduce the acute toxicity of the composition and to adapt any incompatibility between the ingredients. It is known that microencapsulation is a technique that offers a number of advantages in improving the control that can be achieved when dispensing herbicidal formulations, compared to other agrochemical formulation techniques. .
    [0003] Several basic methods for preparing microencapsulation formulations of active herbicidal compounds have been described and are known in the art. In particular, known microencapsulation techniques include coacervation, interfacial polymerization, and in situ polymerization. Most commercially available CS (microcapsule suspension) formulations are manufactured by interfacial polymerization. Examples of commercial CS formulations prepared in this manner include Chlorpyrifos CS, Lambda-cyhalothrin CS, Fluorochloridone CS and CS Methylparation. When these formulations are dried, they form water-dispersible granules containing microcapsules, the active ingredient being contained within the microcapsules. The role of the microcapsules is to contain the active ingredient, so that at the time of application of the formulation, for example in the form of a dispersion in water, the active ingredient is slowly released from the microcapsules and that its Dispersion outside the application locus is limited. Clomazone (2 - [(2-chlorophenyl) methyl] -4,4-dimethyl-3-isoxazolidinone) is a well-known herbicide for the control of soybean, cotton, cassava, maize, rapeseed, sugar cane and tobacco, among others. The formulation of clomazone by microencapsulation is known in the art.
    [0004] However, because of the physical properties of clomazone, for example its high volatility, the determination of the optimal formulation is still very difficult. For example, US 6,380,133 discloses a technique for encapsulating clomazone in microcapsules having a shell composed of a cross-linked polyurea. However, the regulation of the release rate of clomazone is still not satisfactory. A known method of preparing a CS formulation is interfacial polymerization. In this process, the active ingredient is dissolved in a solvent, together with monomers and / or prepolymers. The resulting mixture is dispersed in an aqueous phase containing one or more emulsifiers, optionally one or more protective colloids and, optionally, additional prepolymers. A capsule wall is formed around the oil droplets due to the interfacial polymerization taking place at the oil / water interface in the presence of a catalyst or heat. Solvents, although generally inert in the finished formulation, are used when microencapsulating the active ingredients to perform a number of roles, for example dissolving the active component to allow encapsulation of the solid active ingredients and adjusting the diffusion rate of the active substance through the polymer wall, which in turn enables the release of the active ingredients of the microcapsules when the formulation has been applied. In addition, solvents may be chosen, in addition to their role of dissolving the active components, to influence the quality of the emulsion, for example by maintaining a low viscosity during the emulsification and / or polymerization steps. EP 1 652 433 discloses a herbicidal formulation comprising an aqueous liquid composition in which a plurality of solid microcapsules is in suspension, the microcapsules having a capsule wall composed of a porous polymeric condensate consisting of at least one substance selected from polyurea, a polyamide and an amide-urea copolymer. The microcapsules are formed to encapsulate clomazone acting as an active ingredient. In the capsules, clomazone is dissolved in a high boiling inert organic solvent, in particular a diester of 1,2-benzene dicarboxylic acid and (C 3 -C 6) branched alkyls. EP 0 792 100 describes a process for preparing an encapsulated clomazone formulation. The method comprises a step of obtaining a water immiscible liquid phase consisting of clomazone and polymethylene polyphenyl isocyanate, with or without aromatic hydrocarbon solvent. EP 0 792 100 describes the microencapsulation of clomazone by the preparation of a water-immiscible phase containing specified amounts of clomazone and polymethylene polyphenyl isocyanate (PMPPI), together with an aromatic solvent. The solvent is said to be optional in the case of high-load formulations of clomazone. However, the exemplary formulations generally contain a petroleum solvent in an amount of 4% to 6% by weight. EP 1 840 145 discloses a microencapsulated formulation of clomazone, in which clomazone is dissolved in a solvent, in particular in cyclohexanone, and retained in microcapsules having a shell formed from a polymer prepared by interfacial polymerization. involving the reaction of an isocyanate with an acetylene carbamide derivative. US 5,783,520 discloses a process for preparing an encapsulated clomazone formulation. The method comprises a step of obtaining a water immiscible liquid phase consisting of clomazone and polymethylene polyphenyl isocyanate (PMPPI), with edible oils, such as soybean oil, corn oil, sunflower oil, acting as a high-boiling organic solvent. US 5,783,520 describes the microencapsulation of clomazone by the preparation of a water-immiscible phase containing specified amounts of clomazone and PMPPI together with an edible oil. It is claimed that the formulation reduces the volatility of clomazone in the final formulation. More recently, US 2014/0 031 231 has described a wide variety of different formulations of clomazone, including microencapsulated formulations. Many organic solvents are suggested such as, but not limited to, a range of animal and vegetable oils for clomazone. In particular, linseed oil is exemplified in US 2014/0 031 231 as a solvent for clomazone. There is a need for a better formulation of clomazone, particularly a better formulation of microencapsulated clomazone. Unexpectedly, it has been found that particularly effective microencapsulated clomazone formulations can be prepared using one or more inedible oils as solvents. In particular, the use of non-edible oils has been found to provide clomazone with a high dispersibility, while still allowing the formulation to be easily suspended in water during the formation process. microcapsules. In addition, the formulation has a low wet sieve residue which is a high degree of retention of the clomazone active ingredient in the microcapsules. Inedible oils have been found to be less toxic than the solvents used in the formulations of the prior art, in particular the diester of 1,2-benzenedicarboxylic acid and (C 3 -C 6) branched alkyls. the aromatic and petroleum hydrocarbon solvents of the compositions of the prior art and described above. Therefore, in a first aspect, the present invention provides a herbicidal composition comprising an aqueous suspension of microcapsules, the microcapsules having a capsule wall composed of a porous polymeric condensate, wherein the microcapsules contain a solution of clomazone in a system of solvents comprising one or more inedible oils.
    [0005] Unexpectedly, it has been discovered that microencapsulation of clomazone in a solvent system comprising one or more inedible oils provides a significantly improved formulation, particularly having as properties a high dispersibility, ease of formation, and maintenance. suspension, and a low residue on wet sieve. Another advantage is that the inedible oils used as solvents for clomazone are much less toxic than the known solvents and used in the formulations of the prior art. In addition, the inedible oils used in the formulations of the present invention are available at lower costs than the edible oils suggested in the prior art, and the use of inedible oils does not remove the valuable oils from the present invention. human food chain. In particular, the use of inedible oils has been found to confer increased bioactivity on clomazone. Many inedible oils are used for insecticide and fungicide applications. It has been unexpectedly discovered that the dissolution of clomazone in an inedible oil produces a significant synergistic effect, while edible oils, such as soybean oil, corn oil, sunflower oil, and Linseed oil, used in the prior art, simply have a role of liquid support and are inert with respect to the finished formulation. The clomazone formulation of the present invention comprises microcapsules suspended in an aqueous phase. The microcapsules contain a solution of clomazone in a solvent phase comprising one or more inedible oils, so that the clomazone found in the formulation is retained within the microcapsules. Clomazone is the common name for 2 - [(2-chlorophenyl) methyl] -4,4-dimethyl-3-isoxazolidinone, a compound known to be herbicidally active and commercially available. The formulation of the present invention may include clomazone as the sole herbicidal active ingredient. Alternatively, one or more other active ingredients may be present in the formulation, in the microcapsules and / or in the aqueous phase. The formulation may include clomazone in any amount appropriate to provide the required level of activity when applied to a locus to control plant growth. Preferably, the formulation contains clomazone in an amount of at least 10% by weight, more preferably at least 20%, more preferably at least 40%. Formulations containing at least 50% by weight of clomazone are also contemplated in the present invention. In the formulation of the present invention, clomazone is retained in solution in a system of organic solvents within the microcapsules. The solvent comprises one or more inedible oils. Other solvents may be present in the microcapsules. However, it is preferred that the solvent consists essentially of one or more inedible oils. Inedible oils are not water soluble or water miscible and form an organic phase in the microcapsule preparation process, as described hereinafter.
    [0006] Inedible oils are known in the art and are commercially available. In this document, inedible oils are vegetable oils, essential oils, mineral oils and fatty acid esters that are generally not considered edible by humans.
    [0007] Suitable vegetable oils, particularly pressed vegetable oils, are vegetable oils that are not edible. These oils can be obtained from plants and examples include the fruit oil from the Love cork tree, Burdock oil (Bur oil), Bancoul oil (Walnut oil). Kukui), carrot seed oil (pressed), castor oil, chaulmoogra oil, jojoba oil, neem oil, rose seed oil, soybean oil sea buckthorn oil, snowball seed oil (Viburnum oil), Tamanu or Foraha oil, tonka bean oil. Castor oil and neem oil are particularly preferred inedible oils. Suitable essential oils are also known and are commercially available. Suitable essential oils include sesame oil, pyrethrum, glycerol derived lipids or glycerol fatty acid derivatives, cinnamon oil, cedar oil, clove oil, geranium oil, lemongrass oil, angelica oil, peppermint oil, turmeric oil, wintergreen oil, rosemary oil, fennel oil, cardamom oil, caraway oil (caraway oil), chamomile oil, coriander oil, guaiac wood oil, cumin oil, dill oil, parsley oil, basil oil, camphor oil, ylang-ylang oil, lemongrass oil, eucalyptus oil, fennel oil, ginger oil , bitter with Pakistan incense fat (coconut oil), perilla oil, cedar oil, jasmine oil, Sofia rose grass oil (palmarosa sofia), the 20 peppermint oil from the west, anise oil (star anise essence), oil from you berries, neroli oil, tolu incense, patchouli oil, herb oil, Japan's four-dish white oil (Chamaecyparis obtuse oil), Hiba oil, red sandalwood oil, orange leaf oil, laurel oil, vetiver oil, bergamot oil, Peruvian fat incense, olive oil 25 rose (rosewood oil), grapefruit oil, lemon oil, orange oil, orange oil, oregano oil, lavender oil, l obtusiloba oil (Lindera oil), pine needle oil, pepper oil, rose oil, orange oil, tangerine oil, tea tree oil , tea oil, thyme oil, thymol oil, garlic oil, onion oil, aloe oil, peppermint oil from Japan and spearmint oil.
    [0008] In one embodiment, the oil is an oil from one or more condiment plants. In another embodiment, the oil is selected from citronella oil, geranium oil, tea tree oil, lavender oil, carnation oil (clove oil). ), eucalyptus oil, thyme oil and oregano oil. Pyrethrum oil, lemongrass oil and sesame oil are the favorite essential oils. Suitable mineral oils are commercially available and include petroleum distillation fractions. Preferred mineral oils are mixtures of open chain C14 to C30 hydrocarbons, closed chain hydrocarbons (naphthenes) and aromatic hydrocarbons. The hydrocarbons can be linear or branched. Particularly preferred mixtures are those having a non-aromatic content of less than 8% by weight, and more preferably a non-aromatic content of less than 4% by weight. Examples that may be mentioned here are Exxsol® D140 and white oil. Suitable fatty acid esters are also known and commercially available. Suitable fatty acid esters may be selected from C 10 to C 20 fatty acid esters, more preferably C 12 to C 20 fatty acid esters, or more preferably C 14 to C 18 fatty acid esters, for example myristates, palmitates, oleates and stearates, and mixtures such as cocoates. Examples of suitable fatty acid esters include cetyl alcohol, stearyl alcohol, squalane, isopropyl myristate, isopropyl palmitate, isooctyl palmitate, cetyl palmitate, cocoate glyceryl, glyceryl stearate, glyceryl isostearate, decyl oleate, caprylic / capric acid triglyceride, glyceryl oleate, ethylhexyl palmitate, ethylhexyl stearate and decyl cocoate . Isooctyl palmitate is a preferred fatty acid ester. The microcapsules may contain a solution consisting essentially of one or more inedible oils and clomazone. Other components may be included in the solvent system, if applicable. Other components that may be present in the solution are known in the art and include surfactants, stabilizers and the like. In particular, antioxidants may be included in the solvent system within the microcapsules. As described in detail below, the preparation of the formulation may require heating the formulation to cure the polymer walls of the microcapsules. Heating the formulation can increase the rate of oxidation of the active components. Therefore, one or more antioxidants may be included. Suitable antioxidants are known in the art and are commercially available. Examples include butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA). The antioxidant may be present in any amount appropriate to reduce or prevent oxidation of the active ingredient and maintain its stability. The amount of antioxidant may be in the range of 0.005% to 1.0% based on the weight of the microcapsules, and more preferably 0.01% to 0.05% by weight. The size of the microcapsules can be adjusted by a number of factors in the preparation of the composition of the present invention. In particular, the size of the microcapsules can be adjusted by including one or more additional components in the water immiscible liquid phase within the microcapsules, particularly one or more surfactants. The hydrophilic / lipophilic balance (HLB) of the surfactants used can influence the size of the microcapsules formed in the composition, the surfactants or surfactant combinations having a lower HLB giving microcapsules having a smaller diameter. Suitable oil-soluble surfactants are known and commercially available, for example Atlox 4912, an A-B-A block surfactant copolymer having a low HLB of 5.5. Other block surfactant copolymers can be used, in particular those composed of polyglycol, for example polypropylene glycol and hydroxylated poly (fatty acids). The surfactants may be present in any suitable amount to impart the required particle size to the microcapsules in the preparation of the composition. A preferred concentration in the water immiscible phase is from 1% to 30%, and more preferably from about 5% to 25% by weight of the microcapsules.
    [0009] The non-edible oil solvent system within the microcapsules contains the solvent, particularly the inedible oil (s), in an amount sufficient to dissolve the required amount of clomazone. Preferably, the weight ratio of clomazone to inedible oil is 1/12 to 12/1, more preferably 1/10 to 10/1, more preferably 1 / 7.5 to 7.5 / 1. The liquid phase within the microcapsules preferably contains at least 20% by weight of clomazone, more preferably at least 30%, or more preferably at least 50% by weight of clomazone. Clomazone may be present in the encapsulated material in an amount of 1% to 95% by weight, more preferably 1% to 90%, or more preferably 5% to 90% by weight. The inedible oil type solvent is preferably present in the liquid within the microcapsules in an amount of at least 5% by weight, and more preferably at least 10% by weight.
    [0010] The clomazone solution in the non-edible oil solvent system is contained within the microcapsules. The microcapsules can be formed from any suitable polymer. The polymer of the microcapsules is porous, which allows the controlled release of the active ingredient clomazone from the microcapsules. The rate of release of the active ingredient from the microcapsules can be regulated in a known manner, for example by the appropriate selection of the polymers used to prepare the microcapsules, the selection of the size of the microcapsules, the porosity of the polymer and the presence of components within the microcapsules. Polymeric systems suitable for use in the microencapsulation formulation of the present invention are known in the art. The polymer forming the wall of the microcapsules is preferably formed by interfacial polymerization. Examples of suitable polymers for forming the microcapsules include porous polymeric condensates composed of one or more substances selected from polyurea, polyamide and amide-urea copolymer.
    [0011] Polyureas are the preferred polymers for microcapsules. The polyureas may be formed by the interfacial polymerization of an isocyanate, particularly a polyfunctional isocyanate. The polyisocyanates used as starting components according to the present invention may be aliphatic or aromatic polyisocyanates. For example, the aromatic polyisocyanates may be 1,3- and / or 1,4-phenylene diisocyanates, 2,4-, 2,6-tolylene diisocyanates (TDI), a crude TDI, a diisocyanate of 2, 4'-, 4,4'-diphenylmethane (MDI), crude MDI, 4,4'-diisocyanatebiphenyl, 3,3'-dimethyl-4'-diisocyanate biphenyl, 3,3'-dimethyl -4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, m- and p-isocyanate phenylsulfonylisocyanate, polyaryl polyisocyanate (PAPI), 4,4'-diphenylmethane diisocyanate (PMDI), polymethylene polyphenyl isocyanates (PMPPI) and aromatic isocyanate derivatives and prepolymers The aliphatic polyisocyanates may be ethylene diisocyanate, hexamethylene diisocyanate ( HDI), tetramethylene diisocyanate, dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexa-methyl diisocyanate ylene, lysine diisocyanate, methyl 2,6-diisocyanate caproate, bis (2-isocyanate ethyl fumarate), bis (2-isocyanate ethyl) carbonate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate, trimethylhexamethylene diisocyanate (TMDI), dimer diisocyanate acid (DDI), isophorone diisocyanate (IPDI), dicyclohexyl diisocyanate, dicyclohexylmethane diisocyanate (H-MDI), cyclohexylene diisocyanate, diisocyanate hydrogenated tolylene (HTDI), bis (2-isocyanate ethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate, aryl-aliphatic polyisocyanates containing 8 to 15 carbon atoms, the met / or p-xylylene diisocyanate (XDI), alpha, alpha, alpha, alphatetramethyl xylylene diisocyanate (TMXDI), ethylene diisocyanate, hexamethylene diisocyanate, (HDI), tetramethylene diisocyanate, dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, methyl 2,6-diisocyanate caproate, bis (2isocyanate ethyl) fumarate, bis (2-isocyanate ethyl) carbonate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate, trimethyl hexamethylene diisocyanate (TMDI), dimeric diisocyanate acid (DDI), and aliphatic isocyanate derivatives and prepolymers.
    [0012] The distillation residues obtained from the commercial production of isocyanates which contain isocyanate groups may be used, optionally in the form of solutions in one or more of the aforementioned polyisocyanates. Any mixture of the aforementioned polyisocyanates may also be used.
    [0013] Preferred isocyanates for forming the polyureas are known in the art and are commercially available, including alpha, alpha, alpha, alpha-tetramethylxylylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), derivatives of HDI (trimer HDI, HDI Uredione) which are commercially available Desmodur® N3600, XP2410 and N3400, isophorone diisocyanate (IPDI), polymethylene polyphenyl isocyanates (PMPPI), methylene diphenyl isocyanate (MDI), polyaryl polyisocyanate (PAPI) and toluene diisocyanate (TDI). The microcapsules of the present invention may further be formed from a polyfunctional amine. Amines suitable for use contain two amine groups. Examples of amines suitable for use in the present invention are higher diamine or polyamine type reactants, including ethylene diamine, phenylene diamine, toluene diamine, hexamethylene diamine, diethylene triamine, piperazine, 1,3,5-benzenetriamine trihydrochloride, 2,4,6-triaminotoluene trihydrochloride, tetraethylene pentamine, pentaethylene hexamine, polyethylene imine, 1,3,6-triaminonaphthene, 3,4,5 -triamino-1,2,4-triazole, melamine and 1,4,5,8-tetramino-anthraquinone. Preferred amines for forming the polyureas are known in the art and are commercially available, including ethylenediamine (EDA), diethyltriamine (DETA), triethylenetetramine (TETA) and 1,6-hexanediamine (HDA). .
    [0014] As previously mentioned, the size of the microcapsules can be selected to provide the required properties of the formulation, in particular the release rate of the clomazone active ingredient of the microcapsules. The microcapsules may have a particle size in the range of 0.5 micron to 60 microns, more preferably 1 micron to 60 microns, or more preferably 1 micron to 50 microns. It has been found that a range of particle sizes ranging from 1 micron to 40 microns, and more preferably from 1 micron to 30 microns, is particularly suitable. The microcapsules may comprise the polymer in an amount appropriate to provide the required properties of the formulation. Preferably, the polymer is present in an amount of 2% to 25% by weight of the microcapsules, more preferably 3% to 20%, more preferably 5% to 15% by weight. A particularly suitable amount of polymer in the microcapsules is in the range of 5% to 12% by weight.
    [0015] The formulation of the first aspect of the present invention may comprise the microcapsules as described above suspended in an aqueous phase. The aqueous phase comprises water, together with other components necessary to impart the desired properties of the formulation, for example the stability of the suspension and the dispersibility of the microcapsules. Suitable components that can be included in the aqueous phase of the formulation are known in the art and are commercially available. Suitable components are those which enhance and maintain the dispersibility and suspension of microcapsules, and include one or more surfactants, stabilizers, emulsifiers, viscosity modifiers, protective colloids and the like. The aqueous phase may be any suitable amount of the formulation, provided that the microcapsules are well dispersed and maintained in suspension. Usually, the aqueous phase will comprise from 15% to 50% by weight of the formulation, more preferably from 20% to 40%, more preferably from 25% to 30%.
    [0016] The formulation of the present invention can be used in a known manner to control the growth of plants. In particular, the formulation may be diluted with water to the required concentration of active ingredient and applied to a locus in a known manner, for example by spraying. It has also been found that the formulation of the present invention can be prepared in a dry form, i.e. without the microcapsules being suspended in an aqueous phase. Therefore, in another aspect, the present invention provides a herbicidal composition comprising microcapsules, microcapsules having a capsule wall composed of a porous polymeric condensate, wherein the microcapsules contain clomazone and a solvent comprising one or more non-organic oils. edible. Details of the microcapsules and their composition are described below. The formulation of this aspect of the invention, when used, is usually admixed with water to the required level of dilution to form a suspension of microcapsules in an aqueous phase, which can then be used and applied to the aqueous phase. in a known manner, as described above. The formulations of the present invention may be prepared in a manner analogous to the preparation of known microencapsulation formulations. In general, the polymer-forming reactants of the microcapsule walls are dispersed between an organic liquid phase and an aqueous liquid phase, so that polymerization occurs at the interface between the two phases. For example, in the case of microcapsules formed from a polyurea, the isocyanate, optionally with a crosslinking agent, such as a crosslinking agent based on an acetylene carbamide derivative (ACD), is dispersed in the non-edible oil organic solvent system, together with the active ingredient clomazone, while the adjuvant is dispersed in the aqueous phase.
    [0017] The two phases are then mixed to allow the polymer to form at the interface. Acetylene carbamide derivatives (ACDs) useful as crosslinking agents are known in the art, for example as described in US 2011/0269 063. ACDs are also known as resins of the present invention. glycolurile and include those represented by the following formula: wherein R1, R2, R3 and R4 each independently represent a hydrogen atom or an alkyl containing, for example, 1 to about 12 carbon atoms, 1 to about 8 carbon atoms. carbon, 1 to about 6 carbon atoms or 1 to about 4 carbon atoms. The glycolurile resin can be soluble, dispersible or indispersible in water. Examples of glycolurile resin include highly alkylated / alkoxylated, partially alkylated / alkoxylated or mixed alkylated / alkoxylated glycolurile resins, and more specifically, the glycolurile resin may be methylated, n-butylated or isobutylated. Specific examples of glycolurile resins include CYMEL® 1170, 1171 and 1172 glycoluril resins. CYMEL® glycoluril resins are commercially available from CYTEC Industries, Inc. Acetylene-carbamides, normally liquid, substantially fully alkylated mixed and essentially completely methylolated form a class of crosslinking agents, whose starting compound is acetylene-carbamide, as such, which is also known as acetylene-diurea, and which is prepared by the reaction of two moles of urea with one mole of glyoxal. The precise chemical name of the acetylene carbamide is tetrahydroimidazo (4,5-d) imidazole-2,5 (1H, 3H) -dione. The acetylene carbamide can be fully methylolated by reacting one mole of acetylene carbamide with four moles of formaldehyde. The resulting product is identified as tetramethylol acetylene carbamide. The tetramethylol acetylene carbamide is then reacted with a selected amount of methanol to partially methylate the fully methyloleated acetylene carbamide, which is then followed by alkylation with a higher aliphatic monohydric alcohol containing two to four carbon atoms. . These monohydric alcohols may be primary or secondary alcohols. These higher monohydric aliphatic alcohols containing two to four carbon atoms may be ethanol, n-propane, isopropanol, n-butanol, isobutanol and the like. It is sometimes advantageous to completely methylate tetramethylol acetylene-carbamide and then, through a transesterification reaction, to incorporate the desired amount of ethanol, propanol or butanol into the acetylene-carbamide derivative. These fully etherified and fully methylolated acetylene-carbamide derivatives are not considered to be resinous materials since they are, as individual units, simple pure compounds or mixtures of simple pure compounds, but they are compounds which form Potential resins that enter into chemical reaction with certain ungelled and water-dispersible ionic polymer materials when they are subjected to heat and, in particular, when they are subjected to heat under acidic conditions. The concept of the degree of methylation or, more broadly, of alkylation, on average, and the concept of the degree of methylolation, on average, will be discussed below so that these concepts are fully understood. Theoretically, it is possible to completely methylolize the acetylene carbamide, that is to say, to produce tetramethylol acetylenecarbamide. However, it is common for a commercial composition believed to be tetramethylol acetylene carbamide, when analyzed, to have a fractional degree of methylolation. It is well known that fractional methylolation is not considered possible. Therefore, when a composition contains, in its analysis, a degree of methylolation of 3.70, 3.80 or 3.90, it must be recognized that this is only an average degree of methylolation of the acetylene compound. carbamide and logically establish that the aforementioned methylol composition is composed of a mixture containing a major amount of tetramethylol acetylene-carbamide with comparatively minor amounts of trimethylol acetylene-carbamide and, perhaps, insignificant amounts of derivatives in the state trace amounts, such as dimethylol acetylene-carbamide and even monomethylol acetylene-carbamide. The same concept of means can also be applied to the alkylation or etherification of the tetramethylol acetylene-carbamide composition. On the basis of this reasoning, there can be no fractional alkylation and, therefore, when in an analysis, a given composition has a degree of methylation which is, on average, between about 0.9 and 3 , 60 and that the highest alkylation has an average degree of ethylation, propylation and / or butylation, on average, correspondingly between about 2.80 and 0.40, it must be concluded that is present in such a composition a plurality of mixed ethers tetramethylol acetylene-carbamide. For example, there may be present a certain amount of monomethyl ether, tetramethylol acetylene-carbamide triethyl ether, some dimethyl ether, tetramethylol acetylene-carbamide diethyl ether, some trimethyl ether, tetramethylol acetylene carbamide monoethyl ether. . There may even be traces of tetramethyl ether of tetramethylol acetylene-carbamide. It can also be present with the various methyl ethers of tetramethylol acetylene-carbamide, various mono-, di- and tri-ethyl ethers, mono-, di- and tri-propyl ethers and mono-, di- and tri-butyl ethers. tetramethylol acetylene carbamide. It is possible to produce a monomethyl ether, monoethyl ether, monopropyl ether, tetramethylol acetylene-carbamide monobutyl ether which could be classified as a four-alkylation derivative. However, it is generally preferred to use only a higher monohydric alcohol containing two to four carbon atoms with methyl alcohol to prepare a total mixed ether of tetramethylol acetylene carbamide. Double alkylation products are therefore preferred, although triple alkylation derivatives as well as quadruple alkylation derivatives can also be used. With regard to ACDs, the preferred ACDs are the ACDs of the Powderlink® 1174 and Cymel® type commercial products, more preferably Cymel® 1171 (which is a highly alkylated glycurile resin) and Cymel® 1170 ( which is a butylated glycuril resin). It has been found that the use of Cymel-type prepolymers results in a more irregular evolution of the reaction compared to the use of Powderlink® 1174. Therefore, the most preferred ACD is Powderlink® 1174 (which is the most Tetrakis (methyloxymethyl) glycoluril, CAS No. 17464-88-9). It should be noted that commercial products may contain compounds other than the monomers mentioned on the label (for example, Powderlink® 1174 may contain oligomers). The choice of the crosslinking agent and the amount present may be used to adjust the porosity of the polymer wall of the microcapsules. Preferably, the composition comprises the crosslinking agent in an amount of from 0.1% to 20%, and more preferably from 0.5% to 15% by weight of the microcapsules. In another aspect, the present invention relates to a process for preparing a herbicidal composition, the process comprising the steps of: obtaining a water-immiscible phase comprising clomazone, an isocyanate and optionally an agent ACD crosslinking agent, dissolved in a solvent system comprising one or more inedible oils; Obtaining an aqueous phase comprising one or more surfactants; combining the water immiscible phase and the aqueous phase to form a dispersion of the water immiscible phase in the aqueous phase; forming in this manner polyurea microcapsules containing droplets of the immiscible phase with water; and curing the microcapsules. The process comprises combining a water-immiscible phase and an aqueous phase. This is done under conditions, for example with stirring, to form a dispersion of the immiscible phase with water in the aqueous phase. The aqueous phase contains at least one surfactant or emulsifier to facilitate the formation of the dispersion of the water immiscible phase in the aqueous phase. The other components necessary to impart the desired properties to the final composition, as mentioned above, can be included in the aqueous phase. The microcapsules are formed by interfacial polymerization reactions of the isocyanate and then crosslinked by the ACD resin. Preferably, the polymerization reaction proceeds while the dispersion is agitated. The microcapsules once formed are cured, preferably by heating, to cure the polymer walls of the microcapsules. The curing is usually carried out at a temperature of 30 ° C to 60 ° C, and more preferably at 40 ° C to 50 ° C, for a suitable period of time, usually 1 to 5 hours, more usually about 2 to 5 hours. 4 hours. Then, the resulting composition is preferably filtered, after cooling, to obtain a suspension of the microcapsules in the aqueous phase. The resulting product is a Clomazone CS formulation suitable for use and application as described above, especially by dilution with water and spray application. If necessary to prepare dry microcapsules, the resulting composition is subjected to a drying step to remove the aqueous phase. Any drying technique can be used, spray drying being particularly effective. The composition may be prepared with microcapsules formed from other polymers, as previously mentioned, using the appropriate wall-forming reagents according to a procedure analogous to the above procedure. In another aspect, the present invention provides the use of a clomazone formulation, as previously described, for controlling the growth of a plant.
    [0018] In another aspect, the present invention provides a method of controlling growth of a plant at a locus, the method comprising applying to the locus a microencapsulated clomazone formulation as previously described.
    [0019] Embodiments of the present invention will be described, by way of illustration only, with the aid of the following examples. EXAMPLE 1 Preparation of Clomazone Microencapsulated with Castor Oil A water-immiscible phase and an aqueous phase having the following composition are prepared (the amounts of the components being expressed in% by weight of the final composition). A. A water-immiscible organic phase, prepared just prior to its use, has the following composition: 9.36 g of technical clomazone-0.77 g of polymethylene polyphenyl isocyanate (PMPPI, Suprasec5005) -1, 47 g of castor oil. B. An aqueous solution having the following composition is prepared: - 1.60 g of sorbitan trioleate POE (20) - 0.16 g of the sodium salt of lignosulfonic acid (Kraftsperse 25M) - 0.16 g of the salt of sulfonated aromatic polymer (MORWET D425 POWDER) - 0.03 g of antifoam (Dow Corning®1500) - 6.18 g of water Step 1 0.77 g of isocyanate (Suprasec-5005) dispersed in 1.47 g of castor oil. The resulting combination is perfectly mixed at high speed in a high shear mixer and is stirred for 10 minutes. 9.36 g of clomazone are finally added to form the organic phase. Step 2 1.60 g of POE sorbitan trioleate (20), 0.16 g of the sodium salt of lignosulfonic acid (Kraftsperse 25M), 0.16 g of sodium salt of a sulfonated aromatic polymer (MORWET D-425 POWDER) and 0.03 g of antifoam (Dow Corning® 1500) are added to 6.18 g of water to form an aqueous phase. Step 3 The water immiscible organic phase is added dropwise to the aqueous phase. After mixing with the high shear mixer, an oil-in-water dispersion is formed. Step 4 The oil-in-water dispersion is transferred to an Erlenmeyer flask. 0.77 g of an aqueous solution of diethylenetriamine (0.77 g of diethylenetriamine in 1.73 g of water) is added dropwise with stirring. The dispersion is heated and maintained at about 50 ° C for 4 hours. The resulting mixture is then allowed to cool. Adjuvants, such as stabilizers (1.69 g of calcium chloride, 0.70 g of sodium nitrate), a thickening agent (2% xanthan gum, 0.67 g), antifreeze (1 60 g of ethylene glycol) are added when the temperature is decreased to about 30 ° C. The pH is adjusted by adding a pH adjusting agent (3638% hydrochloric acid) to a pH in the range of 6 to 9. Examples 2 to 13 and Comparative Examples The procedure of Example 1 was repeated with different solvent systems for clomazone including inedible oils, as shown in Table 1 below. For comparison, the procedure of Example 1 was repeated using various edible oils as a solvent, especially corn oil, soybean oil and sunflower oil, again as indicated in US Pat. Table 1 below. Volatility studies Laboratory tests to determine the volatility of clomazone formulated in a capsule suspension (CS) formulation were performed as follows. Sufficient un-sterilized topsoil to conduct the test was passed twice through a 14-mesh screen to remove large particles and debris. The fine particles are then removed through a 30 mesh screen, leaving a topsoil containing in intermediate size particles. This mid-sized topsoil, 240 grams, is spread evenly about one to two millimeters thick over an area of about 27.9 cm x 41.3 cm in a 32.4 cm x 45.7 cm plateau. x 1.9 cm. The topsoil is then sprayed from a calibrated hanging sprayer to deliver 20 gallons of water per acre. The spray mixture consists of a sufficient amount of test clomazone formulation to provide 0.0712 g of active ingredient in 20 ml of water. In this way, the test clomazone formulation is applied to the soil at a rate of 1.0 kg of active ingredient / ha. Immediately after treatment, the soil is enclosed in a glass jar where it remains briefly until use. For each test clomazone formulation, four 22 mm x 300 mm glass chromatography columns, each containing a coarse sintered glass barrier at the bottom, are connected through their lower end to a collector. multi-port air that delivers equal air pressure simultaneously a number of columns. In each of the four columns are placed 59 g of the topsoil treated, which fills about 200 mm of the length of the column. Then, a polyurethane foam plug is placed above each column, the polyurethane foam plug being designed to fit the inner portion of a tube having a diameter of 21 mm to 26 mm. As soon as possible after the soil treatment and installation of the columns, a low airflow (0.75 to 1.00 liters per minute per column) from the multi-port air manifold is passed through the soil in each column, which causes the volatilized clomazone to be collected on the polyurethane foam stopper. The time between the soil treatment and the beginning of the air flow is about one hour. The air flow is continued for about 18 hours. After the 18 hour collection period, the polyurethane foam plug of each column is placed in a 20 ml plastic syringe. The polyurethane foam cap is extracted perfectly by drawing 15 ml of methanol into the syringe and through the stopper, forcing the methanol extract into a beaker and repeating the process several times. An aliquot of 0.04 ml of the 15 ml sample is diluted with 0.96 ml of methanol and 1.0 ml of water. An aliquot of 0.1 ml of this solution is analyzed for clomazone content using an enzyme immunoassay method (ELISA), a method reported by R. V. Darger et al. (J. Agr and Food Chem., 1991, 39, 813-819). The total clomazone content, expressed in microgram (iug), of the foam plug of each sample is recorded. The results are shown in Table 1 below. Example Solvent Amount of clomazone collected (pg) Comparative Examples A Corn oil 20 B Soy 23 C Sunflower 21 Vegetable oil 1 Castor oil 19 2 Neem oil 20 Essential oil 3 Lemongrass oil 23 4 Pyrethrum oil 20 Geranium 19 6 Sesame oil 21 7 Tea tree oil 24 8 Clove oil 20 9 Cottonseed oil 23 Ginger oil 22 Mineral oil 11 Exsol® D140 23 12 White oil 20 Fatty acid esters 13 Isooctyl palmitate 22 Table 1 As shown As shown in Table 1, the formulations of the present invention exhibit lower or same clomazone volatility than comparative formulations using a solvent system comprising an edible oil. Efficacy Studies The biological efficacy of the products of Examples 1 to 13 was compared to the clomazone content of the comparative formulation B sample, i.e., clomazone in an oil solvent system. of soy, following the following procedure.
    [0020] Echinochloa, giant foxtail, green foxtail, sorghum and velvetleaf seeds are planted in a 25 cm x 15 cm x 7.5 cm fiber dish containing topsoil. Each species is planted on a single row in the dish, which contains five rows. Four replicate dishes of the aforementioned weed species are used for each application rate of the tested formulation. Stock solutions of each of the formulations to be tested are prepared by dispersing a sufficient amount of formulation to obtain 0.0356 grams of active ingredient in 40 ml of water. From the stock solution, 20 ml are taken and diluted in series with 20 ml of water to obtain application rates of 0.5 g, 0.25 g, 0.125 g, 0.0625 g and 0.0313 g. g of active ingredient / ha. The formulation solutions to be tested for each application rate are then sprayed onto the soil surface using a slide sprayer and a cover. The dishes are also sprayed as above with the same levels of comparative formulation B (clomazone with soybean oil). At the end of the spraying, the dishes are placed in a greenhouse where they are kept for fourteen days. After this period, the test is visually assessed to determine the percentage of weed control. The percent weed control data for each test formulation compared to clomazone in a soybean oil formulation was subjected to regression analysis to determine the rate of application that would provide 85% weed control. (DE85) of each of the weed species. From these data, the relative potency of the tested formulation (the comparative potency of the comparative clomazone in soybean oil, Formulation B, being 1.0) is determined using the following ratio: Puiss de la Puissaz Format The effectiveness of both the formulation of Example 1 and comparative formulation B above with respect to echinochloa is determined as follows.
    [0021] The results of the field study of the effects of Formulation B and Example 1 on echinochloa control are shown in Table 2 below. Application rate of clomazone Percentage control of echinochloa (g / ha) Formulation B Example 1 0.0313 70 80 0.0625 75 90 0.125 91 95 0.25 98 97 0.5 100 100 Table 2 The rate of The application of clomazone necessary to achieve 85% echinochloa control (DE85) is determined from the data in Table 2. The potency of each formulation is determined to be the reciprocal of the rate of application. The results are shown in Table 3 below. Application rate to achieve a control rate Power (ha / g) of 85% (g / ha) Formulation 0.107 1 / 0.107 = 9.3458 B Example 1 0.042 1 / 0.042 = 23.80 Table 3 The relative power of the formulation of Example 1 is calculated as follows: Relative power of Example 1 = 23.80 / 9.3458 = 2.5 A relative power greater than 1 indicates a power that is greater than that of the comparative formulation B. The results are shown in Table 4 below. Relative potency of the formulation Example Echinochloa Foxtail Foxtail Sorghum Giant Green Velvetleaf 1 2,5 3 2,7 2,5 3 2 3,1 2,9 2,9 3,0 3 3 1,9 2,3 2 1,8 2 4 3 2,6 2,8 3 3,5 2,9 2,5 3 3,2 2,7 6 3,9 4 3,5 4,2 3,1 7 2,8 2,7 3.1 3 3.2 8 3.2 3.5 3.2 3 3.3 9 3 2.9 2.7 3 3 1.9 1.7 1.9 2.1 2 11 2.8 2.7 3 2 , 7 3.1 12 3.2 2.9 3 3.2 3 13 2.9 3 2.7 3.1 2.8 Formulation B 1 1 1 1 1 (clomazone in soybean oil) Table 4 A From the data presented in Table 4 above, it can be seen that the formulations of the examples of the present invention have a significantly improved herbicidal activity compared to that of the B formulation. Of course, the invention is not limited to the embodiments described above and shown, from which we can provide other modes and other embodiments, without departing from the scope of the invention.
    权利要求:
    Claims (6)
    [0001]
    CLAIMS1 / - A herbicidal composition comprising an aqueous suspension of microcapsules, the microcapsules having a capsule wall composed of a porous polymeric condensate, wherein the microcapsules contain a solution of clomazone in a solvent system comprising one or more inedible oils.
    [0002]
    2 / - The composition of claim 1, wherein the clomazone is present in the composition in an amount of at least 20% by weight.
    [0003]
    3 / - The composition of claim 2, wherein the clomazone is present in the composition in an amount of at least 50% by weight.
    [0004]
    4. The composition according to any of the preceding claims, wherein the solvent system consists essentially of one or more inedible oils.
    [0005]
    5 / - Composition according to any one of the preceding claims, wherein the solvent system comprises a vegetable oil.
    [0006]
    6 / - The composition of claim 5, wherein the vegetable oil is selected from the fruit oil of the cork tree of Love, burdock oil (Bur oil), oil of bancoul (Kukui nut oil), carrot seed oil (pressed), castor oil, chaulmoogra oil, jojoba oil, neem oil, seed oil roseberry fruit, sea buckthorn oil, snowball seed oil (Viburnum oil), Tamanu or Foraha oil, tonka bean oil, and mixtures thereof. 7. The composition of claim 6, wherein the vegetable oil is castor oil or neem oil. 8 / - Composition according to any one of the preceding claims, wherein the solvent system comprises an essential oil. 9 / - The composition of claim 8, wherein the essential oil is selected from sesame oil, pyrethrum, lipids derived from glycerol or glycerol fatty acid derivatives, cinnamon oil, dechedron oil, clove oil, geranium oil, lemongrass oil, angelica oil, peppermint oil, turmeric oil, wintergreen oil, rosemary oil, fennel oil, cardamom oil, caraway oil (caraway oil), chamomile oil, coriander oil, guaiac oil, oil of cumin, dill oil, parsley oil, basil oil, camphor oil, ylang-ylang oil, lemongrass oil, eucalyptus oil, fennel oil, ginger oil, bitter with Pakistan incense fat (coconut oil), perilla oil, cedar oil, jasmine oil, coconut oil pink Sofia herb (palmarosa sofia), western peppermint oil, olive oil nis (star anise essence), tuberose oil, neroli oil, tolu incense, patchouli oil, herb oil, Japanese four-dish Chamaecyparis obtuse), Hiba oil, red sandalwood oil, orange leaf oil, laurel oil, vetiver oil, bergamot oil, incense of Peruvian fat, rosewood oil (rosewood oil), grapefruit oil, lemon oil, orange oil, orange oil, olive oil oregano, lavender oil, obtusiloba oil (Lindera oil), pine needle oil, pepper oil, rose oil, orange oil, l tangerine oil, tea tree oil, tea oil, thyme oil, thymol oil, garlic oil, onion oil, aloe oil, Japanese peppermint oil, spearmint oil, and mixtures thereof. 10 / - The composition of claim 9, wherein the essential oil is selected from pyrethrum oil, lemongrass oil and sesame oil. 11. The composition according to any one of the preceding claims, wherein the solvent system comprises a mineral oil. 12 / - The composition of claim 11, wherein the mineral oil is selected from open chain C14 to C30 hydrocarbon mixtures, closed chain hydrocarbons (naphthenes) and aromatic hydrocarbons. The composition of claim 12, wherein the mixture has a nonaromatic content of less than 8% by weight. A composition according to any one of the preceding claims, wherein the solvent system comprises a sodium ester. 'fatty acid. 15 / - The composition of claim 14, wherein the fatty acid ester is selected from C10 to C20 fatty acid esters. 16. The composition according to claim 15, wherein the fatty acid ester is chosen from myristates, palmitates, oleates and stearates, and cocoates. 17. The composition as claimed in claim 16, in which the fatty acid ester is chosen from cetyl alcohol, stearyl alcohol, squalane, isopropyl myristate, isopropyl palmitate and palmitate. isooctyl, cetyl palmitate, glyceryl cocoate, glyceryl stearate, glyceryl isostearate, decyl oleate, caprylic / capric acid triglyceride, glyceryl oleate, ethylhexyl palmitate, ethylhexyl stearate and decyl cocoate. 18. The composition of claim 17, wherein the fatty acid ester is isooctyl palmitate. 19 / - Composition according to any one of the preceding claims, wherein the microcapsules further contain one or more surfactants, stabilizers or a mixture thereof. 20. The composition as claimed in any one of the preceding claims, in which the weight ratio of clomazone to inedible oil is 1/12 to 12/1. 21 / - The composition of claim 20, wherein the clomazone weight ratio on inedible oil is 1/10 to 10/1. 22. The composition according to claim 21, wherein the weight ratio of clomazone to inedible oil is from 1: 7.5 to 7.5: 1. 23 / - Composition according to any one of the preceding claims, wherein the liquid phase within the microcapsules contains at least 20% by weight of clomazone.24 / - The composition of claim 23, wherein the liquid phase within the microcapsules contains at least 30% by weight of clomazone. 25. The composition according to claim 24, wherein the liquid phase within the microcapsules contains at least 50% by weight of clomazone. 26. The composition according to any one of the preceding claims, wherein the clomazone is present in the encapsulated liquid phase in an amount of from 1% to 95% by weight. 27. The composition of claim 26, wherein the clomazone is present in the encapsulated liquid phase in an amount of 5% to 90% by weight. 28. The composition according to any one of the preceding claims, wherein the inedible oil is present in the liquid within the microcapsules in an amount of at least 5% by weight. 29 / - The composition of claim 28, wherein the inedible oil is present in the liquid within the microcapsules in an amount of at least 10% by weight. 30. The composition as claimed in any one of the preceding claims, wherein the walls of the microcapsules are formed from a porous polymeric condensate composed of one or more substances chosen from a polyurea, a polyamide or a copolymer of amide-urea. 31. The composition of claim 30, wherein the walls of the microcapsules are formed from a polyurea formed by the interfacial polymerization of an isocyanate and, optionally, an ACD crosslinking agent. 32. The composition according to claim 31, wherein the isocyanate is chosen from alpha, alpha, alpha, alphatetramethylxylylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), a derivative of HDI, diisocyanate of isophorone (IPDI), polymethylenepolyphenyl isocyanates (PMPPI), methylene diphenyl isocyanate (MDI), polyaryl polyisocyanate (PAPI) and toluene diisocyanate (TDI). 33 / - The composition of claim 31 or 32, wherein the ACD crosslinking agent is selected from tetrakis (methyloxymethyl) glycolurile or an alkylated glycolurile resin. 34. Composition according to any one of the preceding claims, in which the microcapsules have a particle size in the range of 0.5 micron to 60 microns. The composition of claim 34, wherein the microcapsules have a particle size in the range of 1 micron to 50 microns. 36. The composition of claim 35, wherein the microcapsules have a particle size in the range of 1 micron to 30 microns. A composition according to any one of the preceding claims, wherein the polymer is present in the microcapsules in an amount of 2% to 25% by weight of the microcapsules. 38. The composition according to claim 37, wherein the polymer is present in the microcapsules in an amount of 5% to 15% by weight. 39. Composition according to any one of the preceding claims, in which the aqueous phase comprises one or more surfactants, stabilizing agents, viscosity modifiers or protective colloids. 40. The composition according to any one of the preceding claims, wherein the aqueous phase comprises from 15% to 50% by weight of the formulation. 41 / - Herbicidal composition comprising microcapsules, the microcapsules having a capsule wall composed of a porous polymeric condensate, wherein the microcapsules contain clomazone and a solvent comprising an inedible oil.42 / - Process for the preparation of a herbicidal composition, the process comprising the steps of: obtaining a water immiscible phase comprising clomazone, an isocyanate and optionally an ACD crosslinking agent, dissolved in a solvent system comprising an inedible oil; obtaining an aqueous phase comprising one or more surfactants; combining the water immiscible phase and the aqueous phase to form a dispersion of the water immiscible phase in the aqueous phase; forming in this manner polyurea microcapsules containing droplets of the water immiscible phase; and curing the microcapsules. The method of claim 42, further comprising drying the resulting composition to remove the aqueous phase. 44 / - Use of a composition according to any one of claims 1 to 41, in the fight against the growth of a plant. 45 / - A method of controlling the growth of a plant at a locus, the method comprising applying to the locus a composition according to any one of claims 1 to 41.
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    同族专利:
    公开号 | 公开日
    TWI687160B|2020-03-11|
    GB2509431B|2016-09-14|
    US20170079272A1|2017-03-23|
    US10499639B2|2019-12-10|
    EP3122183A4|2017-09-13|
    GB201405446D0|2014-05-07|
    RU2016141861A|2018-04-26|
    WO2015143979A1|2015-10-01|
    CN106061251A|2016-10-26|
    TW201545652A|2015-12-16|
    EP3122183A1|2017-02-01|
    FR3018998B1|2018-11-16|
    RU2657457C2|2018-06-14|
    RU2016141861A3|2018-04-26|
    GB2509431A|2014-07-02|
    UA118282C2|2018-12-26|
    CN106061251B|2020-06-02|
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    优先权:
    申请号 | 申请日 | 专利标题
    GB1405446.4A|GB2509431B|2014-03-26|2014-03-26|Herbicidal composition, a method for its preparation and the use thereof|
    GBGB1405446.4|2014-03-26|
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