Aqueous capsule suspension concentrate containing herbicide safener and pesticide active ingredients

Abstract

This invention relates to an aqueous capsule suspension concentrate based on 2-[(2,4-dichlorophenyl)methyl]-4,4'-dimethyl-3-isoxazolidinone and pyrazolium bromide, its preparation, mixtures thereof with suspension concentrates of other active substances, and its use as an agricultural chemical agent.

Description

[0001] This invention relates to an aqueous capsule suspension concentrate based on 2-[(2,4-dichlorophenyl)methyl]-4,4'-dimethyl-3-isoxazolidinone and mefenpyr-diethyl, its preparation, mixtures thereof with suspension concentrates of other active ingredients, and its use as an agricultural chemical agent.

[0002] Active ingredients can be formulated in many different ways, and the characteristics of the active ingredient and the properties of the formulation may present problems regarding the manufacturability, stability, usability, and efficacy of the formulation. Furthermore, certain formulations are more advantageous than others for economic and environmental reasons.

[0003] Herbicide safeners are difficult to formulate due to their low and wide melting range and amorphous structure. Commercially available products consist of organic dispersions, emulsion concentrates, and suspensions, where the low-melting-point active ingredient is in dissolved or emulsified form. An advantage is the rapid bioavailability of dissolved safeners. A disadvantage is that these formulations cannot be mixed with aqueous formulations. Also a disadvantage is the very rapid bioavailability of the safener, and in some cases, its absorption in plants too early, resulting in reduced protective efficacy if the active ingredient is absorbed subsequently. The closest prior art describes a new variant in WO 2017 / 144497 A1. Here, the safener is added to water in liquid form, crystallizes, and is used as a suspension concentrate (SC). The advantage of this SC is its miscibility with other suspension concentrates. The disadvantage is its miscibility with the low-melting-point active ingredient in suspension concentrates, which leads to formulation agglomeration. Another disadvantage of dissolved formulations is the lower initial bioavailability, as the particles in the concentrate must first dissolve before being absorbed into the plant.

[0004] Herbicide safeners (such as pyrazole-methyl or cloquintocet-mexyl) often exist in the form of esterified acids, which can be used as solidified melts with a melting range in industrial-grade quality. They rapidly agglomerate with the low-melting-point active ingredients in the finished formulation.

[0005] For certain active ingredients, safeners are needed to prevent damage to crops. A new active ingredient on the market is 2-[(2,4-dichlorophenyl)methyl]-4,4'-dimethyl-3-isoxazolidinone (CAS No. 81777-95-9 or IUPAC 2-(2,4-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, hereinafter abbreviated as DCPMI). It is the chemical representative of clonazolone (hereinafter abbreviated as CPMI, CAS 81777-89-1, IUPAC 2-(2-chlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one). Compared to isoxaflutole, DCPMI has significantly lower water solubility (39.5 ppm instead of 1000 ppm) and a slightly lower vapor pressure (0.88 mPa compared to 19.2 mPa), and therefore the calculated Henry's constant (distribution of the active ingredient through the aqueous vapor phase) is at a similar level. Both active ingredients belong to the category of volatile active ingredients that can cause undesirable damage to neighboring crops. The low vapor pressure may also be associated with an undesirable broad distribution, which should be avoided for human and environmental toxicology reasons, as well as for economic reasons.

[0006] DCPMI is used in herbicidal compositions and mixtures or as a selective grass herbicide, as described, for example, in WO-A 2015 / 127259 or WO-A 2012 / 148689. The closest prior art can be considered to be WO 2018 / 024839 A1.

[0007] Therefore, the object of the present invention is to provide suitable encapsulation of low-melting-point active ingredients that reduces volatility by at least 70% (relative to unencapsulated active ingredients) while simultaneously achieving optimal release and action of the safety agent and ensuring storage stability of formulations combined with other active ingredients.

[0008] Therefore, there is a need for novel formulations comprising an aqueous dispersion of a low-melting-point herbicide safener with a melting temperature range, wherein the low-melting-point herbicide safener with a melting temperature range can be mixed with the active ingredient, preferably a low-melting-point active ingredient, without forming aggregates, and the safener has high, targeted bioavailability.

[0009] In addition, there is a need for formulations in which the safety agent has been encapsulated separately without the active ingredient to ensure the stability of the formulation combined with the low-melting-point active ingredient.

[0010] Therefore, one object of the present invention is to provide an aqueous formulation containing a safe agent that does not form unwanted aggregates.

[0011] Therefore, one object of the present invention is to provide a formulation containing a safener and other active ingredients (z), wherein the formulation is free of unwanted agglomerates and combines the high efficacy of the safener, preferably with active ingredient b also present in the capsule.

[0012] It has been found, surprisingly, that although capsules are sustained-release formulations known to those skilled in the art, in the formulations of the present invention, the safety agent (s) still has a good effect despite encapsulation.

[0013] In the context of this invention, suitable active ingredients z) and b) are all active agrochemical herbicides that are soluble in water-insoluble organic solvents.

[0014] Preferred active ingredients b) with a melting temperature range of 50°C to 85°C include:

[0015] Anilofos, acephate, benfluralin, bifenthrin, bupirimate, butralin, chloroacetic acid, cyfluthrin, cynmethylin, cypermethrin, demeton-S-methylsulfone, dimethametryn, dimethoate, dioxabenzofos, diphenylamine, dithiopyr, dodemorph Acetate), esfenvalerate, etalfluralin, ethofumesate, fenazaquin, finitropan, fenoxycarb, fenuron-TCA, fenvalerate, fluoroglycofen-ethyl, flupyradifuron, flurazole, flurochloridone, fluroxypyr-meptyl, flusilazole, furalaxyl, haloxyfop-etotyl, haloxyfop-methyl, imazalil, ioxynil octanoate, isoprothiolane, metalaxyl, methomyl, methomyl, monocrotophos, nitrapyrin, nitrothal-isopropyl, penconazole, pendimethalin, permethrin, propamocarb hydrochloridehydrochloride, propaquizafop, pyrazophos, quizalofop-P-tefuryl, resmethrin, trichloroacetic acid, tetramethrin, thiofanox, triflumizole, pyridaphenthion, 2-phenylphenol, dimethylvinphos, β-cypermethrin, famur, clodinafop-propargyl, triazamate, tebufenpyrad, pyrimidifen, aldrin, bromophos, dialifos, pyriminobac-methyl, benzoylprop, ethyl benzoylprop Benzoylprop-ethyl, binapacryl, camphechlor, chlorfenethol, chlorfenprop, chlorfenprop-methyl, chlorphoxim, crufomate, cyometrinil, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane, dimetilan, dinobuton, fenson, fenthiaprop, fenthiaprop-ethyl, fluenetil, glyodine, 2-isovalerylindane-1,3-dione, methoxyphenone, 2-methoxyethylmercuryThe following herbicides are mentioned: chloride, nitrofen, indanofan, acequinocyl, ipsdienol and (S)-cis-verbenol, fenoxanil, piraclostrobin, trifloxystrobin, cyflufenamid, gamma-cyhalothrin, proquinazid, 2,6-diisopropylnaphthalene, isothiazine, and 2-[(2,4-dichlorophenyl)methyl]-4,4'-dimethyl-3-isooxazolidinone.

[0016] Particularly preferred is b) 2-[(2,4-dichlorophenyl)methyl]-4,4'-dimethyl-3-isoxazolidinone (CAS No. 81777-95-9 or IUPAC 2-(2,4-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, hereinafter abbreviated as DCPMI).

[0017] DCPMI-based formulations are described in WO 2018 / 024839 and WO 2015127259.

[0018] The formulation may optionally contain other unencapsulated active ingredients (z).

[0019] Another object of the present invention is to incorporate the safety agent into the formulation in the following manner:

[0020] - It will not mix with other active ingredients to form any aggregates.

[0021] -Active ingredient b) or z), preferably DCPMI, has consistently high activity.

[0022] - The volatility of active ingredient b) or z) did not increase.

[0023] - The safety agent remains effective and is highly effective.

[0024] This objective is achieved through the capsule suspension concentrate (CS) of the present invention, which can be further formulated with other active ingredients to obtain ZC formulations. ZC formulations are mixtures of CS and suspension concentrate (SC).

[0025] Therefore, the present invention provides a capsule suspension concentrate containing...

[0026] A) Particulate dispersion (capsules), which contains

[0027] a) The reaction product of at least one compound a1) having an isocyanate reactive group and an isocyanate mixture a2),

[0028] b) Optional active ingredient b),

[0029] s) safety agent s), soluble in an organic, water-insoluble solvent L),

[0030] c) Optionally one or more additives, and

[0031] B)d) Liquid aqueous phase,

[0032] The median particle size of the dispersed phase A is 1 to 50 μm.

[0033] In a preferred embodiment, the CS of the present invention comprises at least one active ingredient b) of A).

[0034] In a preferred embodiment, the CS of the present invention comprises at least one or more of additives c) of A).

[0035] More preferably, the CS of the present invention comprises at least one protective colloid c1).

[0036] Particle size was determined according to CIPAC (Collaborative International Pesticides Analytical Council; www.cipac.org) method MT 187 as d50 or D90 = active ingredient particle size (50% or 90% laser scattering of all volumetric particles). Median particle size refers to the d50 value.

[0037] The median particle size d50 of the dispersed phase A is typically 1 to 50 μm, preferably 1 to 20 μm, and most preferably 3 to 15 μm.

[0038] This invention also provides a method for preparing the capsule suspension concentrate of this invention, characterized in that, in

[0039] In step (1), the safer s) dissolved in the organic water-insoluble solvent L) is mixed with the isocyanate mixture a2) and optionally with the organic solvent and / or emulsifier, and then the solution thus prepared is...

[0040] In step (2), emulsification is performed in water, which optionally contains a protective colloid (c1), optionally mixed with other additives (d), and the resulting emulsion E is then subjected to…

[0041] In step (3), it is mixed with isocyanate reactive groups a1), and then optionally, other additives d) are added.

[0042] In a preferred embodiment, in step 1, the active ingredient b, which is dissolved in an organic water-insoluble solvent L), is further added.

[0043] In step 2, it is even more preferable to use a protective colloid (c1).

[0044] Unless otherwise stated, the quantities described below refer to the total amounts of A) and B).

[0045] In another embodiment of the method of the present invention, in step 3 of the method of the present invention, the emulsion E obtained in step 2 may first be mixed with at least one diamine, polyamine, diol, polyol and / or amino alcohol (a1) while stirring. The amine or alcohol component (a1) is preferably added in an aqueous solution. Optionally, additive (c) is added after the reaction causing capsule formation is completed. It is preferred to use an amine as component (a1) in the method of the present invention.

[0046] To prepare the CS of this invention, any conventional equipment used for such purposes, which generates strong shear forces, can be used. Examples include rotor-stator mixers and jet dispersers.

[0047] In the implementation of the method of the present invention, the ratio of NCO groups from component a2) to NCO-reactive groups from component a1) can vary within a specific range. Typically, 0.8 to 1.5 equivalents of amine or alcohol component are used per 1 mol of isocyanate. Preferably, the amounts of isocyanate and amine or alcohol are selected such that there are equimolar amounts of isocyanate groups and amino or hydroxyl groups.

[0048] In the implementation of the method of the present invention, the reaction temperature can be varied within a specific range.

[0049] The first stage (1) of the method of the present invention is generally carried out at a temperature of -10°C to 80°C, preferably 0°C to 50°C, more preferably 2°C to 40°C, and most preferably 2°C to 30°C; the second stage (2) is generally carried out at a temperature of -10°C to +80°C, preferably 0°C to 80°C; and in the third stage (3), the temperature is generally 0°C to 80°C, preferably 10°C to 75°C.

[0050] The method of the present invention is preferably carried out under atmospheric pressure.

[0051] The capsules of the capsule suspension concentrate of the present invention have a wall thickness of 0.001 to 4 μm, preferably 0.01 to 2 μm, and most preferably 0.01 to 1 μm (calculated wall thickness).

[0052] In the reactions a1) and a2), the sum of the number-average functionality X of the isocyanate groups and the isocyanate reactive groups is 2≤X≤6, preferably 2≤X≤4.5, more preferably 2.0≤X≤3.5 and most preferably 2.2≤X≤2.8.

[0053] The "average functionality X" characteristic of the method of this invention is explained below. In this document, the compound with higher functionality is key, and the result of subtracting 2 from the compound with lower functionality is added to the compound with higher functionality. For example, if the (average) functionality of a1) is 2.1, and the (average) functionality of a2) is 2.6: 2.1 - 2 = 0.1. This difference is added to 2.6: 2.6 + 0.1 = 2.7. Therefore, the average functionality is 2.7. Or, if a1) is 2.7 and a2) is 2.3, then the average functionality is found to be 2.7 + 2.3 - 2 = 3.0.

[0054] The capsule suspension concentrates of the present invention have many advantages. For example, they are able to release the active ingredient in the amount required in each case over a long period of time. It is also advantageous that the plant compatibility of the active ingredient is improved, and volatility and therefore damage to neighboring crops are reduced. Furthermore, the acute toxicity of the active ingredient is reduced, so the use of microencapsulated formulations is without problems for operators and in terms of potential phototoxic reactions.

[0055] Useful compounds with isocyanate reactive groups (a1) include aliphatic, aromatic, cyclic, and alicyclic primary and secondary diamines, as well as polyamines. Examples include ethylenediamine (1,2), diethylenetriamine, monoisopropylamine, 4-aminopyridine (4-AP), n-propylamine, polyaziridine based on ethylene or propyleneimine, triethylenetetramine (TETA), tetraethylenepentamine, 2,4,4'-triaminodiphenyl ether, bis(hexamethylene)triamine, ethylenediamine (EDA), trimethylenedipiperidine (TMDP), guanidine carbonate (GUCA), phenylenediamine, toluenediamine, pentamethylenehexamine, 2,4-diamino-6-methyl-1,3,5-triazine, 1,2-diaminocyclohexane, 4,4'-diaminodiphenyl ether ... triaminodiphenyl ether, ethylenediamine (EDA), ethylenediamine (EDA), ethylenediphenyl ether, ethylenediphenyl ether, ethylenediamine (EDA), ethylenediamine (EDA), ethylenediphenyl ether, ethylenediphenyl ether, ethylenediamine (EDA), ethylenediamine (EDA), ethylenediphenyl ether, ethylenediphenyl ether, ethylenediamine (EDA), ethylenediamine (EDA), ethylenediphenyl ether, ethylenediphenyl ether, ethylenediphenyl ether, ethylenediphenyl ether, ethylenediphenyl ether, ethylenediphenyl ether, ethylenediphenyl ether, ethylenediphenyl ether, ethylenediphenyl ether, ethylenediphenyl ether Phenylmethane, 1,5-diaminonaphthylisophorone diamine, diaminopropane, diaminobutane, piperazine, aminoethylpiperazine (AEP), poly(propylene glycol) bis(2-aminopropyl ether) or o,o'-bis(2-aminopropyl)polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol, hexamethylenediamine, bis(3-aminopropyl)amine, bis(2-methylaminoethyl)methylamine, 1,4-diaminocyclohexane, 3-amino-1-methylaminopropane, N-methylbis(3-aminopropyl)amine, 1,4-diamino-n-butane, and 1,6-diamino-n-hexane. Hexamethylenediamine and diethylenetriamine are preferred.

[0056] Useful compounds with isocyanate reactive groups (a1) also include primary and secondary, aliphatic and aromatic diols and polyols. Examples include: ethylene glycol, propylene glycol (1,2), propylene glycol (1,3), butanediol (1,4), pentanediol (1,5), hexanediol (1,6), glycerol, and diethylene glycol. Glycerol and propane-1,2-diol are preferred.

[0057] Compounds a1) having isocyanate reactive groups also include amino alcohols. Examples include triethanolamine, monoethanolamine, triisopropanolamine, diisopropylamine, N-methylethanolamine, and N-methyldiethanolamine.

[0058] In a very particularly preferred embodiment, an amine is used as the isocyanate reactive component (a1).

[0059] The isocyanate mixture a2) is a reaction product of a mixture of monoisocyanates, diisocyanates, and / or polyisocyanates, or a mixture of isocyanates. Suitable compounds a2) are, for example, butylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4-trimethylhexamethylene diisocyanate and / or 2,4,4-trimethylhexamethylene diisocyanate, isomerized bis(4,4'-isocyanate-cyclohexyl)methane (H12-MDI) and mixtures thereof with any isomer content, cyclohexene 1,4-diisocyanate, 4-isocyanate-methyloctane 1,8-diisocyanate (nonane triisocyanate), phenylene 1,4-diisocyanate, and toluene-2,4-diisocyanate. Esters and / or toluene 2,6-diisocyanate (TDI), naphthylene 1,5-diisocyanate, diphenylmethane 2,2'-diisocyanate and / or diphenylmethane 2,4'-diisocyanate and / or diphenylmethane 4,4'-diisocyanate (MDI), 1,3-bis(2-isocyanate prop-2-yl)benzene and / or 1,4-bis(2-isocyanate prop-2-yl)benzene (TMXDI), 1,3-bis(isocyanate methyl)benzene (XDI), alkyl esters of 2,6-diisocyanate hexanoate (lysine diisocyanate) having 1 to 8 carbon atoms, and mixtures thereof. Compounds containing modifiers such as urea esters, uretdiones, urethanes, isocyanurates, biurets, iminooxadiazine diones, or oxadiazine triones, and based on the structure of said diisocyanate, are also suitable units of component a2), and are also polycyclic compounds, such as polymeric MDI (pMDI, e.g., PAPI-27 purchased from Dow or Covestro AG). 44V20 products) and combinations thereof.

[0060] Modifiers with an isocyanate (NCO) functionality of 2 to 6 are preferred, more preferably 2.0 to 4.5, more preferably 2.3 to 4.2, and most preferably 2.3 to 3.8. Modifiers with an NCO functionality of 2.4 to 2.8 are particularly preferred.

[0061] Modification is preferably performed using diisocyanates selected from HDI, IPDI, H12-MDI, TDI, and MDI. TDI and MDI, and their derivatives, are particularly preferred. A particularly preferred MDI is polymeric MDI, such as PAPI-27 used in blends with TDI. The preferred NCO content of the isocyanate or polyisocyanate or blend is 3% to 50% by weight, more preferably 10% to 40% by weight, more preferably 15% to 35% by weight, and most preferably 18% to 30% by weight. The isocyanate groups may also be present in a partially or completely capped form before reacting with the isocyanate reactive groups, preventing them from reacting immediately. This ensures that the reaction does not occur until a specific temperature (capping temperature) is reached. Typical capping agents are found in the prior art, and their selection ensures that they are eliminated from the isocyanate groups again at a temperature of 60°C to 220°C, and only thereafter react with the isocyanate reactive groups. End-capping agents are incorporated into polyurethane, and also those that remain in the polyurethane as solvents or plasticizers, or those that are released from the polyurethane as gases. The term "end-capped NCO value" is sometimes used. When used in this invention, "NCO value" always refers to the uncapped NCO value. Typical end-capping levels are up to <0.5%. Examples of typical end-capping agents are caprolactam, methyl ethyl ketoxime, pyrazoles (e.g., 3,5-dimethyl-1,2-pyrazole or 1,-pyrazole), triazoles (e.g., 1,2,4-triazole), diisopropylamine, diethyl malonate, diethylamine, phenol and its derivatives, and imidazoles.

[0062] Component a2) may also be used in the form of a mixture of the above compounds or in the form of a prepolymer. In this case, for example, a compound containing isocyanate groups and having an NCO content of 3% to 50% by weight reacts with a compound containing isocyanate reactive groups and having an OH value of 10 mg KOH / g to 150 mg KOH / g.

[0063] A mixture of polymeric (p)MDI and TDI is particularly preferred. The ratio of pMDI to toluene diisocyanate in this document may vary within a specific range, but 0.2% to 2% by weight of pMDI and 0.2% to 2% by weight of TDI are preferred.

[0064] The aqueous phase B) of the capsule suspension concentrate of the present invention may contain other additives c) in addition to water, such as emulsifiers, protective colloids, preservatives, defoamers, cold stabilizers, thickeners, pH stabilizers, and neutralizers. Preferred components c) are emulsifiers, thickeners, and protective colloids c1).

[0065] Useful organic solvents (L) include all conventional organic solvents that, on the one hand, are poorly miscible with water, but on the other hand, dissolve the active agricultural chemicals used, which have good solubility. Preferred examples include aliphatic and aromatic, optionally halogenated hydrocarbons, such as toluene, xylene, etc. 100, 100ND, 150, 150ND or 200, 200ND (mineral oil), tetrachloromethane, chloroform, dichloromethane and dichloroethane; and esters, such as ethyl acetate; and alkane carboxamides, such as N,N-dimethyloctylamide and N,N-dimethyldecylamide. In addition, there are vegetable oils and modified oils (e.g., modified by methylation, ethylation and hydrogenation and hydration), based on, for example, rapeseed oil, corn kernel oil, coconut oil, etc. Mineral oil is particularly preferred, and solvents based on dialkylnaphthalene (e.g., diisopropylnaphthalene) and mixtures of 1-methylnaphthalene and 2-methylnaphthalene and naphthalene (e.g.) are very particularly preferred. 200ND product, CAS No.: 64742-94-5.

[0066] Useful emulsifiers (c) include standard surfactants present in formulations of active agrochemical ingredients. Examples include ethoxylated nonylphenol, polyethylene glycol ethers of straight-chain alcohols, reaction products of alkylphenols with ethylene oxide and / or propylene oxide, and fatty acid esters, alkyl sulfonates, alkyl sulfates, and aryl sulfates.

[0067] Useful protective colloids (c1) (dispersants) include all substances commonly used for this purpose. Preferred examples include natural and synthetic water-soluble polymers such as gelatin, starch, and cellulose derivatives, particularly cellulose esters and cellulose ethers, such as methylcellulose, as well as polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, lignin sulfonates (e.g., NA, 88 or 25S), modified naphthalene sulfonate (e.g., Morwet D-425), polyvinylpyrrolidone, and polyacrylamide. Polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, and lignin sulfonate are particularly preferred. Polyvinyl alcohol and lignin sulfonate are very, very preferred. Lignosulfonate is very, very preferred.

[0068] Useful thickeners (c) include organic and inorganic thickeners. Useful organic thickeners include organically natural, biotechnologically modified, or organically synthesized thickeners. Typical synthetic thickeners are... (Croda) or or The Elementis series. These are typically based on acrylates. Typical organic thickeners are based on xanthan gum or cellulose (e.g., hydroxyethyl cellulose or carboxymethyl cellulose) or combinations thereof. Other typical representatives are based on cellulose or lignin. Naturally modified thickeners based on xanthan gum are preferred. Typical examples include... (Solvay) and (Kelco Corp.) and (Cargill). Silica and palygorskite are also preferred.

[0069] Useful preservatives (c) include all substances typically present in crop protection compositions for this purpose. Examples include... SPX (Thor) and GXL (Lonza).

[0070] Useful defoamers (c) include all substances commonly used for this purpose in crop protection compositions. Preferred are silane derivatives, such as polydimethylsiloxane and magnesium stearate. Typical products are those used... 484 (Solvay, Silioxane Emulsion) and SAG 1571 (Momentive).

[0071] Substance c) used as a cold stabilizer can be any substance that is commonly used for this purpose in crop protection compositions. Examples include urea, glycerol, and propylene glycol.

[0072] Useful neutralizing agents (c) include common acids and bases. Examples include phosphoric acid, citric acid, sodium hydroxide solution, and ammonia solution.

[0073] In this invention, in formulas such as (I), unless otherwise stated, the optionally substituted groups may be monosubstituted or polysubstituted, wherein in the case of polysubstituted groups, the substituents may be the same or different. Furthermore, even if only one structure or trade name is given, meso and tautomer forms known to those skilled in the art are included without issue.

[0074] Furthermore, within the scope of preference described in this invention, it should be understood that different preference levels can be combined with each other in an arrangement, and in any case, the same preference level, especially the most preferred embodiment / preferred level, should be combined with each other in each case and indeed disclosed in such a combination.

[0075] Compositions consisting only of the necessary components (not optional components) as described above should also be considered as disclosed.

[0076] Percentages—unless otherwise stated—should be understood as weight percentages, where the weight % of the composition typically totals 100, or is made up to 100% with the appropriate solvent / dispersant.

[0077] The composition of the capsule suspension concentrate of the present invention can vary within a specific range. The proportion of the dispersed phase A) relative to the whole formulation is typically 10% to 90% by weight, preferably 30% to 70% by weight, and more preferably 40% to 60% by weight.

[0078] a) The proportion of reaction products a1+a2 is typically 0.1 wt% to 8 wt%, preferably 0.2 wt% to 4.5 wt%, more preferably 0.3 wt% to 2.5 wt%; the proportion of active agricultural chemical components b) is typically 1 wt% to 50 wt%, preferably 5 wt% to 40 wt%, more preferably 10 wt% to 20 wt%; the proportion of organic solvent L) is typically 1 wt% to 90 wt%, preferably 10 wt% to 60 wt%, more preferably 20 wt% to 40 wt%; the proportion of protective colloid c1) is typically 0.1 wt% to 5 wt%, preferably 0.2 wt% to 3 wt%, more preferably 0.3 wt% to 1.5 wt%; and the proportion of additive c) is typically 0.1 wt% to 15 wt%, preferably 0.3 wt% to 10 wt%, and more preferably 0.4 wt% to 3 wt%.

[0079] Preferably, the ratio of the active agricultural chemical component b) to the isocyanate mixture a2) is 7:1 to 40:1, more preferably 8:1 to 20:1, and even more preferably 9:1 to 18:1.

[0080] If an amino-functional compound is used as component a1), the preferred ratio of the amino isocyanate reactive group a1) to the isocyanate mixture a2) is 0 to 1.

[0081] In a preferred embodiment, the capsule suspension concentrate (CS) of the present invention is mixed with one or more suspension concentrates (SC) to obtain the ZC formulation.

[0082] The present invention also provides a ZC formulation comprising the CS formulation of the present invention and at least one suspension concentrate (SC) comprising the following components:

[0083] -One or more preferred herbicidal active ingredients (z),

[0084] - at least one or more thickeners (c),

[0085] - One or more anionic emulsifiers (e1), and / or

[0086] -One or more nonionic emulsifiers e2).

[0087] The preferred active ingredient (z) is an active fungicide, insecticide, and herbicide. Preferably, known active ingredients based on the inhibition of substances such as acetyllactate synthase, acetyl-CoA carboxylase, cellulase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, or protoporphyrinogen oxidase can be used, as described, for example, in Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 17th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2017, and the references cited therein. The examples described below are known herbicides that can be combined with the compounds of the present invention. These active ingredients are identified by their common names in English variants according to the International Organization for Standardization (ISO) or by their chemical names or code numbers. Even if not explicitly mentioned, they always include all forms of use, such as acids, salts, esters, and all isomers, such as stereoisomers and optical isomers.

[0088] Typical active ingredients (z) are selected from a list containing the following substances: acetochlor, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicabazone, acetamide, amidosulfuron, and aminopyridinic acid. (yclopyrachlor), aminocyclopyrachlor-potassium, aminocyclopyrachlor-methyl, aminopyralid, amitrol, ammonium sulfamate, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benzolin Herbicides including benzolin-ethyl, benzsulfuron, benzsulfuron-methyl, benzulide, bentazone, benzobicyclon, benzofenap, bicyclopyron, bifenox, bilanafos, bilanafos-sodium, bispyribac, and bispyribac. Sodium bispyribac, bromacil, bromobutide, bromofenoxim, bromoxynil, bromoxynil-butyrate, bromoxynil-potassium, bromoxynil-heptanoate, bromoxynil-octanoate, busoxinone, butachlor, and butafenacil.Butamifos, butenachlor, butroxydim, butylate, cefenstrole, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chlorbromuron, chlorfenac, chlorfenac-sodium, oat ester, chlorflurenol ), chlorflurenol-methyl, chloridazon, chlorimuron-ethyl, chlorophthalim, chlorotoluron, chlorthal-dimethyl, chlorsulfuron, 3-[5-chloro-4-(trifluoromethyl)pyridin-2-yl]-4-hydroxy-1-methylimidazolidine-2-one, cinidon, cinidon-ethyl ), cinmethylin, cinosulfuron, clacyfos, clethodim, clodinafop, clodinafop, isoxaflutole, comeprop, clopyralid, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cycloate, cyclopyranil, Cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D, 2,4-D-butotyl, 2,4-D-butyl, 2,4-D-dimethylammonium, 2,4-D-diolamin, 2,4-D-ethyl2,4-D-2-ethylhexyl ester, 2,4-D-isobutyl ester, 2,4-D-isooctyl ester, 2,4-D-isopropylammonium, 2,4-D-potassium, 2,4-D-triisopropanolammonium and 2,4-D-triethanolamine, 2,4-DB, 2,4-DB-butyl ester, 2,4-DB-dimethylammonium, 2,4-DB-isooctyl ester, 2,4-DB-potassium and 2,4-DB-sodium, daimuron (dymron), dalapon, dazomet, n-decanol, desmedipham, detosyl-pyrazolate (D TP), dicamba, dichlobenil, 2-(2,4-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, 2-(2,5-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, difenzoquat, pyrfluthrin Diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron, dimepiperate, dimethachlor, dimethenamid, dimethenamid-P, dimetrasulfuron, dinitramine, dinoterb, diphenamid, diquat Diquat dibromid, flusulfuron, diuron, DNOC, endothal, EPTC, esprocarb, ethametsulfuron, ethametsulfuron-methyl, ethiozin, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanid, F-9600,F-5231 (i.e., N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]phenyl]ethanesulfonamide), F-7967 (i.e., 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)pyrimidin-2,4(1H,3H)-dione), fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenq uinotrione, fentrazamide, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, florpyrauxifen, fluazifop, fluazifop-P, fluazifop-butyl butyl), fluazifop-P-butyl, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac-pentyl, f... Lumioxazin, fluometuron, flurenol, flurenol-butyl, flurenol-dimethylammonium, flurenol-methyl, fluoroglycofen, fluoroglycofen-ethyl, flupropanate, flupyrsulfuron, and flupyrsulfuron-methyl-sodium.Fluridone, fluroxypyr, fluroxypyr, isooctyl clopyralid, flurtamone, fluthiacet, fluthiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, fosamine, glufosinate Glufosinate-P-sodium, glyphosate, glyphosate ammonium, glyphosate isopropylammonium, glyphosate diammonium, glyphosate dimethylammonium, glyphosate potassium, glyphosate sodium, and glyphosate trimesium, H-9201 (i.e., O-(2,4-dimethyl-6-nitrophenyl)O-ethyl isopropyl thiophosphoramide ester) isopropylphosphoramidothioate), halauxifen, halauxifen-methyl, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop ethoxyethyl, haloxyfop ethoxyethyl, haloxyfop-P-methyl, hexazinone, HW-02 (i.e., (2,4-dichlorophenoxy)acetic acid 1-(dimethoxyphosphoryl)ethyl ester), 4-hydroxy-1-methoxy-5-methyl- 3-[4-(trifluoromethyl)pyridin-2-yl]imidazolidine-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)pyridin-2-yl]imidazolidine-2-one, imidacloprid, imidacloprid-methyl, methoxyimidacloprid, methoxyimidacloprid ammonium, imidacloprid nicotinic acid, imidacloprid ammonium, imidacloprid nicotinic acid, imidacloprid isopropyl ammonium, imidazoquinic acid, imidazoquinic acid ammonium, imazethapyr, imazethapyr-immonium, imazosulfuron, indaziflam, triazine indaziflumIodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxynil-octanoate, potassium and sodium iooxynil, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, karbutilate, KUH-0 43 (i.e., 3-({[5-(difluoromethyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-5,5-dimethyl-4,5-dihydro-1,2-oxazole), ketospiradox, lactoferrin, lenacil, linuron, MCPA, MCPA-butoxyethyl ester, MCPA-dimethylammonium, MCPA-2-ethylhexyl ester, MCPA-isopropylammonium, MCPA-potassium and MCPA-sodium, MCPB, MCPB-methyl ester, MCPB-ethyl ester and MCPB-sodium, 2-methyl-4-chloropropionic acid (mecoprop), sodium 2-methyl-4-chloropropionate and 2-methyl-4-chloropropionate butoxyethyl ester (mecoprop-butotyl), purified 2-methyl-4-chloropropionic acid (mecoprop-P), purified 2-methyl-4-chloropropionate butoxyethyl ester, purified 2-methyl-4-chloropropionate dimethylammonium, purified 2-methyl-4-chloropropionate-2-ethylhexyl ester and purified 2-methyl-4-chloropropionate potassium, mefenacet, mefluidide, mesosulfuron, and so on. Mesosulfuron-methyl, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methylbenzthiazuron, methiopyrsulfuron, methiozolin, methyl isothiocyanate, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron.Metsulfuron-methyl, molinat, monolinuron, monosulfuron, monosulfuron-ester, MT-5950 (N-[3-chloro-4-(1-methylethyl)-phenyl]-2-methylpentanamide), NGGC-011, napropamide, NC-310 (4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole), neburon, nicosulfuron, nonanoic acid (pelargonic acid) (acid), norflurazon, oleic acid (fatty acid), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefon, lancotrione, oxyfluorfen, paraquat, paraquat dichloride, pebulate, penoxsulam, pentachlorphenol, penoxazone, pethoxamid, petroleum Oils), phenmedipham, picloram, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, oxadiazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron.Propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole, pyrazolynate (pyrazolate), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz z-isopropyl, pyribambenz-propyl, pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac-sodium, pyroxasulfone, pyroxul am), quinclorac, quinmerac, quinoclamine, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, sulfadiazine ( sulcotrion, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, SYN-523, SYP-249 (i.e., 1-ethoxy-3-methyl-1-oxobut-3-en-2-yl5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate), SYP-300 (i.e., 1-[7-fluoro-3-oxo-4-(prop-2-yn-1-yl)-3,4-dihydro-2H-1,4-benzoxazin-6-yl]-3-propyl-2-thionimidazolidine-4,5-dione),2,3,6-TBA, TCA (trifluoroacetic acid), sodium trifluoroacetate (TCA-sodium), tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumeton, terbuthylazin, terbutryn, thenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiafenacil, tolpyralate, toramezone, trimethylbenzene Tralkoxydim, triafamone, triallate, triasulfuron, triaziflam, tribenuron-methyl, trilopyr, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazin, trifluralin, triflusulfuron-methyl, tritosulfuron, urea sulfate, vernolate, ZJ-0862 (i.e., 3,4-dichloro-N-{2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl}aniline).

[0089] The active ingredient (z) is preferably selected from the list of substances including:

[0090] Phosphate, acephate, ethylbutyric acid, bifenthrin, ethirimol sulfonate, sec-butylpyrethrin, chloroacetic acid, cypermethrin, cypermethrin, sulfadiazine, isoamyl, dimethoate, phosmet, diphenylamine, flufenoxuron, phosmet acetate, cis-cypermethrin, ethylbutyric acid, ethoxysulfuron, quinclorac, seed dressing ester, phenoxycarb, trifluralin, cypermethrin, ethoxysulfuron, flupyradifuron, chlorpyrifos, fluroxypyr, chlorpyrifos Flupyroxypyr isooctyl ester, flusilazole, furazolidone, flupyroxypyr haloxyfop-R-methyl, flupyroxypyr, imazalil, iodobenzoyl octanoate, isoprothiolane, metalaxyl, methomyl, cypermethrin, chlorpyrifos, trichloromethylpyridine, isoprothiolane, tebuconazole, pendimethalin, permethrin, cymoxanil hydrochloride, oxadiazine, difenoconazole, quizalofop-P-ethyl, cypermethrin, trichloroacetic acid, methamidophos, chlorpyrifos, flufenoxuron, pyridaben, 2-phenylphenol, methyl parathion, β-cypermethrin, chlorpyrifos, clodinafop-propargyl, clodinafop-propargyl Azoxystrobin, pyrimethanil, pyrimethanil, aldrin, bromoxynil, chlorpyrifos, pyrimethanil, methyl methoxynil, ethyl methoxynil, chlorfenapyr, chlorfenprop-methyl, chlorfenapyr oxime, chlorfenapyr, chlorfenapyr, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane, difenoconazole, chlorfenapyr, fenthiaprop, fenthiaprop-methyl Fenthiazine, fenthiaprop-ethyl, fenfluridine, isochoridone, methoxybenzone, methoxyethoxychloromercurate, chlorfenapyr, indicarb, fenfluridine, bark beetle diene alcohol and (S)-cis-verbenol, cyhalothrin, azoxystrobin, oxadiazon, cycloflufenoxam, γ-trifluorocypermethrin, propoxyquin, 2,6-diisopropylnaphthalene, isothiazine and 2-[(2,4-dichlorophenyl)methyl]-4,4'-dimethyl-3-isooxazolidinone.

[0091] In an alternative preferred embodiment, the active ingredient z) is a herbicide selected from the list of substances including:

[0092] Betahistine, chlorpyrifos, pyrazosulfuron, carboxymethyl chlorpyrifos, bromobenzonitrile, butyroyl bromoxynil, potassium heptaate and potassium octanoate, butachlor, cinmethlylin, isoxaflutole, dichloropyridine, and also including common forms of 2,4-D (2,4-D-butoxyethyl ester, 2,4-D-butyl ester, 2,4-D-dimethylammonium, 2,4-D-diethanolamine), 2,4-D-ethyl ester, 2,4-D-2-ethylhexyl ester, 2,4-D-isobutyl ester, 2,4-D-isooctyl ester, etc. 2,4-D-isopropyl ester, 2,4-D-isopropylammonium, 2,4-D-sodium, 2,4-D-triisopropanolammonium, 2,4-D-triethanolamine, pyrfluthrin, metolachlor, fenfluridine, ethoxysulfuron, quizalofop-p-ethyl, fenquinotrione, tetrazolium-methyl, diflubenzuron, fluthiamethoxam, clopyralid, clopyralid isooctyl ester, formyl... Ammonium sulfate, fluchloropyridinium chloride, iodosulfuron, iodosulfuron sodium, isoxaflutole, and also common forms of MCPA (4-chloro-2-methylphenoxy)acetic acid (MCPA-butoxyethyl ester, MCPA-dimethylammonium, MCPA-isooctyl ester, MCPA-sodium, MCPA-potassium, MCPA-2-ethylhexyl ester), benzylsulfuron, mesosulfuron-methyl, mesosulfuron-methyl, pyrazosulfuron, metolachlor, S-metolachlor, sulfadiazine, and methamidophos. Ketone, napropamid, nicosulfuron, propyzoxystrobin, oxadiazon, pendimethalin, clethodim, ampicillin, propensulfuron-methyl, propyzamid, bensulfuron-methyl, sulfosulfuron-methyl, sulfosulfuron-methyl, methoxysulfuron-methyl, chlorpyrifos, furazolidone, cyclosulfuron, thiencarbazone, thiencarbazone-methyl, fluoxetine, DCPMI, and triallate.

[0093] The active herbicidal ingredients are particularly preferred. More preferably, z) is selected from:

[0094] Fluthiamethoxam, bensulfuron-methyl, pendimethalin, pyrfluthrin, bensulfuron-methyl, methamidophos, sulfonylpyrazol, propanilsulfuron-methyl, oxazolidinyl, bromobenzonitrile (and its esterified variants), fluchloropyridine, 2,4-D, MCPA.

[0095] The highly preferred active herbicidal ingredients are fluthiamethoxam, sulfonylpyrazosulfuron, pyrfluthrin, bensulfuron-methyl, and cypermethrin.

[0096] A mixture of one or more active herbicidal ingredients (z) selected from the following substances is particularly preferred:

[0097] Fluthiamethoxam and clethodim; Fluthiamethoxam and bensulfuron; Fluthiamethoxam and metribuzin; Fluthiamethoxam and flupyridine ester; Benzoylbutazone and pyrfluthrin; Benzoylbutazone and bensulfuron; Benzoylbutazone and metribuzin; Benzoylbutazone and fluthiamethoxam; Pendimethalin and pyrfluthrin; Pendimethalin and bensulfuron; Pendimethalin and metribuzin; Pendimethalin and flupyridine ester; Metribuzin and pyrfluthrin; Flupyridine ester and pyrfluthrin; Fluthiamethoxam and pyrfluthrin; Metribuzin and bensulfuron; Flupyridine ester And bensulfuron; sulfonylpyrazole and pyrflufenican; bensulfuron and pyrflufenican; sulfonylpyrazole and bensulfuron; sulfonylpyrazole and dilflufenican; sulfonylpyrazole and dilflufenican; sulfonylpyrazole and dilflufenican; dilflufenican and dilflufenican; dilflufenican and dilflufenican; dilflufenican and dilflufenican, bensulfuron, dilflufenican, bensulfuron and dilflufenican, dilflufenican and dilflufenican, cyclohexane and DCPMI.

[0098] Most preferably, the mixture is selected from: fluthiamethoxam and pyrfluthiamethoxam; fluthiamethoxam and sulfonylpyrazol; bensulfuron and pyrfluthiamethoxam; metribuzin and pyrfluthiamethoxam; fluthiamethoxam and bensulfuron; fluthiamethoxam and metribuzin; fluthiamethoxam and sulfonylpyrazol and pyrfluthiamethoxam; bensulfuron and pyrfluthiamethoxam and fluthiamethoxam; metribuzin and pyrfluthiamethoxam and fluthiamethoxam, cyclohexane and DCPMI.

[0099] DCPMI, pyrfluthrin, and fluthiamethoxam are preferred as active ingredients, with DCPMI being the most preferred.

[0100] In addition, a mixture of the above-mentioned active ingredients can be used, preferably a mixture of DCPMI, more preferably a mixture of DCPMI and pyrifluquinazon, a mixture of DCPMI and fluthiamethoxam, and a mixture of pyrifluquinazon and fluthiamethoxam.

[0101] The component s) used is preferably a compound (safety agent) from the following group:

[0102] s1) Compounds derived from heterocyclic carboxylic acid derivatives:

[0103] s1 a Compounds of the dichlorophenylpyrazoline-3-carboxylic acid class (S1) aPreferred compounds include, for example, 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid, ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid (S1-1) (“pyrazoline”), and related compounds, as described in WO-A-91 / 07874;

[0104] s1 b )Derivatives of dichlorophenylpyrazole carboxylic acid (S1) b Preferred compounds include, for example, ethyl 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S1-2), ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (S1-3), ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (S1-4), and related compounds, as described in EP-A-333131 and EP-A-269 806;

[0105] s1 c )1,5-Diphenylpyrazole-3-carboxylic acid derivatives (S1 c Preferred compounds include, for example, ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-5), methyl 1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-6), and related compounds, such as those described in EP-A-268554.

[0106] s1 d Triazole carboxylic acid compounds (S1) d Preferred compounds include, for example, fenchlorazole (ethyl ester), namely ethyl 1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylate (S1-7), and related compounds, such as those described in EP-A-174 562 and EP-A-346 620;

[0107] s1 e Compounds of the class 5-benzyl-2-isooxazoline-3-carboxylic acid, 5-phenyl-2-isooxazoline-3-carboxylic acid, or 5,5-diphenyl-2-isooxazoline-3-carboxylic acid (S1) ePreferred compounds include, for example, ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (S1-8) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (S1-9) and related compounds, as described in WO-A-91 / 08202, or 5,5-diphenyl-2-isoxazolinecarboxylic acid (S1-10) or ethyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (S1-11) (“isoxadifen-ethyl”) or n-propyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (S1-12) or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (S1-13), as described in patent application WO-A-95 / 07897.

[0108] s2) Compounds derived from 8-quinolinoxy derivatives (S2):

[0109] s2 a )8-quinolinoxyacetic acid compounds (S2) a Preferred are (5-chloro-8-quinolinoxy)acetic acid 1-methylhexyl ester (“detoxifying quinone”) (S2-1), (5-chloro-8-quinolinoxy)acetic acid 1,3-dimethylbut-1-yl ester (S2-2), (5-chloro-8-quinolinoxy)acetic acid 4-allyloxybutyl ester (S2-3), (5-chloro-8-quinolinoxy)acetic acid 1-allyloxypropyl-2-yl ester (S2-4), (5-chloro-8-quinolinoxy)acetic acid 1-allyloxypropyl-2-yl ester (S2-4), (5-chloro-8-quinolinoxy)acetic acid 1-methylhexyl ester (S2-5), (5-chloro-8-quinolinoxy)acetic acid 1-methylhexyl ester (S2-1), (5-chloro-8-quinolinoxy)acetic acid 1-methylhexyl ester (S2-2), (5-chloro-8-quinolinoxy)acetic acid 1-methylhexyl ester (S2-3 ...methylhexyl ester (S2-4), (5-chloro-8-quinolinoxy)acetic acid 1-methylhexyl ester (S2-5), (5-chloro-8-quinolinoxy)acetic acid 1 Ethyl acetate (S2-5), methyl (5-chloro-8-quinolinoxy)acetate (S2-6), allyl (5-chloro-8-quinolinoxy)acetate (S2-7), 2-(2-propyliminooxy)-1-ethyl (5-chloro-8-quinolinoxy)acetate (S2-8), 2-oxopropyl-1-yl (5-chloro-8-quinolinoxy)acetate (S2-9), and related compounds such as EP-A-86 As described in 750, EP-A-94 349 and EP-A-191 736 or EP-A-0 492 366, and (5-chloro-8-quinolinoxy)acetic acid (S2-10), its hydrate and its salts, such as its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as described in WO-A-2002 / 34048;

[0110] s2 b (5-Chloro-8-quinolinoxy)malonic acid compounds (S2) b Preferred compounds include, for example, diethyl (5-chloro-8-quinolinoxy)malonate, diallyl (5-chloro-8-quinolinoxy)malonate, methyl ethyl (5-chloro-8-quinolinoxy)malonate, and related compounds, as described in EP-A-0 582 198.

[0111] S3) Dichloroacetamide compounds (S3) are commonly used as pre-emergence safeners (safeners that act on the soil), for example...

[0112] "Dichloropropyleneamide (N,N-diallyl-2,2-dichloroacetamide) (S3-1)"

[0113] Purchased from Stauffer, “R-29148” (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) (S3-2).

[0114] Purchased from Stauffer, “R-28725” (3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine) (S3-3).

[0115] "benoxacor" (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4)

[0116] "PPG-1292" (N-allyl-N-[(1,3-dioxolane-2-yl)methyl]dichloroacetamide) (S3-5) purchased from PPG Industries.

[0117] Purchased from Sagro-Chem, "DKA-24" (N-allyl-N-[(allylaminocarbonyl)methyl]dichloroacetamide) (S3-6).

[0118] Purchased from Nitrokemia or Monsanto, “AD-67” or “MON 4660” (3-dichloroacetyl-1-oxa-3-azaspiro[4.5]decane) (S3-7).

[0119] "TI-35" (1-dichloroacetylazheptanane) (S3-8) purchased from TRI-Chemical RT

[0120] Purchased from BASF "diclonon" (dicyclonon) or "BAS145138" or "LAB145138" ((RS)-1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[1,2-a]pyrimidin-6-one) (S3-9).

[0121] "furilazole" or "MON 13900" ((RS)-3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyloxazolidine (S3-10), and its (R) isomer (S3-11).

[0122] s4) Compounds derived from acylsulfonamides (S4):

[0123] s4 a ) formula (S4 a N-acylsulfonamides and their salts, as described in WO-A-97 / 45016,

[0124]

[0125] in

[0126] R A 1 Representing (C1-C6)-alkyl and (C3-C6)-cycloalkyl, wherein the latter two groups are v A The substituents are selected from the following: halogen, (C1-C4)-alkoxy, (C1-C6)-haloalkoxy and (C1-C4)-alkylthio, and in the case of cyclic groups, are further substituted by (C1-C4)-alkyl and (C1-C4)-haloalkyl.

[0127] R A 2 Represents halogens, (C1-C4)-alkyl groups, (C1-C4)-alkoxy groups, and CF3.

[0128] m A Represents 1 or 2;

[0129] v A Represents 0, 1, 2, or 3;

[0130] s4 b ) formula (S4 b Compounds of the 4-(benzoylaminosulfonyl)benzamide class and their salts, as described in WO-A-99 / 16744,

[0131]

[0132] in

[0133] R B 1 R B 2 Each of these groups independently represents hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C3-C6)-alkenyl, and (C3-C6)-ynyl.

[0134] R B 3 Represents halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, or (C1-C4)-alkoxy, and

[0135] m B Represents 1 or 2.

[0136] For example, those compounds, in which

[0137] R B 1 =Cyclopropyl, R B 2 = Hydrogen, and (R B 3 ) = 2-OMe("cyprosulfamide", S4-1),

[0138] R B 1 =Cyclopropyl, R B 2 = Hydrogen, and (R B 3 )=5-Cl-2-OMe(S4-2),

[0139] R B 1 =Ethyl, R B 2 = Hydrogen, and (R B 3 ) = 2 - OMe(S4-3),

[0140] R B 1 =Isopropyl, R B 2 = Hydrogen, and (R B 3 )=5-Cl-2-OMe(S4-4), and

[0141] R B 1 =Isopropyl, R B 2 = Hydrogen, and (R B 3 ) = 2 - OMe(S4-5);

[0142] s4 c ) from formula (S4) c ) benzoylaminosulfonylphenylurea compounds, such as those described in EP-A-365484,

[0143]

[0144] in

[0145] R C 1 R C 2Each of these groups independently represents hydrogen, (C1-C8)-alkyl, (C3-C8)-cycloalkyl, (C3-C6)-alkenyl, and (C3-C6)-ynyl.

[0146] R C 3 Representing halogens, (C1-C4)-alkyl groups, (C1-C4)-alkoxy groups, CF3, and

[0147] m C Represents 1 or 2;

[0148] For example

[0149] 1-[4-(N-2-methoxybenzoylaminosulfonyl)phenyl]-3-methylurea,

[0150] 1-[4-(N-2-methoxybenzoylaminosulfonyl)phenyl]-3,3-dimethylurea,

[0151] 1-[4-(N-4,5-dimethylbenzoylaminosulfonyl)phenyl]-3-methylurea;

[0152] s4 d ) formula (S4 d N-phenylsulfonyl terephthalamide compounds and their salts, such as those known from CN101838227,

[0153]

[0154] in

[0155] R D 4 Represents halogens, (C1-C4)-alkyl groups, (C1-C4)-alkoxy groups, and CF3.

[0156] m D Represents 1 or 2;

[0157] R D 5 Represents hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, and (C5-C6)-cycloalkenyl.

[0158] s5) Compounds derived from hydroxy aromatic compounds and aromatic-aliphatic carboxylic acid derivatives, such as ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicylic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid, as described in WO-A-2004 / 084631, WO-A-2005 / 015994, and WO-A-2005 / 016001.

[0159] S6) Active ingredients derived from 1,2-dihydroquinoxaline-2-ones, such as 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxaline-2-one, 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxaline-2-thione, 1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxaline-2-one hydrochloride, 1-(2-methylsulfonylaminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxaline-2-one, as described in WO-A-2005 / 112630.

[0160] s7) Compounds derived from diphenylmethoxyacetic acid derivatives, such as methyl diphenylmethoxyacetate (CAS Registry No. 41858-19-9) (S7-1), ethyl diphenylmethoxyacetate or diphenylmethoxyacetic acid, as described in WO-A-98 / 38856.

[0161] Compounds of formula (S8) or salts thereof, as described in WO-A-98 / 27049,

[0162]

[0163] in

[0164] The symbols and subscripts are defined as follows:

[0165] R D 1 Representing halogens, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, and (C1-C4)-haloalkoxy.

[0166] R D 2 Represents hydrogen or (C1-C4)-alkyl.

[0167] R D 3 Represents hydrogen, (C1-C8)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl or aryl, wherein each of the above carbon-containing groups is unsubstituted or substituted by one or more, preferably up to three identical or different groups selected from halogens and alkoxy groups;

[0168] n D Represents integers from 0 to 2.

[0169] s9) Compounds derived from the 3-(5-tetrazolylcarbonyl)-2-quinolone class, such as 1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Registry No.: 219479-18-2) and 1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Registry No.: 95855-00-8), as described in WO-A-1999 / 000020.

[0170] S10) formula (S10) a ) or (S10 b ) compounds,

[0171] As described in WO-A-2007 / 023719 and WO-A-2007 / 023764,

[0172]

[0173] in

[0174] R E 1 Representing halogens, (C1-C4)-alkyl groups, methoxy groups, nitro groups, cyano groups, CF3, OCF3, and Y. E Z E Each can represent O or S independently.

[0175] n E Represents integers from 0 to 4.

[0176] R E 2 Representative (C1-C) 16 (C2-C6)-alkyl, (C3-C6)-alkenyl, (C3-C6)-cycloalkyl, aryl; benzyl, halobenzyl,

[0177] R E 3 It represents hydrogen or (C1-C6)-alkyl.

[0178] S11) Oxy-imino compounds (S11) are known as seed dressing agents, such as oxabetrinil ((Z)-1,3-dioxolane-2-ylmethoxyimino(phenyl)acetonitrile) (S11-1), which is known as a seed dressing safener for millet / sorghum to resist isopropyl alachlor damage.

[0179] Fluxofenim (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethylone O-(1,3-dioxolane-2-ylmethyl)oxime) (S11-2) is known as a seed safener for millet / sorghum to resist metolachlor damage, and

[0180] "Metolachlor" or "CGA-43089" ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3) is known as a seed treatment safer for millet / sorghum to resist isopropyl acetylene damage.

[0181] S12) Compounds derived from the isothiochromanone class, such as methyl acetate [(3-oxo-1H-2-benzothiaran-4(3H)-ylidene)methoxy]acetate (CAS Registry No.: 205121-04-6) (S12-1) and related compounds in WO-A-1998 / 13361.

[0182] s13) One or more compounds from group (S13):

[0183] "Naphthalenedicarboxylic anhydride" (1,8-naphthalenedicarboxylic anhydride) (S13-1) is known as a seed-treating safener for corn to resist damage from thiocarbamate herbicides.

[0184] Fenclorim (4,6-dichloro-2-phenylpyrimidine) (S13-2) is known as a safener for propachlor in sown rice.

[0185] "Metolachlor" (2-chloro-4-trifluoromethyl-1,3-thiazolyl-5-carboxylate benzyl ester) (S13-3) is known as a seed treatment safener for millet / sorghum to resist damage from metolachlor and isopropylate.

[0186] "CL 304415" (CAS Registry No. 31541-57-8) (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4) from American Cyanamid is known as a safener for maize to resist imidazolinone damage. "MG 191" (CAS Registry No. 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia is known as a safener for maize.

[0187] Purchased from Nitrokemia "MG 838" (CAS Registry No. 133993-74-5) (1-oxa-4-azaspiro[4.5]decane-4-dithiocarboxylic acid 2-propenyl ester) (S13-6),

[0188] "Disulfoton" (S-2-ethylthioethyl dithiophosphate O,O-diethyl ester) (S13-7)

[0189] "Diettholate" (O-phenyl thiophosphate O,O-diethyl ester) (S13-8)

[0190] “mephenate” (4-chlorophenyl methylcarbamate) (S13-9).

[0191] s14) Compounds that, in addition to their herbicidal effect on harmful plants, also act as safeners for crops such as rice, for example...

[0192] "Piperazan" or "MY-93" (1-phenylethylpiperidine-1-thiocarboxylic acid S-1-methyl ester) is known as a safe agent for rice to resist damage from the herbicide molinate.

[0193] "Kelazon" or "SK 23" (1-(1-methyl-1-phenylethyl)-3-p-tolylureuron) is known as a safe agent for rice to resist damage from the herbicide azoxystrobin. "Bensulfuron" = "JC-940" (3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)urea, see JP-A-60087254) is known as a safe agent for rice to resist damage from some herbicides.

[0194] "Methoxybenzone" or "NK 049" (3,3'-dimethyl-4-methoxybenzone) is known as a safe agent for rice to resist damage from some herbicides.

[0195] "CSB" (1-bromo-4-(chloromethylsulfonyl)benzene) (CAS Registry No. 54091-06-4), purchased from Kumiai, is known as a safe agent in rice to resist damage from some herbicides.

[0196] Compounds of formula (S15) or their tautomers

[0197]

[0198] As described in WO-A-2008 / 131861 and WO-A-2008 / 131860,

[0199] in

[0200] R H 1 Represents (C1-C6)-haloalkyl, and

[0201] R H 2 Represents hydrogen or halogen, and

[0202] R H 3 R H4 Each independently represents hydrogen, (C1-C) 16 )-alkyl, (C2-C 16 )-Alkenyl or (C2-C 16 )-Alkyne group,

[0203] The last three groups are each unsubstituted or substituted by one or more groups selected from the following: halogen, hydroxyl, cyano, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylamino, di[(C1-C4)-alkyl]amino, [(C1-C4)-alkoxy]carbonyl, [(C1-C4)-haloalkoxy]carbonyl, unsubstituted or substituted (C3-C6)-cycloalkyl, unsubstituted or substituted phenyl, and unsubstituted or substituted heterocyclic groups.

[0204] (C3-C6)-cycloalkyl, (C4-C6)-cycloalkenyl, or (C3-C6)-cycloalkyl fused to one side of the ring to form a 4- to 6-membered saturated or unsaturated carbon ring, or (C4-C6)-cycloalkenyl fused to one side of the ring to form a 4- to 6-membered saturated or unsaturated carbon ring.

[0205] The last four groups are each unsubstituted or substituted by one or more groups selected from the following: halogen, hydroxyl, cyano, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylamino, di[(C1-C4)-alkyl]amino, [(C1-C4)-alkoxy]carbonyl, [(C1-C4)-haloalkoxy]carbonyl, unsubstituted or substituted (C3-C6)-cycloalkyl, unsubstituted or substituted phenyl, and unsubstituted or substituted heterocyclic groups.

[0206] or

[0207] R H 3 Representing (C1-C4)-alkoxy, (C2-C4)-olefin, (C2-C6)-alkynoxy, or (C2-C4)-haloalkoxy, and

[0208] R H 4 Represents hydrogen or (C1-C4)-alkyl, or

[0209] R H 3 and R H 4Together with the directly attached nitrogen atom, it represents a four- to eight-membered heterocycle, which may contain other cyclic heteroatoms besides the nitrogen atom, preferably up to two other cyclic heteroatoms selected from N, O and S, and the heterocycle is unsubstituted or substituted by one or more groups selected from: halogen, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy and (C1-C4)-alkylthio.

[0210] s16) Compounds that are primarily used as herbicides but also act as safeners for crops, such as

[0211] (2,4-Dichlorophenoxy)acetic acid (2,4-D),

[0212] (4-Chlorophenoxy)acetic acid,

[0213] (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (2-methyl-4-chloropropionic acid),

[0214] 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),

[0215] (4-Chloro-o-tolyloxy)acetic acid (MCPA),

[0216] 4-(4-chloro-o-tolyloxy)butyric acid,

[0217] 4-(4-Chlorophenoxy)butyric acid,

[0218] 3,6-Dichloro-2-methoxybenzoic acid (dicamba),

[0219] 3,6-Dichloro-2-methoxybenzoic acid 1-(ethoxycarbonyl)ethyl ester.

[0220] The highly preferred safer (s) is selected from bis(oxazolyl) acid, cyclopropanesulfonamide, quinalazine, and pyrazosulfuron. Pyrazosulfuron and quinalazine are particularly preferred. Pyrazosulfuron is highly preferred. A cereal safer is highly preferred.

[0221] Suitable anionic dispersants (e.g., emulsifiers, surfactants, wetting agents, and dispersants) are, for example, alkali metal salts, alkaline earth metal salts, or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof, such as alkyl sulfonates or alkyl phosphates and alkyl aryl sulfonates or alkyl aryl phosphates, diphenyl sulfonates, α-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecylbenzene and tridecylbenzene, sulfonates of naphthalene and alkylnaphthalenes, sulfosuccinates, or sulfosuccinamides. Examples of sulfates are sulfates of fatty acids and oils, sulfates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols, or sulfates of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates and carboxylated alcohol ethoxylates or alkylphenol ethoxylates. Also suitable are this group of anionic emulsifiers: alkali metal salts, alkaline earth metal salts, and ammonium salts of polystyrene sulfonic acid; salts of polyvinyl sulfonic acid; salts of alkylnaphthalene sulfonic acid; salts of alkylnaphthalene sulfonic acid-formaldehyde condensation products; and salts of condensation products of naphthalene sulfonic acid, phenol sulfonic acid, and formaldehyde. An example is calcium dodecylbenzenesulfonate, for instance. 70 / B (Solvay), Phenylsulfonat CA100 (Clariant), or isopropylamine dodecylbenzenesulfonate, for example 3300B (Croda).

[0222] Other typical examples include Phenylsulfonat CA (calcium dodecylbenzenesulfonate). Product (optional esterified derivative of thiastyrene-phenylphenol ethoxylate) 3510 (alkylated EO / PO copolymer), EL 400 (ethoxylated castor oil) Product (Fat-acylated dehydrated sorbitol ethoxylate) AR 100 (calcium dodecylbenzenesulfonate). Preferably alkylated aromatic sulfonates (e.g., calcium phenylsulfonate and / or...) AR 100) with alkylated copolymers of ethylene oxide and propylene oxide (e.g. Compositions of 3510). Particularly preferred are dodecylbenzene sulfonates (e.g., AR 100) with alkylated copolymers of ethylene oxide and propylene oxide (e.g. The composition of 3510).

[0223] Examples of other anionic emulsifiers derived from naphthalene sulfonate (e1) are: MT 800 (Sodium dibutylnaphthalenesulfonate) IP (sodium diisopropylnaphthalenesulfonate) and BX (alkyl naphthalene sulfonate). An example of anionic surfactant derived from the condensation of naphthalene sulfonate and formaldehyde is... DT 201 (a hydroxy polymer of naphthalenesulfonic acid with formaldehyde and sodium methylphenol), DT 250 (a condensate of phenol sulfonate and naphthalene sulfonate), C (condensate of phenol sulfonate and naphthalene sulfonate) or D-425 2020. Preferred are 1,2-dibutyl-substituted naphthalene sulfonates or 1,2-diisobutyl-substituted naphthalene sulfonates, for example, products such as... MT 800 (CFPI-Nufarm) and BX (BASF). Other typical surfactants are... 3D33 4D384 BSU CY / 8 (Solvay) and S3474, and The form of product T (Clariant), for example T 100.

[0224] Useful nonionic dispersants (e.g., emulsifiers, wetting agents, surfactants, and dispersants) include standard surfactants present in formulations of active agricultural chemicals. Examples include ethoxylated nonylphenol, reaction products of straight-chain or branched alcohols with ethylene oxide and / or propylene oxide, ethylene oxide-propylene oxide block copolymers, alkoxylated straight-chain and branched saturated and unsaturated alcohols (e.g., butoxylated polyethylene propylene glycol), reaction products of alkylphenols with ethylene oxide and / or propylene oxide, ethylene oxide-propylene oxide block copolymers, polyethylene glycol and polypropylene glycol, as well as fatty acid esters, fatty acid polyethylene glycol ether esters, alkyl sulfonates, alkyl sulfates, aryl sulfates, ethoxylated arylalkylphenols (e.g., tristyrylphenol ethoxylates having an average of 16 ethylene oxide units per molecule), and ethoxylated and propoxylated arylalkylphenols, as well as sulfated or phosphorylated arylalkylphenol ethoxylates or ethoxylates and propoxylates. Tristyrylphenol alkoxylates and fatty acid polyethylene glycol ether esters are particularly preferred. Tristyrylphenol ethoxylate, tristyrylphenol ethoxypropoxylate, and castor oil polyethylene glycol ether ester are particularly preferred, either alone or in combination, in each case. Additives can be additionally useful, such as surfactants or fatty acid esters, which contribute to improved bioavailability. Suitable nonionic emulsifiers (b2) include, for example... 796 / P CO30, HOT PSI 100 or T304.

[0225] Suitable nonionic dispersants (e2) can also be selected from polyvinylpyrrolidone (PVP), polyvinyl alcohol, copolymers of PVP and dimethylaminoethyl methacrylate, butylated PVP, copolymers of vinyl chloride and vinyl acetate, as well as partially hydrolyzed vinyl acetate, phenolic resins, and modified cellulose types, for example... (polyvinylpyrrolidone) (Polyvinyl alcohol) or modified cellulose. Polyvinylpyrrolidone type is preferred, especially low molecular weight type, such as... K30 or K30.

[0226] Other useful nonionic emulsifiers (e2) from diblock and triblock copolymers of alkylene oxides are, for example, compounds based on ethylene oxide and propylene oxide, with an average molar mass of 200 to 10,000, preferably 1,000 to 4,000 g / mol, wherein the mass proportion of polyethoxylated blocks varies between 10% and 80%, for example... PE series (Uniqema) PE series (BASF) 32 or PF series (Clariant).

[0227] For ZC formulations, carrier material f) can be added to SC formulations.

[0228] The carrier material f) is preferably selected from minerals, carbonates, sulfates, and phosphates of alkaline earth metals and earth metals (e.g., calcium carbonate), polymeric carbohydrates, silica, and (natural) framework silicates (e.g., kaolin). Typical examples of suitable fillers c) are, for example... -GA (Green Slope Stone), 300 (perlite) HV (modified starch) chalk (calcium carbonate), Tec 1 (kaolin, hydrated aluminum silicate) OOS (talc, magnesium silicate).

[0229] For f), this paper also prefers natural framework silicates and calcium carbonate products, such as Chalk (calcium carbonate), KaolinTec (Kaolin) and 300 (perlite), with a preference for natural framework silicates, such as 1 (kaolin, hydrated aluminum silicate) and 300 (perlite). Other fillers in the SC formulations of this invention are selected from: minerals, carbonates, sulfates, and phosphates of alkaline earth metals and earth metals (e.g., calcium carbonate), polymeric carbohydrates, framework silicates (e.g., precipitated silica with low absorbency), and natural framework silicates (e.g., kaolin). Typical representatives of suitable fillers c) are, for example... -GA (Green Slope Stone), 300 (perlite) HV (modified starch) chalk (calcium carbonate), Tec 1 (kaolin, hydrated aluminum silicate) OOS (talc, magnesium silicate). Suitable examples are modified natural silicates, such as chemically modified bentonite, lithium montmorillonite, palygorskite, montmorillonite, or other silicate minerals, such as... (Elementis) (Engelhard) (Oil-Dri Corporation) or (AkzoNobel) or Van Gel series (RTVanderbilt).

[0230] Particularly preferred are carrier materials selected from the following: highly absorbent carriers (based on the BET surface area of ​​ISO 9277) that absorb at least 200g of dibutyl phthalate per 100g of carrier material, such as highly absorbent synthetic fumed silica. Type) and pyrogenic silica ( type).

[0231] The capsule suspension concentrates of the present invention are highly adaptable to the application of existing active agricultural chemicals to plants and / or their habitats. They ensure the release of the active components in the appropriate amounts over a relatively long period of time.

[0232] The capsule suspension concentrate of the present invention can be used in practice either on its own or after being pre-diluted with water. It is applied by conventional methods, i.e., by pouring or spraying.

[0233] The application rate of the capsule suspension concentrate of the present invention can vary over a relatively wide range. It is guided by the active agrochemical components discussed and their content in the microcapsule formulation.

[0234] The preferred use of the capsule suspension concentrate of the present invention is as a herbicide in cereals and rapeseed, most preferably in winter barley, and is applied herein by pre-emergence and post-emergence methods. Therefore, it is preferred to use it in the fall shortly after sowing the cereals and shortly before or shortly after the germination of weeds, especially grassy weeds.

[0235] The capsule suspension concentrate of the present invention can be prepared by known methods, for example, as a mixture of individual components, optionally as a mixture with other active ingredients, additives and / or conventional formulation adjuvants, and then applied in a conventional manner by dilution with water, or as a tank mix by co-diluting separately or partially separately formulated individual components with water. It is also possible to apply separately or partially separately formulated individual components at different times (separate application). Individual components or the capsule suspension concentrate of the present invention can also be applied in multiple portions (sequential application), for example by pre-emergence application followed by post-emergence application; or by early post-emergence application followed by mid- or late post-emergence application. Preferably, the active ingredients are applied in combination or immediately and continuously.

[0236] Therefore, the present invention also provides a method for controlling unwanted plants in plant crops, characterized in that the capsule suspension concentrate of the present invention is applied to plants (e.g., harmful plants, such as monocot or dicot weeds or unwanted crop plants) or areas where plants grow.

[0237] Unwanted plants should be understood to mean all plants growing in unwanted locations. These can be, for example, harmful plants (such as monocot or dicot weeds or unwanted crop plants).

[0238] Monocotyledonous weeds from genera such as: *Aegilops*, *Agropyron*, *Agrostis*, *Alopecurus*, *Apera*, *Avena*, *Brachiaria*, *Bromus*, *Cenchrus*, *Commelina*, *Cynodon*, *Cyperus*, *Dactyloctenium*, *Digitaria*, *Echinochloa*, *Eleocharis*, *Eleusine*, and *Eragrostia*. The genera are: *Is*, *Eriochloa*, *Festuca*, *Fimbristylis*, *Heteranthera*, *Imperata*, *Ischaemum*, *Leptochloa*, *Lolium*, *Monochoria*, *Panicum*, *Paspalum*, *Phalaris*, *Phleum*, *Poa*, *Rottboellia*, *Sagittaria*, *Scirpus*, *Setaria*, and *Sorghum*.

[0239] From the following genera of dicotyledonous weeds, such as: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Thistle Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Geranium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Motherwort Genus: Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex x), Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, and Xanthium.

[0240] The capsule suspension concentrate of the present invention is preferably used for the control of grass weeds.

[0241] The present invention also provides the use of the formulations of the invention in vegetable crops, and particularly in potatoes herein.

[0242] The present invention also provides the use of the capsule suspension concentrate of the present invention for the prevention of unwanted plant growth, preferably for use in crops with beneficial plants.

[0243] If the capsule suspension concentrate of the present invention is applied to the soil surface before germination, it completely prevents the emergence of weed seedlings or the growth of weeds until they reach the cotyledon stage, after which they stop growing and eventually die completely after three to four weeks.

[0244] When the capsule suspension concentrate composition of the present invention is applied to the green parts of plants after emergence, growth also stops rapidly within a very short time after treatment, and weeds remain at the growth stage at the time of application, or die completely after a certain period of time, thereby eliminating competition from harmful weeds for crop plants very early and in a lasting manner.

[0245] The capsule suspension concentrate of the present invention is characterized by rapid onset of action and long duration of herbicidal effect. These properties and advantages are beneficial in practical weed control, enabling crops to avoid unwanted competing plants and thus ensuring and / or improving yields in both quality and quantity. Considering these properties, these novel compositions significantly surpass the level of expertise in the art.

[0246] Although the capsule suspension concentrate of the present invention exhibits excellent herbicidal activity against both monocot and dicot weeds, it causes only negligible damage (if any) to economically important crop plants (e.g., dicot crops such as soybean, cotton, rapeseed, sugar beets, or gramineous crops such as wheat, barley, rye, oats, millet / sorghum, rice, or corn). For these reasons, the capsule suspension concentrate of the present invention is ideally suited for the selective control of unwanted plant growth in agriculturally useful or ornamental plants.

[0247] Furthermore, the capsule suspension concentrates of the present invention exhibit excellent growth-regulating properties in crop plants. They intervene in the plant's own metabolism through regulatory action, and thus can be used to controllably influence plant components and promote harvesting, for example, by inducing drying and dwarfing growth. In addition, they are suitable for the general control and suppression of unwanted vegetative growth without killing the plant. The suppression of vegetative growth plays a major role in many monocot and dicot crops because it can reduce or completely prevent lodging.

[0248] The capsule suspension concentrate of the present invention, by virtue of its herbicidal and plant growth-regulating properties, can also be used to control harmful plants in crops of known or undeveloped genetically modified plants. Generally, transgenic plants are characterized by particularly advantageous traits, such as resistance to certain pesticides (especially certain herbicides); resistance to plant diseases or pathogens of plant diseases (e.g., certain insects or microorganisms such as fungi, bacteria, or viruses). Other specific characteristics relate to, for example, the quantity, quality, storability, composition, and specific components of the harvest. For example, there are known transgenic plants with increased starch content or altered starch quality, or those transgenic plants with different fatty acid compositions in their harvests.

[0249] Preferred use of the capsule suspension concentrate of the present invention is in genetically modified crops of economically important useful and ornamental plants, such as gramineous crops like wheat, barley, rye, oats, millet / sorghum, rice, rapeseed, and maize. Preferably, the compositions of the present invention can be used as herbicides in crops of useful plants that are resistant to the phytotoxic effects of herbicides or have been genetically engineered to be resistant. Particularly preferred applications are in wheat, barley, rye, and rapeseed, with winter rapeseed being a preferred choice.

[0250] When the capsule suspension concentrate of the present invention is used in genetically modified crops, it not only produces the effects on harmful plants observed in other crops, but also often has specific effects on application in specific genetically modified crops, such as altered or specifically broadened spectrum of controllable weeds, altered application rates, preferably good compatibility with herbicides to which genetically modified crops are resistant, and influences on the growth and yield of genetically modified crop plants.

[0251] The present invention further provides a method for preventing unwanted plant growth, preferably in plant crops such as cereals (e.g., wheat, barley, rye, oats, rice, corn, millet / sorghum), more preferably in monocotyledonous crops such as cereals (e.g., wheat, barley, rye, oats, their hybrids (e.g., black wheat), rice, corn, and millet / sorghum), wherein one or more capsule suspension concentrates of the present invention are applied to the harmful plant, plant parts, plant seeds, or areas of plant growth (e.g., cultivation areas). Preferably, the capsule suspension concentrates of the present invention are applied via pre-emergence and post-emergence methods. More preferably, the pre-emergence method.

[0252] Therefore, the present invention also provides the use of the capsule suspension concentrate of the present invention for the prevention and control of harmful plants in genetically modified crops.

[0253] The present invention is illustrated by the following examples. Example

[0254] Substances and abbreviations used:

[0255] The terms used in the following embodiments have the following meanings:

[0256] Pyrazosulfuron (RS)-1-(2,4-dichlorophenyl)-5-methyl-2-pyrazoline-3,5-dicarboxylic acid diethyl ester (Bayer AG), melting point range 50-55℃, MPR

[0257] Fluthiamethoxam 4'-fluoro-N-isopropyl-2-(5-trifluoromethyl-1,3,4-thiadiazol-2-yloxy)acetanilide (Bayer AG), FFA

[0258] Pyrfluthrin 2',4'-difluoro-2-(α,α,α-trifluoro-m-tolyloxy)nicotinamide (Bayer AG), DFF

[0259] Syngenta (RS)-1-methylhexyl(5-chloroquinoline-8-yloxy)acetate, melting point range 60-70℃, CQM

[0260] DCPMI 2-[(2,4-dichlorophenyl)methyl]-4,4'-dimethyl-3-isoxazolidinone (CAS No. 81777-95-9 or IUPAC 2-(2,4-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, abbreviated as DCPMI below)

[0261] D-425 Naphthalenesulfonic acid / formaldehyde condensate, sodium salt (Akzo Nobel)

[0262] PE 10500 propylene oxide-ethylene oxide (PO-EO) block polymer (BASF)

[0263] Citric acid polyacid

[0264] G xanthan gum derivative (Solvay)

[0265] 426R, 411 silicone defoamer (Solvay)

[0266] Glycerol antifreeze

[0267] GXL preservative (biocide, Proxel)

[0268] 200ND mineral oil, ExxonMobil, naphthalene-free

[0269] 44V20L polymeric MDI, Covestro AG, functionality 2.7.

[0270] HDA (hexamethylene-1,6-diam), BASF

[0271] Reax 88B is a lignin sulfonate purchased from MeadWestVaco.

[0272] Preparation Examples

[0273] Example 1 (Invention) (CS Formulation) :

[0274] Dissolve 14.23g of DCPMI and 7.14g of pyrazosulfuron-methyl in 21.4g of [a solution / concentrate] at 50°C. In 200ND.

[0275] The solution was added together with 0.36 g of hexamethylenediamine to 1.1 g of water in 53.78 g of water. 44V20L, 1.51g Reax 88B, and 0.2g 426R and 0.18g In a CG / ICP mixture, disperse the mixture at 15000 rpm for 10 minutes using a disperser. Heat the resulting reaction mixture to a maximum temperature of 70°C over one hour and maintain this temperature at 70°C for another 4 hours with gentle stirring. After cooling to room temperature, use 0.1 g of the mixture... G thickening. In this manner, a microcapsule formulation with a content of 150 g / L DCPMI and 75 g / L pyrazosulfuron-methyl and a particle size of 8.3 μm (d90) was obtained.

[0276] The result was a CS formulation with a density of 1.05.

[0277] Example 2 (Invention) (CS Formulation) :

[0278] Dissolve 14.23g of DCPMI and 7.14g of antidote quinine in 21.4g of [a solution / concentrate] at 50°C. In 200ND.

[0279] The solution was added together with 0.36 g of hexamethylenediamine to 1.1 g of water in 53.78 g of water. 44V20L, 1.51g Reax 88B, and 0.2g 426R and 0.18g In a CG / ICP mixture, disperse the mixture at 15000 rpm for 10 minutes using a disperser. Heat the resulting reaction mixture to a maximum temperature of 70°C over one hour and maintain this temperature at 70°C for another 4 hours with gentle stirring. After cooling to room temperature, use 0.1 g of the mixture... G thickening. In this manner, a microcapsule formulation (CS) with a DCPMI content of 150 g / L and an antidote quinolone content of 75 g / L and a particle size of 8.3 μm (d90) was obtained.

[0280] Comparative Example 1 (CS Formulation) :

[0281] Dissolve 14.23g of DCPMI in 21.4g of [a solution] at 50°C. In 200ND.

[0282] The solution was added together with 0.36 g of hexamethylenediamine to 1.1 g of water containing 60.92 g of water. 44V20L, 1.51g Reax 88B, and 0.2g 426R and 0.18g In a CG / ICP mixture, disperse the mixture at 15000 rpm for 10 minutes using a disperser. Heat the resulting reaction mixture to a maximum temperature of 70°C over one hour and maintain this temperature at 70°C for another 4 hours with gentle stirring. After cooling to room temperature, use 0.1 g of the mixture... G thickening. In this way, a microcapsule formulation with a DCPMI content of 150 g / L and a particle size of 8.3 μm (d90) was obtained.

[0283] SC formulations :

[0284] The ZC formulation of the present invention is prepared by preparing an SC formulation which is subsequently used as a mixing agent. These are then blended with the formulation of the present invention to obtain other formulations of the present invention.

[0285] Preparation of SC formulations based on safety agents

[0286] The preparation of SC formulations based on safeners (such as quinalazine or pyrazosulfuron-methyl) is similar to that in BCS 153 070, by adding the safener in its warm form as a melt to the formulation. The mixture is stirred for 2 to 24 hours until crystals form. Then, wet milling is performed, for example, using a bead mill. Finally, an organic thickener is added.

[0287] Preparation of aqueous suspension concentrate :

[0288] To prepare the examples described in Table 1, water was first added at room temperature. Then, the other components (in no particular order) were added with stirring. The mixture was then wet-milled, for example, using a bead mill. Finally, an organic thickener was added.

[0289] Table 1: Prepared Formulations (Figures are expressed as a percentage by weight, % by weight)

[0290]

[0291]

[0292] Prepared ZC formulation (ready-mix formulation)

[0293] The various formulations of the present invention are mixed with other active ingredients. Then water is added to bring the volume up to 1L.

[0294]

[0295]

[0296] The formulation of Comparative Example 3 showed agglomerates and crystal growth in this formulation. In a wet sieve test of the product, 3% of the active ingredient remained on a 150 μm sieve.

[0297] Determining the relative volatility of active ingredients

[0298] In a laboratory fume hood at a constant airflow of 1.6 m / s, 22°C, and 60% relative humidity, a spray solution (0.5 g active ingredient / L) was placed on each of three Teflon membranes in a top-opening glass container. After drying, residues on the Teflon membranes were determined by HPLC at 0 and 72 hours. Volatility was based on the 0-hour value. In other words, a relative volatility of 85% means that 85% of the active ingredient is non-volatile and retained on the Teflon membrane.

[0299] The results in the table above indicate that volatility is not adversely affected by the safener in the capsule, therefore the volatility of DCPMI is controlled at a very high level.

[0300] Greenhouse experiment:

[0301] In the standard implementation of the experiment, seeds of various broadleaf and grassy weed biotypes (of origin) were sown in pots with a diameter of 8-13 cm in natural soil containing standard field soil (loamy silt; non-sterile) and covered with a soil cover layer of about 1 cm. The pots were then cultivated in a greenhouse (12-16 hours light, daytime temperature 20-22°C, nighttime temperature 15-18°C) until application. The pots were treated using a spray containing the mixtures / compositions of the present invention, mixtures of the prior art, or components applied alone, on a laboratory track sprayer. Application of the active ingredient, or a composition formulated as WG, WP, EC, or other active ingredient, was carried out at the appropriate growth stage of the plants. The water volume used for spraying was 100-600 L / ha. After treatment, the plants were returned to the greenhouse.

[0302] Approximately 3 weeks after application, soil effects and / or foliar effects were visually assessed on a scale of 0-100% compared to the untreated control group: 0% = no significant effect compared to the untreated control group; 100% = complete effect compared to the untreated control group.

[0303] (Note: The term "seed" also includes asexual reproduction forms, such as rhizome slices; abbreviations used: h_light = hours of light, g_AS / ha = grams of active substance per hectare, L / ha = liters per hectare, S = susceptible, R = resistant)

[0304] 1. Pre-emergence action on weeds: Seeds of various broadleaf and grassy weed biotypes (of origin) are sown in pots with a diameter of 8-13 cm in natural soil containing standard field soil (loam; non-sterile) and covered with a soil cover layer of approximately 1 cm. The pots are then cultivated in a greenhouse (12-16 hours of light, daytime temperature 20-22°C, nighttime temperature 15-18°C) until application. At the BBCH stage 00-10 of the seeds / plants, the pots are treated with a spray containing the mixtures / compositions of the present invention, or a mixture or individual component in the form of WG, WP, EC, or other formulations, using a laboratory track sprayer. The water volume used for spraying is 100-600 L / ha. After treatment, the plants are returned to the greenhouse and fertilized and watered as needed.

[0305] 2. Post-emergence action on weeds: Seeds of various broadleaf and grassy weed biotypes (of origin) are sown in pots with a diameter of 8-13 cm in natural soil containing standard field soil (loam; non-sterile) and covered with a soil cover layer of approximately 1 cm. The pots are then cultivated in a greenhouse (12-16 hours of light, daytime temperature 20-22°C, nighttime temperature 15-18°C) until application. At different BBCH stages between 11-25 of the seed / plant, typically two to three weeks after the start of cultivation, the pots are treated with a spray containing the mixture / composition of the present invention, a mixture in the form of WG, WP, EC or other formulations, or the components applied alone, on a laboratory track sprayer. The water volume used for spray application is 100-600 L / ha. After treatment, the plants are returned to the greenhouse and fertilized and watered as needed.

[0306] 3. Pre-emergence action on weeds with or without active ingredient incorporation: Seeds of various broadleaf and grass weed biotypes (of origin) were sown in pots 8-13 cm in diameter filled with standard field soil (loam; non-sterile). For comparison, at the BBCH stage 00-10 of the seed / plants, typically two to three weeks after the start of cultivation, the seed-filled pots were treated with a spray containing the mixture / composition of the present invention, or a mixture or individual component in the form of WG, WP, EC, or other formulations, applied on a laboratory track sprayer; or an equal amount of the mixture / composition of the present invention, or a mixture or individual component in the form of WG, WP, EC, or other formulations, was incorporated into a 1 cm cover layer. The water volume used for spraying was 100-600 L / ha. After treatment, the plants were returned to the greenhouse and fertilized and watered as needed. The pots were cultivated in the greenhouse (12-16 hours of light, daytime temperature 20-22°C, nighttime temperature 15-18°C).

[0307] 4. Selective Pre-emergence Treatment: Seeds of various crop species (origin) are sown in pots with a diameter of 8-13 cm in natural soil containing standard field soil (loam; non-sterile) and covered with a soil cover layer of approximately 1 cm. The pots are then cultivated in a greenhouse (12-16 hours of light, daytime temperature 20-22°C, nighttime temperature 15-18°C) until application. At the BBCH stage 00-10 of the seeds / plants, the pots are treated with a spray containing the mixtures / compositions of this invention, or a mixture or individual component in the form of WG, WP, EC, or other formulations, using a laboratory track sprayer. The water volume used for spray application is 100-600 L / ha. After treatment, the plants are returned to the greenhouse and fertilized and watered as needed.

[0308] 5. Selective Post-emergence Treatment: Seeds of various crop species (origin) are sown in natural soil containing standard field soil (loam; non-sterile) and covered with a 1 cm layer of topsoil in pots with a diameter of 8-13 cm. The pots are then cultivated in a greenhouse (12-16 hours light, daytime temperature 20-22°C, nighttime temperature 15-18°C) until application. At different BBCH stages 11-32 of the seed / plant, typically two to four weeks after the start of cultivation, the pots are treated with a spray containing the mixture / composition of the present invention, a mixture in the form of WG, WP, EC or other formulations, or the components applied alone, using a laboratory track sprayer. The water volume used for spray application is 100-600 L / ha. After treatment, the plants are returned to the greenhouse and fertilized and watered as needed. The pots are then cultivated in a greenhouse (12-16 hours light, daytime temperature 20-22°C, nighttime temperature 15-18°C).

[0309] 6. Effects of Pre-Sowing Application on Weeds: Sow seeds of various broadleaf and grassy weed biotypes (of origin) in pots 8-13 cm in diameter filled with standard field soil (loam; non-sterile). Before sowing, treat the seed-filled pots with a spray solution containing the mixture / composition of the present invention, a mixture in the form of WG, WP, EC, or other formulations, or the components applied alone, using a laboratory track sprayer. The water volume for spray application is 100-600 L / ha. After sowing, place the pots in a greenhouse and fertilize and water as needed. Cultivate the pots in the greenhouse (12-16 hours of light, daytime temperature 20-22°C, nighttime temperature 15-18°C).

[0310] 7. Pre-emergence and post-emergence effects on weeds under different cultivation conditions: Seeds of various broadleaf and grass weed biotypes (of origin) were sown in pots with a diameter of 8-13 cm in natural soil containing standard field soil (loam; non-sterile) and covered with a soil cover layer of about 1 cm. The pots were then cultivated in a greenhouse (12-16 hours of light, daytime temperature 20-22°C, nighttime temperature 15-18°C) until application. At different BBCH stages 00-25 of the seeds / plants, the pots were treated with a spray containing the mixtures / compositions of the present invention, in the form of WG, WP, EC or other formulations, or the components applied alone, on a laboratory track sprayer. The water volume used for spray application was 100-600 L / ha. After treatment, the plants were returned to the greenhouse and fertilized and watered as needed. The pots were cultivated in the greenhouse (12-16 hours of light, daytime temperature 20-22°C, nighttime temperature 15-18°C). Irrigation varied depending on the problem. In this study, gradually different amounts of water were provided to each comparison group from above the PWP (permanent wilting point) to the maximum field capacity.

[0311] 8. Pre-emergence and post-emergence effects on weeds under different irrigation conditions: Seeds of various broadleaf and grassy weed biotypes (of origin) were sown in pots with a diameter of 8-13 cm in natural soil containing standard field soil (loam; non-sterile) and covered with a soil cover layer of about 1 cm. The pots were then cultivated in a greenhouse (12-16 hours of light, daytime temperature 20-22°C, nighttime temperature 15-18°C) until application. At different BBCH stages 00-25 of the seeds / plants, the pots were treated with a spray containing the mixtures / compositions of the present invention, or in the form of WG, WP, EC, or other formulations, or the components applied alone, on a laboratory track sprayer. The water volume used for spray application was 100-600 L / ha. After treatment, the plants were returned to the greenhouse and fertilized and watered as needed. The pots were cultivated in the greenhouse (12-16 hours of light, daytime temperature 20-22°C, nighttime temperature 15-18°C). The comparison groups were subjected to different irrigation techniques. Irrigation began either from below or gradually from above (simulating rainfall).

[0312] 9. Pre-emergence and post-emergence effects on weeds under different soil conditions: Seeds of various broadleaf and grassy weed biotypes (origin) were sown in pots with a diameter of 8-13 cm containing natural soil and covered with a 1 cm layer of topsoil. To compare weed control effects, plants were planted in different cultivation soils ranging from sandy to heavy clay and with varying amounts of organic matter. The pots were then cultivated in a greenhouse (12-16 hours light, daytime temperature 20-22°C, nighttime temperature 15-18°C) until application. At different BBCH stages (00-25) of the seeds / plants, the pots were treated with a spray containing the mixtures / compositions of the present invention, or in the form of WG, WP, EC, or other formulations, or the components applied alone, using a laboratory track sprayer. The water volume used for spraying was 100-600 L / ha. After treatment, the plants were returned to the greenhouse and fertilized and watered as needed. Cultivate the pots in a greenhouse (12-16 hours of light, daytime temperature 20-22℃, nighttime temperature 15-18℃).

[0313] 10. Pre-emergence and post-emergence action for controlling resistant grass / broadleaf weed species: Seeds of various broadleaf and grass biotypes (of origin) with different resistance mechanisms against different action modes were sown in 8cm diameter pots filled with standard field soil (loam, LSI; pH 7.4; %C org 2.2) and covered with a soil cover layer of about 1cm. The pots were then cultivated in a greenhouse (12-16 hours light, daytime temperature about 23°C, nighttime temperature about 15°C) until application. At different BBCH stages 00-25 of the seeds / plants, the pots were treated with a spray containing the mixtures / compositions of the present invention, in the form of WG, WP, EC or other formulations, or the components applied alone, on a laboratory track sprayer. The water volume for spray application was 300L / ha. After treatment, the plants were returned to the greenhouse and fertilized and watered as needed. Cultivate the pots in a greenhouse (12-16 hours of light, daytime temperature of about 23℃, and nighttime temperature of about 15℃).

[0314] 11. Pre-emergence and post-emergence effects on weeds and crop selectivity under different sowing conditions: Seeds of various broadleaf and grass weed biotypes (origin) and crop species (origin) were sown in pots with a diameter of 8-13 cm filled with natural soil and covered with a soil cover layer of about 0-5 cm. The pots were then cultivated in a greenhouse (12-16 hours of light, daytime temperature 20-22°C, nighttime temperature 15-18°C) until application. At different BBCH stages 00-25 of the seeds / plants, the pots were treated with a spray containing the mixtures / compositions of the present invention, or a mixture or individual component in the form of WG, WP, EC or other formulations, on a laboratory track sprayer. The water volume used for spray application was 100-600 L / ha. After treatment, the plants were returned to the greenhouse and fertilized and watered as needed. The pots were cultivated in the greenhouse (12-16 hours of light, daytime temperature 20-22°C, nighttime temperature 15-18°C).

[0315] 12. Pre-emergence and post-emergence effects on weeds at different soil pH values: Seeds of various broadleaf and grass weed biotypes (of origin) were sown in pots with a diameter of 8-13 cm containing natural soil and covered with a 1 cm top dressing layer. To compare herbicidal activity, plants were grown in standard field soil (loam; non-sterile) with different pH values: pH 7.4 and pH 8.4. Therefore, the soil was mixed with lime to obtain a higher pH. The pots were then cultivated in a greenhouse (12-16 hours light, daytime temperature 20-22°C, nighttime temperature 15-18°C) until application. At different BBCH stages 00-10 of the seed / plant, the pots were treated on a laboratory track sprayer using a spray containing the mixtures / compositions of the present invention, in the form of WG, WP, EC, or other formulations, or the components applied alone. The water volume used for spray application was 100-600 L / ha. After treatment, return the plants to the greenhouse and fertilize and water them as needed. Cultivate the pots in the greenhouse (12-16 hours of light, daytime temperature 20-22℃, nighttime temperature 15-18℃).

[0316] The result of greenhouse :

[0317] In each case, formulation 1 (MPR safener in capsule) and comparative formulation 1 (MPR safener outside capsule) were compared. Typical field application rates were 200 g ai / ha DCPMI and 100 g ai / ha pyrazosulfuron. The application window was early pre-emergence (BBCH 11). To produce maximum damage, the application rate was increased by up to 2 times in greenhouses.

[0318]

[0319]

[0320] The formulations of the present invention, containing active herbicidal ingredients, exhibit very high activity and low damage. Surprisingly, even with the presence of a safener in the sustained-release formulation (CS) of the embodiments of the present invention, no difference in formulation could be determined.

[0321] Outdoor testing:

[0322] In outdoor trials under natural conditions, fields were prepared in a manner commonly used in practice, and harmful plants were naturally or artificially infected. The compositions of the present invention, mixtures of the prior art, or individual components were applied before or after crop sowing, or before or after the emergence of the harmful plants. Visual scoring was performed over a period of 4 weeks to 8 months post-treatment by comparison with untreated portions (plots). Damage to crop plants and activity against harmful plants are recorded here as percentages, along with other effects related to the respective experimental questions.

[0323] b) Results

[0324] Use the following abbreviations:

[0325] BBCH = BBCH codes provide information about the stages of plant morphological development. Formally, the abbreviation stands for Biologische Bundesanstalt, Bundessortenamt und Chemische Industrie [Federal Institute of Agricultural and Forestry Biology, Federal Office of Crop Varieties and Chemical Industries]. The range BBCH 00-10 indicates the germination stage up to seed germination. The range BBCH 11-25 indicates the leaf development stage up to stocking (corresponding to the number of tillers or lateral branches).

[0326] PE = applied to the soil before emergence; BBCH 00-10 for seeds / plants.

[0327] PO = applied to the green parts of the plant after emergence; BBCH 11-25 for plants.

[0328] HRAC stands for Herbicide Resistance Action Committee, which classifies approved active ingredients according to their mode of action (MoA).

[0329] HRAC group A = Acetyl-CoA carboxylase inhibitor (MoA: ACCase).

[0330] HRAC group B = acetolactate synthase inhibitor (MoA: ALS).

[0331] AS = Active substance (based on 100% active ingredients; synonym (syn.)ai).

[0332] AS dosage g / ha = application rate of active substance per hectare in grams.

[0333] To name each blackgrass biotype (plant name: Alopecurus myosuroides; EPPO code or former Bayer code: ALOMY), use the EPPO code and additional identifier:

[0334] -ALOMY_DEU12053 indicates a biotype with enhanced metabolic ALS resistance (EMR) but without ALS target site resistance (TSR).

[0335] -ALOMY_DEU12061 indicates a biotype with enhanced metabolic ACCase resistance (EMR) but without ACCase target site resistance (TSR).

[0336] -ALOMY_R35 indicates a biotype sensitive to herbicides with an ALS or ACCase mode of action (MoA).

[0337] The herbicidal composition of the present invention has the activity to meet the aforementioned requirements, and thus achieves the goal of improving the application characteristics of the herbicidal active ingredient 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-3-isoxazolidinone (including providing a more flexible solution for improving activity without changing the application rate).

[0338] In cases where the focus is on the herbicidal effect of the compositions of the present invention on economically significant monocotyledonous and dicotyledonous pests compared to mixtures of the prior art or to components applied alone, the synergistic herbicidal activity is calculated using the Colby formula (see SRColby; Weeds 15 (1967), 20-22):

[0339] Field results of the herbicidal efficacy of aqueous dispersions:

[0340] Methods: The standard autumn field application was a 200 L / ha spray solution, with a dosage of 150 g fluthiamethoxam, 200 g DCPMI, and 100 g pyrazosulfuron per hectare. The herbicidal efficacy against Alopecurus myosuroides (ALOMY), phytotoxicity to winter barley and winter wheat, and damage to adjacent crops (tree planting, sugar beets, broccoli) were evaluated. Visual assessment was performed within the 0-100% range, comparing to an untreated control group: 0% = no significant effect compared to the untreated control group; 100% = complete effect compared to the untreated control group.

[0341] surface Field results – After early emergence, BBCH 11

[0342]

[0343]

[0344] The evaluation was conducted at the end of March (administration at the end of September). The formulation of this invention exhibited very high activity without causing further harm. Even though the safener was still released only slowly, no difference in formulation could be detected.

Claims

1. A ZC formulation comprising a capsule suspension concentrate and at least one suspension concentrate, said capsule suspension concentrate comprising: A) The particulate dispersion phase comprises: The reaction product of at least one compound a1) having an isocyanate reactive group and an isocyanate mixture a2). At least one active ingredient (b) The safety agent (s) is dissolved in an organic, water-insoluble solvent (L). Optionally one or more additives, and B) Liquid aqueous phase, The median particle size of the dispersed phase A) is 1 to 50 µm; and The active ingredient b) is 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-3-isoxazolidinone; The safener (s) is selected from quinoline and pyrazolium acetonitrile, and The at least one suspension concentrate comprises: One or more active ingredients (z). At least one or more thickeners (c). One or more anionic emulsifiers (e1) and / or one or more nonionic emulsifiers (e2). The active ingredient z) is selected from fluthiamethoxam and pyrfluthiamethoxam.

2. The ZC formulation according to claim 1, characterized in that, The capsule suspension concentrate contains at least one protective colloid, C1.

3. The ZC formulation according to claim 1 or 2, characterized in that, The capsule suspension concentrate contains at least one unencapsulated active ingredient (z).

4. The use of the ZC formulation according to any one of claims 1 to 3 as a herbicide in cereals and rapeseed, and by pre-emergence and post-emergence methods.

5. A method for controlling unwanted plants in plant crops, characterized in that, The ZC formulation according to any one of claims 1 to 3 is applied to plants or the area where plants grow.

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