EA047067B1 - CAPSULE SUSPENSION CONCENTRATE FOR COMBATING UNWANTED PLANTS IN PLANT CROPS, METHOD OF ITS OBTAINING AND ITS APPLICATION - Google Patents

Description

The present invention relates to a capsule suspension concentrate for controlling unwanted plants in plant crops, its preparation, a ZC formulation for controlling unwanted plants in plant crops containing said capsule suspension concentrate and suspension concentrate (SC), use of said capsule suspension concentrate or said ZC-preparative form, as well as a method for controlling unwanted plants in plant crops using the specified capsule suspension concentrate or the specified ZC-preparative form.

The active substances can in principle be obtained in various ways, and it is necessary to improve the properties of the active substances and types of preparative forms regarding their preparation, stability, use and effectiveness of the preparative forms. In addition, certain formulations are more preferable for economic and environmental reasons than others.

Herbicidal protectants are difficult to prepare due to their low melting points, which vary over a wide range, and their amorphous structure. Products on the market consist of organic dispersions, emulsion concentrates, suspoemulsions, and the active substance with a low melting point is present in dissolved or emulsified form. Preferred is rapid bioavailability of the protective agent present in dissolved form. The disadvantage is that these formulations cannot be mixed with aqueous formulations. Another disadvantage is that the protective agent has high bioavailability and is partially absorbed by the plant too early, thus the protective effect may be weakened when the active substance is taken later. New, most obvious options described in modern technologies are presented in WO 2017/144497 A1. Here, the protective agent is added to water in liquid form, crystallized and used in the form of a suspension concentrate (SC). The advantage of this SC is its miscibility with other suspension concentrates. The disadvantage is miscibility with active substances having a low melting point in suspension concentrates, which leads to agglomeration of the formulation. Another disadvantage with respect to these formulations is the low initial bioavailability, since the particles in the concentrate must first be dissolved before application to the plant.

The herbicidal protectant (for example, mefenpyr-diethyl or cloquintocet-mexyl) is often present in the form of esterified acids, which are available with their technical properties in the form of a solidified melt with a range of melting points, which in finished formulations quickly leads to clumping with the active substances with a low melting point.

For certain active substances, protective agents are necessary to prevent damage in crop plants. A new active ingredient on the market is the active ingredient [(2,4-dichlorophenyl)methyl]-4,4'-dimethyl-3-isoxazolidinone (CAS No. 81777-95-9 or IPUAC 2-(2,4-dichlorobenzyl)-4 ,4-dimethyl-1,2-oxazolidin-3-one, hereafter abbreviated as DCPMI). It is a chemical relative of clomazone (hereinafter abbreviated as CPMI, CAS 81777-89-1, IUPAC 2-(2-chlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one). Compared to clomazone, DCPMI has a reduced solubility in water (39.5 ppm instead of 1000 ppm) and a slightly reduced vapor pressure (0.88 mPa instead of 19.2 mPa), thus the calculated Henry's constant (distribution active substances above the water-gas phase) remains at the same level. Both active ingredients belong to the class of volatile active ingredients that can cause unwanted damage to neighboring crops. A low vapor pressure connection may also result in undesirable widespread distribution, which must be prevented for reasons of harm to humans, ecotoxicological as well as economic reasons.

DCPMI is used in herbicidal compositions and mixtures or as a selective grass herbicide, as for example described in WO-A 2015/127259 or WO-A 2012/148689. WO 2018/024839 A1 can be considered as the closest analogue.

Therefore, the object of the present invention was to obtain suitable formulations in capsules with a low melting point of the active substances, which should reduce the volatility by at least 70% (relative to non-encapsulated active substances) and at the same time promote the release and activity of the protective agents and ensure the stability of the formulation during storage in combination with other active ingredients.

There is therefore a need for new aqueous dispersion formulations that contain low melting point protectants that can be mixed with the active ingredient, preferably the low melting point active ingredient, without forming agglomerates and that have high, targeted bioavailability protective agent.

There is further a need to obtain formulations in which the protective agent is contained in a capsule without the active ingredient, in order to provide a combination of low melting point active ingredients with stable formulations.

- 1 047067

Thus, the object of the present invention was to provide aqueous formulations containing a protective agent that does not form undesirable agglomerates.

Thus, the object of the present invention was to obtain aqueous formulations containing a protective agent and an additional active ingredient z), without the formation of undesirable agglomerates in the formulations with a high effect of the protective agent, the active ingredients b) also being preferably contained in a capsule.

Surprisingly, it was found that in the formulations according to the invention, the protective agent s) exhibits good activity despite being capsules, although capsules are known to those skilled in the art as delayed-release formulations.

Suitable active ingredients z) and b) within the meaning of the present invention are all agrochemical herbicidal active ingredients that can be dissolved in a water-insoluble organic solvent.

Preferred active ingredients b) with a melting point range of 50-85°C are anilophos, acephate, benfluralin, bifenthrin, bupyrimate, butralin, chloroacetic acid, cyfluthrin, cinmethylin, cypermethrin, demethone-methylsulfone, dimethamethrin, dimethoate, dioxabenzophos, diphenylamine , dithiopyr, dodemorphacetate, esfenvalerate, ethalfluralin, etofumesate, phenazaquin, phenitropan, fenoxycarb, fenuron-TSA, fenvalerate, fluoroglycophen-ethyl, flupyradifuron, flurazole, flurochloridone, fluroxypyr-meptyl, flusilazole, furalaxyl, haloxyfop-ethyl, haloxyfop-methyl, imazalil , ioxynyl octanoate, isoprothiolane, metalaxyl, methomyl, methoprothrin, monocrotophos, nitrapyrin, nitrotal-isopropyl, penconazole, pendimethalin, permethrin, propamocarb hydrochloride, propaquizafop, pyrazophos, quizalofop-R-tefuryl, resmethrin, trichloroacetic acid, tetramethrin, fanox, triflumizole, pyridafenthione, 2-phenylphenol, dimethylvinphos, beta-cypermethrin, famfur, clodinafap-propargyl, triazamate, tebufenpyrad, pyrimidifen, aldrin, bromophos, dialifos, pyriminobac-methyl, benzoylprop, benzoylprop-ethyl, binapacryl, camphechlor, chlorphenetol, chlorfenprop, chlorfenprop- methyl, chlorphoxime, crufomate, ciometrinil, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane, dimethylane, dinobuton, fenson, fentiaprop, fentiaprop-ethyl, fluenethyl, glyodine, 2-isovalerylindan-1,3dione, methoxyphenone, 2-methoxyethylmercuric chloride, nitrophen, indanophane, acequinocyl, ipsdienol with (b)-cis-verbenol. phenoxanil, pyraclostrobin, trifloxystrobin, cyflufenamide, gammacyhalothrin, proquinazide, 2,6-diisopropylnaphthalene, isothianyl and 2-[(2,4-dichlorophenyl)methyl]-4,4'dimethyl-3-isoxazolidinone.

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

Formulations based on DCPMI are described in WO 2018/024839 as well as in WO 2015127259.

If necessary, the formulations may contain additional non-encapsulated active ingredients z).

A further object of the present invention was to introduce protective agents into the composition in such a way that they do not form any agglomerates in mixture with other active substances; active substance b) or z), preferably DCPMI, had a consistently high effect; there was no increase in the volatility of active ingredients b) or z); the effectiveness of protective equipment remained consistently high.

The problem is solved using capsule suspension concentrates (CS) according to the invention, which, together with other active ingredients, can be further added to ZC formulations. The ZC-preparative form is a mixture of CS and suspension concentrate (SC).

Therefore, the subject of the present invention is a capsule suspension concentrate for controlling unwanted plants in plant crops, containing

A) granular dispersed phase (capsule) containing

a) a reaction product of at least one compound with isocyanate-reactive groups a1) and an isocyanate mixture a2),

b) active substance b),

s) a protective agent s) dissolved in an organic, water-insoluble solvent L), wherein the protective agent s) is selected from the group consisting of isoxadifen-ethyl, cyprosulfonamides, cloquintocet-mexyl and mefenpyr-diethyl, and

B) d) liquid aqueous phase, wherein the particles of the dispersed phase A) have an average particle size of 1-50 μm.

In a preferred embodiment, the CS according to the invention contains A) one or more additives c).

Further preferably, the CS according to the invention contains at least one protective colloid c1).

Further preferably, the CS according to the invention contains at least one non-encapsulated active ingredient z).

Particle size determined according to the CIPAC method (CIPAC = International Collaborative Analyze

- 2 047067 lytic advice on pesticides; www.cipac.org) MT 187 is defined as d50 or D90=pa3Mep of particles of the active substance (laser scattering of 50 or 90% of all volumetric particles). The average particle size is d50.

The dispersed phase particles A) have an average particle size d50, which is generally 1-50 µm, preferably 1-20 µm, very preferably 3-15 µm.

Also the subject of the present invention is a method for producing capsule suspension concentrates according to the invention, characterized in that in step (1) the protective agent s), dissolved in an organic, water-insoluble solvent L), is mixed with an isocyanate mixture a2), and the active substance b) is additionally added. , dissolved in an organic, water-insoluble solvent L), then the solution thus obtained in step (2) is emulsified in water, and the thus obtained emulsion E is mixed in step (3) with isocyanate-reactive groups a1).

Next, preferably, in step 2, protective colloid c1) is used.

The following quantity indications refer, unless otherwise stated, to the total quantity of A) and B).

In another embodiment of the method according to the invention, the emulsion E obtained in step 2 can be mixed in step 3 of the method according to the invention by stirring first with at least a diamine, a polyamine, a disalcohol, a polyalcohol and/or an amino alcohol a1). In this case, the amine or alcohol components a1) are added preferably to the aqueous solution. After completion of the reaction leading to the formation of shells (encapsulation), if necessary, also mixed with additives c). Preferably, in the method according to the invention, an amine is used as component a1).

To obtain the CS according to the invention, all suitable devices that produce strong shearing forces can be used. For example, a rotor-stator mixer and a jet disperser should be named.

When carrying out the method according to the invention, the ratio of the NCO group from component a2) to the NCO-reactive groups from component a1) can vary within certain ranges. In general, 0.8-1.5 equivalents of the amine or alcohol component are used per 1 mole of isocyanate. Preferably, the amount of isocyanate and amine or alcohol is selected such that an equimolar amount of isocyanate groups and amino or hydroxy groups is present.

When carrying out the method according to the invention, the reaction temperatures can vary within a certain range.

In the first step (1) of the method according to the invention, the temperature is generally -10-80°C, preferably 0-50°C, particularly preferably 2-40°C, very preferably 2-30°C, in the second step (2) the temperature in general is -10-+80°C, preferably 0-80°C, and in the third step (3) the temperature is generally 0-80°C, preferably 10-75°C.

The method according to the invention is preferably carried out at low atmospheric pressure.

The capsule wall thickness of the capsule suspension concentrates according to the invention is 0.001-4 µm, preferably 0.01-2 µm and very preferably 0.01-1 µm (calculated wall thickness).

When carrying out the reaction a1) with a2), the sum of the number-average functionality of X isocyanate groups and isocyanate-reactive groups is 2<X<6, preferably 2<X<4.5, especially preferably 2.0<X<3.5 and very preferably 2.2<X<2.8.

The number-average functionality X is further discussed in more detail as a feature in the method according to the invention as follows. Here the higher functionality compound is decisive, with the difference of the low functionality compounds minus 2 being added to the higher functionality compound. For example, if a1) has an (average) functionality of 2.1, and a2) has 2.6, then we get 2.1-2=0.1. This difference is added to 2.6: 2.6+0.1=2.7. Thus, the number average functionality is 2.7. Alternatively, if a1) is 2.7 and a2) is 2.3, then the number-average functionality is 2.7+2.3-2 = 3.0.

The capsule suspension concentrates according to the invention have a number of advantages. Thus, they are capable of releasing active components over a longer period of time in the quantity required in each case. Another advantage is that the compatibility with plants of the active ingredients present is improved, and volatility and therefore damage to neighboring crops is reduced. In addition, the acute toxicity of the active components is reduced, so that when applying microcapsule formulations there are no problems either for operating personnel or for potential phototoxic reactions.

As compounds with isocyanate-reactive groups a1), aliphatic, aromatic, cyclic and alicyclic primary and secondary diamines as well as polyamines are taken into account. Examples to be mentioned are ethylenediamine (1,2), diethylenetriamine, monoisopropylamine, 4-aminopyridine (4-AP), n-propylamine, ethylene or propyleneimine-based polyaziridine, triethylene tetraamine (TETA), tetraethylenepentamine, 2,4,4- triaminodiphenyl ether, bis(hexamethylene)

- 3 047067 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'-diaminodiphenylmethane, 1,5-diaminonaphthaleneisophoronediamine, diaminopropane, diaminobutane, piperazine, aminoethylenepiperazine (AEP), poly(propylene glycol)-bis(2-aminopropylether) or o,o-bis(2aminopropyl)polypropylene glycol-blockpolyethylene glycol-blockpolypropylene glycol, hexamethylenediamine, bis-(3-aminopropyl)amine, bis-(2-methylaminoethyl)methylamine, 1,4-diaminocyclohexane, 3-amino1-methyl-aminopropane, Nmethyl-bis-(3-aminopropyl)amine, 1, 4-diamino-n-butane and 1,6 diamino-n-hexane. Preferred is hexamethylenediamine and also diethylenetriamine.

As compounds with isocyanate-reactive groups a1), primary and secondary aliphatic as well as aromatic disalcohols and polyalcohols are also taken into account. Mentioned as examples are ethanediol, propanediol (1,2), propanediol (1,3), butanediol (1,4), pentanediol (1,5), hexanediol (1,6), glycerol and diethylene glycol. Preferably, glycerol and 1,2-propanediol are used.

Amino alcohols are also taken into account as compounds with isocyanate-reactive groups a1). Mention may be made, as examples, of triethanolamine, monoethanolamine, triisopropanolamine, diisopropylamine, N-methylethanolamine, N-methyldiethanolamine.

In a very preferred embodiment, an amine is used as the isocyanate-reactive component a1).

Isocyanate mixture a2) means a mono, di- and/or polyisocyanate mixture or a reactive product of an isocyanate mixture. Suitable compounds a2) are, for example, 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4 and/or 2,4,4-trimethylhexamethylene diisocyanate, isomeric bis-(4, 4'-isocyanatocyclohexyl)methane (H12 - MDI) or mixtures thereof with any isomer content, 1,4-cyclohexylene diisocyanate, 4-isocyanatomethyl-1,8 octane diisocyanate (nonane triisocyanate), 1,4-phenylene diisocyanate, 2,4- and/or 2 ,6-toluylene diisocyanate (TDI), 1,5-naphthylene diisocyanate, 2,2'- and/or 2,4'- and/or 4,4'-diphenylmethane diisocyanate (MDI), 1,3- and/or 1,4 -bis-(2-isocyanato-prop-2-yl)-benzene (TMXDI), 1,3-bis(isocyanatomethyl)benzene (XDI), alkyl-2,6diisocyanatohexanoate (lysine diisocyanate) with alkyl groups with 1-8 carbon atoms , as well as their mixtures. Further modifications to be mentioned are compounds containing allophanate, urethdione, urethane, isocyanurate, biuret, iminooxadiazinedione or oxadiazinetrione structures, suitable structural elements of component a2 based on said diisocyanates, as well as polycyclic compounds, such as MDI polymers (pMDI, such as PAPI-27 from Dow or Desmodur® type 44V20 from Covestro AG), as well as combinations thereof.

Preferably, modifications with an isocyanate functionality (NCO) of 2-6 are used, more preferably 2.0-4.5, particularly preferably 2.3-4.2 and very preferably 2.3-3.8. Particularly preferred is the NCO functionality 2.4-2.8.

Preferably, diisocyanates from the series HDI, IPDI, H12 - MDI, TDI and MDI are used for modification. Particularly preferred are TDI and MDI, as well as their derivatives. Particularly preferably, polymeric MDIs such as PAPI-27 mixed with TDI are used as MDIs. The preferred NCO content of isocyanates or polyisocyanates or mixtures is 3-50 wt%, particularly preferably 10-40 wt%, particularly preferably 15-35 wt% and very preferably 18-30 wt%. The isocyanate groups may be present in a partially or completely blocked form prior to reaction with the isocyanate-reactive groups, so that they can immediately react with the isocyanate-reactive groups. This ensures that the reaction occurs at certain temperatures (blocking temperatures). Conventional blocking agents are known in modern technology and are chosen in such a way that at temperatures of 60-220°C, depending on the substance, they are separated from the isocyanate group and only then react with the isocyanate-reactive group. There are blocking agents that are built into the polyurethane and also those that are present in the polyurethane as solvents or emollients or that are released from the polyurethane as a gas. We are also talking about the values of blocked NCOs. Whenever the invention refers to NCO values, this always refers to non-blocked NCO values. Most often blocked to <0.5%. Common blocking agents are, for example, caprolactam, methylethylketoxime, pyrazoles, such as 3,5-dimethyl-1,2-pyrazole or 1pyrazole, triazoles, such as 1,2,4-triazole, diisopropylamine, diethyl malonate, diethylamine, phenol or their derivatives or imidazole.

Component a2) can also be used in the form of mixtures of the above compounds or also as a prepolymer. In this case, a transformation occurs, for example, of a compound containing an isocyanate group, with an NCO content of 3-50 wt.%, with compounds containing groups reactive towards isocyanates, with an OH number of 10-150 mg KOH/g.

Very preferably a mixture of polymeric(p)MDI as well as TDI is used. In this case, the ratio of pMDI to toluene diisocyanate can vary within certain ranges, preferably 0.2-2 wt.% pMDI and 0.2-2 wt.% TDI are used.

- 4 047067

The aqueous phase B) of capsule suspension concentrates according to the invention, in addition to water, may also contain additional additives c), such as emulsifiers, protective colloids, preservatives, defoamers, cooling stabilizing agents, thickeners, pH stabilizers and neutralizers. Preferably, emulsifiers, thickeners and protective colloids c1) are used as component c).

As organic solvents L), all conventional organic solvents are taken into account, which, on the one hand, do not mix well with water, and, on the other hand, dissolve well the agrochemical active substances used. Preference should be given to aliphatic and aromatic, optionally halogenated hydrocarbons such as toluene, xylene, Solvesso® 100, 100 ND, 150, 150 ND or 200, 200 ND (mineral oil), carbon tetrachloride, chloroform, methylene chloride and dichloroethane, in addition , esters such as ethyl acetate, and alkanecarboxylic acid amides such as octanecarboxylic acid dimethylamide and decanecarboxylic acid dimethylamide. Further, vegetable oils are taken into account, as well as modified oils (eg by methylation, ethylation and also hydrogenation and hydration) based on, for example, rapeseed oil, corn oil, coconut oil or the like. Particular preference is given to using mineral oil, more preferably a solvent based on dialkylnaphthalene (such as diisopropylnaphthalene), as well as mixtures of 1-methyl-, 2-methylnaphthalene and naphthalene (for example, Solvesso® type 200 ND, CAS No. 64742-94-5) .

As emulsifiers (c), the usual surfactants present in the formulations of agrochemicals are taken into account.

For example, ethoxylated nonylphenols, polyethylene glycol ethers of linear alcohols, decomposition products of alkylphenols with ethylene oxide and/or propylene oxide, further fatty acid esters, alkyl sulfonates, alkyl sulfates and aryl sulfates should be named.

As protective colloids c1) (dispersants), all substances suitable for this purpose are usually taken into account. Preference should be given to natural and synthetic water-soluble polymers such as gelatins, starch and cellulose derivatives, in particular cellulose esters and ethers such as methylcellulose, also polyvinyl alcohols, partially hydrolyzed polyvinyl acetate, lignosulfonate (such as Borresperse®NA, REAX® 88 or Kraftsperse® 25 S), modified naphthalene sulfonates (as Morwet D-425), polyvinylpyrrolidones and polyacrylamides. Particular preference is given to using polyvinyl alcohols, partially hydrolyzed polyvinyl acetate and lignosulfonates. Polyvinyl alcohols as well as lignosulfonates are highly preferred. Particularly preferably, a lignosulfonate is used.

As thickeners c) organic thickeners as well as inorganic thickeners are taken into account. Organic thickeners are taken into account in the form of organic natural or biotechnology modified thickeners, or organic synthetic thickeners. Common synthetic thickeners are Rheostrux® (Croda), Thixin® series or Thixatrol® (Elementis). They are usually based on acrylates. Common organic thickeners are those based on xanthan or cellulose (such as hydroxyethyl or carboxymethylcellulose) or a combination of both. Other typical representatives are based on cellulose or lignin. Preferably, natural modified xanthan-based thickeners are used. Common representatives are, for example, Rhodopol® (Solvay) and Kelzan® (Kelco Corp.), as well as Satiaxane® (Cargill). Also preferred are silicic acid and attapulgite.

As preservatives c) usually take into account all substances suitable for this purpose in plant preparations. Examples to be mentioned are Acticide® SPX (Thor) as well as Proxel® GXL (Lonza).

As defoamers c) all suitable substances used in plant treatment products are generally taken into account. Preferred are silane derivatives such as polydimethylsiloxylane and magnesium stearate. Common products used are Silcolapse® 484 (Solvay, Silioxane emulsion) as well as SAG 1571 (Momentive).

As cooling stabilizing substances c), all suitable substances used in plant treatment products are generally taken into account. For example, urea, glycerin and propylene glycol should be named.

As neutralizers c) the usual acids and bases are taken into account. For example, phosphoric acid, citric acid, sodium lye and aqueous solutions of ammonia should be named.

In the present invention, in formulas, for example, in formula (I), if necessary, substituted residues, unless otherwise indicated, can be single or multiple substituted, and in case of multiple substitution, the substituents can be the same or different. Furthermore, if only one structure or trade name is indicated, mesomeric and tautomeric forms are present, which are known to the person skilled in the art without any problem.

Moreover, in the ranges of preferences specified in the present invention, the different levels of preference should be understood to mean that they can be combined with each other in various ways, but in any case identical levels of preference and, in particular, the most preferred

- 5 047067 embodiment/level of preference in each case must be combined with each other and indeed disclosed as such a combination.

The compositions described above, consisting solely of essential components (and not of optional components), are also to be considered as disclosed.

Percentage numbers, unless otherwise stated, are to be understood as percentages by weight, typically adding the weight percent of the formulations to 100 or supplementing to 100% with the appropriate solvent/dispersant.

The composition of the capsule suspension concentrates according to the invention may vary within certain ranges. The amount of dispersed phase A) relative to the entire formulation is generally 10-90% by weight, preferably 30-70% by weight, particularly preferably 40-60% by weight.

The amount of a) (reaction product a1+a2) is generally 0.1-8 wt.%, preferably 0.2-4.5 wt.%, particularly preferably 0.3-2.5 wt.%, the amount of agrochemical active substance b) is generally 1-50 wt.%, preferably 5-40 wt.%, particularly preferably 10-20 wt.%, the amount of organic solvents L) is generally 1-90 wt.%, preferably 10-60 wt. .%, especially preferably 20-40 wt.%, the amount of protective colloids c1) is generally 0.1-5 wt.%, preferably 0.2-3 wt.%, especially preferably 0.3-1.5 wt. % and the amount of additives c) is generally 0.1-15 wt.%, preferably 0.3-10 wt.% and particularly preferably 0.4-3 wt.%.

Preferably, the ratio of agrochemical active substance b) to isocyanate a2) is 7:1-40:1, more preferably 8:1-20:1, particularly preferably 9:1-18:1.

If amino-functional compounds are used as component a1), then preferably the ratio of amine isocyanate-reactive groups a1) to isocyanate a2) is 0-1.

In a preferred embodiment, capsule suspension concentrates (CS) according to the invention with one or more suspension concentrates (SC) are mixed to form a ZC formulation.

Also the subject of the present invention is a ZC formulation for the control of unwanted plants in plant crops, containing a capsule suspension concentrate according to the invention and at least one suspension concentrate (SC) containing one or more active substances z), at least one or more thickeners c), one or more anionic emulsifiers e1) and/or one or more nonionic emulsifiers e2).

In a preferred embodiment, the ZC formulation contains at least one additional protective agent.

Preferably, fungicides, insecticidal and herbicidal active substances are used as active substances z). Preference is given to known active substances which are based, for example, on the inhibition of, for example, the enzyme acetolactate synthase, the enzyme acetyl-CoA carboxylase, cellulose synthase, enolpyruvate-shikimate-3-phosphate synthase, glutamine synthase, p-hydroxyphenyl-pyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, protoporphyrinogen oxidases, as described, for example, in Weed Research, 26 (1986), 441-445; or The Pesticide Manual, 17th ed., The British Crop Protection Council and the Royal Soc. of Chemistry, 2017 and the literature mentioned there. Below, by way of example, known herbicides are mentioned that can be combined with the compounds according to the invention, these active substances being either indicated by a general name in the English version according to the International Organization for Standardization (ISO) or by a chemical name, or by a code number. All forms of use are present, such as acids, salts, esters, as well as all isomeric forms, such as stereoisomers and optical isomers, even if they are not expressly indicated.

Common active ingredients z) selected from the list are acetochlor, acifluorphene, acifluorphene-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametrine, amicarbazone, amidochlor, amidosulfuron, aminocyclopyrapyrachlor, aminocyclopyrachlor-potassium, aminopyralide , amitrol, ammonium sulfamate, anilofos, asulam, atrazine, azadenidine, azimsulfuron, beflubutamide, benazoline, benazolin-ethyl, benfluralin, benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazone, benzobicyclop, benzophenap, bicyclopyrone, bifenox, aphos, bilanaphos- sodium, bispiribac, bispiribac-sodium, bromacil, bromobtide, bromophenoxime, bromoxynil, bromoxynyl butyrate, -potassium, -heptanoate and -octanoate, busoxynon, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrol, carfenthra, zones , carfentrazone-ethyl, chloramben, chlorbromuron, chlorfenac, chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlorophthalim, chlorothoduron, chlorthal-dimethyl, chlorsulfuron, 3-[5-chloro-4- (trifluoromethyl)pyridin-2-yl]-4-hydroxy-1methylimidazolidin-2-one, cynidone, cynidone-ethyl, cinmethylin, cinosulfuron, clacifos, clethodim, clodinafop, clodinafop-propargyl, clomazone, clomeprop, clopyralid, cloransulam, cloransulammethyl, cumyluron, cyanamide, cyanazine, cycloate, cyclopyrimorate, cyclosulfomoron, cycloxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D, 2,4-E-butotyl, -butyl, -dimethylammonium, -diolamine, ethyl, 2-ethylhexyl , -isobutyl, -isooctyl, -isopropylammonium, -potassium, -triiso-propanolammonium and - 6 047067 trolamine, 2,4-DB, 2.4-DB-6vth.t -dimethylammonium, -isooctyl, -potassium and -sodium, daimuron ( dimron), dalapon, dazomet, n-decanol, desmedipham, detosil-pyrazolate (DTP), dicamba, diclobenil, 2-(2,4dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, 2- (2,5-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin3-one, dichlorprop, dichlorprop-R, diclofop, diclofop-methyl, diclofop-R-methyl, diclosulam, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr- sodium, dimefuron, dimepiperate, dimethachlor, dimethamethrin, dimethenamid, dimethenamid-R, dimethrasulfuron, dinitramine, dinoterb, diphenamide, diquat, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTS, esprocarb, ethalfluralin, etamethsulfuron, etamethsulfuron-methyl, etiosin, etofumesate, ethoxyphene, ethoxyphene-ethyl, ethoxysulfuron, etobenzanide, F-9600, F-5231, i.e. No. [2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazol-1yl]-phenyl]-ethanesulfonamide, F-7967, i.e. . 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione, fenoxaprop, fenoxaprop- R, fenoxaprop-ethyl, fenoxaprop-R-ethyl, fenoxasulfone, fenquinotrione, fentrisamide, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, florpyrauxifen, florpyrauxifen-benzyl, fluazifop, fluazifop-R, fluazifop- butyl, fluazifop-R-butyl, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazin, fluometuron, flurenol, flurenol-butyl,

-dimethylammonium and -methyl, fluoroglycophene, fluoroglycophene-ethyl, flupropanate, flupirsulfuron, flupirsulfuron-methyl-sodium, fluridone, flurochloridone, fluroxypyr, fluroxypyr-meptyl, flurtamone, flutiacet, flutiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, osamine, glufosinate, glufosinate-ammonium, glufosinate-R-sodium, glufosinate-R-ammonium, glufosinate-R-sodium, glyphosate, glyphosate-ammonium, -isopropylammonium, -diammonium, -dimethylammonium, -potassium, -sodium and -trimesium, H- 9201, i.e. O-(2,4-dimethyl-6-nitrophenyl)-O-ethyl-isopropylphosphoramidothioate, halauxifen, halauxifen-methyl, halosaphen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-R, haloxyfop-ethoxyethyl, haloxyfop-R-ethoxyethyl, haloxyfop-methyl, haloxyfop-R-methyl, hexazinone, HW-02, i.e. 1-(dimethoxyphosphoryl)-ethyl-(2,4-dichlorophenoxy)acetate, 4-hydroxy-1-methoxy-5-methyl-3[4-(trifluoromethyl)pyridin-2-yl]imidazolidin-2-one, 4- hydroxy-1-methyl-3-[4-(trifluoromethyl)pyridin2-yl]imidazolidin-2-one, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-immonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxynyl-octanoate, -potassium and sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, carbutylate, 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, lactofen, lenacyl, linuron, MCPA, MCPA-butyl, -dimethylammonium, -2-ethylhexyl, -isopropylammonium, -potassium and -sodium, MSRP, MSRP-methyl, -ethyl and -sodium, mecoprop, mecopropsodium, and - butotyl, mecoprop-R, mecoprop-R-butotyl, -dimethylammonium, -2-ethylhexyl and -potassium, mefenacet, mefluidide, mesosulfuron, mesosulfuron-methyl, mesotrione, metabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, metabenzthiazuron, methio, pirsulfuron , methiozoline, methyl isothiocmanate, methobromuron, metolachlor, S-metolachlor, metosulam, methoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinate, monolinuron, monosulfuron, monosulfuron ester, MT-5950, i.e. No.[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide, NGGC-011, napropamide, NC-310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole, neburon, nicosulfuron, nonylic acid (pelargonic acid), norflurazon, oleic acid (fatty acid), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazop, oxasulfuron, oxacyclomefone, oxotrione (lancotrione), oxyfluorfen, paraquat, paraquat dichloride, pebulate, pendimethalin, penoxsulam, pentachlorophenol, pentoxazone, petoxamide, mineral oil, phenmedipham, picloram, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron-methyl, prodiamine, oxidim , promethone, prometrin, propachlor, propanil, propaquizafop, propazine, profam, propisochlor, propoxycarbazone, propoxycarbazone sodium, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotol, pyrazolinate (pyrazolate), pyrazosulfuron, sulfuron- ethyl, pyrazoxifene, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, piribambenzoxime, pyributicarb, pyridafol, pyridate, pyrifthalide, pyriminobac, pyriminobac-methyl, pirimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, vinoklamine, quizalofop, quizalofop-ethyl, quizalofop-R, quizalofop-R-ethyl, quizalofop-R-tefuryl, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simethrine, sulcotrione, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, SYN-523, SYP- 249, i.e. 1-ethoxy-3-methyl-1ohobut-3-en-2-yl-5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, SYP-300, i.e. 1-[7-fluoro-3-oxo-4(prop-2-in-1-yl)-3,4-dihydro-2H-1,4-benzoxazin-6-yl]-3-propyl-2-thioxoimidazolidine -4,5-dione, 2,3,6TBA, TCA (trifluoroacetic acid), TCA-sodium, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumetone, terbutylazine, terbutryn, tenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl , thifensulfuron, thifensulfuron-methyl, thiobencarb, thiaphenacyl, tolpiralate, topramesone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tribenuronmethyl, triclopyr, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazine,

- 7 047067 trifluralin, trifluusulfuron, triflusulfuron-methyl, tritosulfuron, urea sulfate, vernolate, XDE-848, ZJ-0862, i.e. 3.4-dichloro-H-{2-[(4.6-dimethoxypyrimidin-2-yl)oxy|benzyl}aniline. as well as the following connections:

Preferably, the active substance z) is selected from the list including anilophos, acephate, benfluralin, bifenthrin, bupyrimate, butralin, chloroacetic acid, cyfluthrin, cinmethylin, cypermethrin, demethone-methylsulfone, dimethamethrin, dimethoate, dioxabenzophos, diphenylamine, dithiopyr, dodemorphoacetate, fenvalerate, ethalfluralin, etofumesate, phenazaquin, phenytropan, fenoxycarb, fenuron-TSA, fenvalerate, fluoroglycophene-ethyl, flupyradifuron, flurazole, flurochloridone, fluroxypyrmeptyl, flusilazole, furalaxyl, haloxyfop-ethyl, haloxyfop-methyl, imazalil, ioxynyl octanoate, prothiolane, metalaxyl, methomyl , methoprothrin, monocrotophos, nitrapyrin, nitrotal-isopropyl, penconazole, pendimethalin, permethrin, propamocarb hydrochloride, propaquizafop, pyrazophos, quizalofop-R-tefuryl, resmethrin, trichloroacetic acid, tetramethrin, thiophanox, triflumizole, pyridafenthione, 2-phenylphenol, vinfos, beta -cypermethrin, famfur, clodinafap-propargyl, triazamate, tebufenpyrad, pyrimidifen, aldrin, bromophos, dialifos, pyriminobac-methyl, benzoylprop, benzoylprop-ethyl, binapacryl, camphechlor, chlorphenetol, chlorfenprop, chlorfenprop-methyl, chlorfoxime, crufomate, ciometrinil, 1 ,1-dichloro-2,2-bis(4-ethylphenyl)ethane, dimethylane, dinobutone, fenson, fentiaprop, fentiaprop-ethyl, fluenethyl, glyodine, 2-isovalerylindane-1,3-dione, methoxyphenone, 2-methoxyethylmercuric chloride, nitrophen, indananophan, acequinocyl, ipsdienol with ^)-cis-verbenol, fenoxanil, pyraclostrobin, trifloxystrobin, cyflufenamide, gamma-cyhalothrin, proquinazide, 2,6-diisopropylnaphthalene, isothianyl and 2-[(2,4-dichlorophenyl)methyl] - 4,4'-dimethyl-3-isoxazolidinone.

In an alternative preferred embodiment, the active substance z) is a herbicide selected from the list including aclonifen, aminopyralid, benzophenap, bifenox, bromoxynil, bromoxynyl-butyrate, potassium heptanoate and -octanoate, butachlor, cinmetlinin, clomazone, clopyralid, 2,4-D, also including commonly used forms: 2,4-O-butothyl, 2,4-O-butyl, 2,4-Ddimethylammonium, 2,4-O-diolamine (2,4-O-diethanolammonium), 2,4-O -ethyl, 2,4-O-2-ethylhexyl, 2,4-Diisobutyl, 2,4-O-iso-octyl, 2,4-O-isopropyl, 2,4-O-isopropylammonium, 2,4-O -sodium, 2,4-O-triisopropanolammonium, 2,4-E-trolamine (2,4-E-triethanolammonium, diflufenican, dimethachlor, dimethenamid, dimethenamid-R, ethoxysulfuron, fenoxaprop, fenoxaprop-R, penoxaprop-ethyl, fenoxaprop -P-ethyl, fenquinotrione, phentrazamide, florasulam, flufenacet, fluroxypyr, fluroxypyr-meptyl, foramsulfuron, halauxifen-methyl, iodosulfuron, iodosulfuron-methyl-sodium, isoxaflutole, MCPA (4chloro-2-methylphenoxy)acetic acid, also including commonly used forms: MCPAbutotyl, MCPA-dimethylammonium, MCPA-isoctyl, MCPA-sodium, MCPA-potassium, MCPA-2-ethylhexyl, mefenaset, mesosulfuron, mesosulfuron-methyl, metazachlor, metolachlor, S-metolachlor, methosulam, metribuzin, napropamide, nicosulfuron, Oksadiargil, oxadiazone, pendimetalin, petoxamid, pikoxicarbazon, pro-Popoxicarbazon-nrivation, propizamide, intransigns, pyraisipotol, pyroxoniphon, pyroxesul, quincerrak, teruryuralrio, Tienkarbazon, tienkarbazon-metalline, triafami, DCPMI as well as triallates.

Particularly preferred are herbicidal active substances. Particularly preferred are z) selected from the group consisting of flufenacet, prosulfocarb, pendimethalin, diflufenican, aclonifen, metribuzin, pyroxasulfone, propoxycarbazone, thiencarbazone-methyl, fenoxaprop, bromoxynil (and esterified variants thereof), halauxifen-methyl, 2,4-D ,MCPA.

Very preferred herbicidal active substances are flufenacet, pyroxasulfone, diflufenican, aclonifen and metribuzin.

Particularly preferred are also mixtures of one or more herbicidal active ingredients z) selected from the following group: flufenacet and petoxamide; flufenacet and aclonifen; flufenacet and metribuzin; flufenacet and halauxifen-methyl; prosulfocarb and diflufenican; prosulfocarb and aclonifen; prosulfocarb and metribuzin; prosulfocarb and flufenacet; prosulfocarb and halauxifen-methyl; pendimethalin and diflufenican; pendimethalin and aclonifen; pendimethalin and metribuzin; pendimethalin and halauxifen-methyl; metribuzin and diflufenican; halauxifen-methyl and diflufenican; flufenacet and diflufenican; metribuzin and aclonifen, halauxifen-methyl and aclonifen; pyroxasulfone and diflufenican; aclonifen and diflufenican; pyroxasulfone and prosulfocarb; pyroxasulfone and aclonifen; pyroxasulfone and metribuzin; pyroxasulfone and flufenacet; pyroxasulfone and halauxifen-methyl or flufenacet and pyroxasulfone and diflufenican; aclonifen and diflufenican and flufenacet; metribuzin and diflufenican and flufenacet, aclonifen, metribuzin, aclonifen and diflufenican, metribuzin and diflufenican, cinmethylin and DCPMI.

Very preferred are mixtures selected from flufenacet and diflufenican; flufenacet and pyroxasulfone; aclonifen and diflufenican; metribuzin and diflufenican; flufenacet and aclonifen; flufenacet and metribuzin; flufenacet and pyroxasulfone and diflufenican; aclonifen and diflufenican and flufenacet; metribuzin and diflufenican and flufenacet, cinmethylin and DCPMI.

Further preferably, DCPMI, diflufenican and flufenacet are used as active ingredients, especially preferably DCPMI.

- 8 047067

It is further possible to use mixtures of the said active substances, preferably mixtures in which one mixing partner is DCPMI, especially preferably mixtures of DCPMI and diflufenican, DCPMI and flufenacet and diflufenican and flufenacet.

The following groups of compounds (protective agents) are preferably used as components s).

S1) Compounds from the group of heterocyclic carboxylic acid derivatives.

S1 ^a ) Compounds of the dichlorophenylpyrazoline-3-carboxylic acid type (S1 ^a ), preferably compounds such as

1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid,

Carboxylic acid 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-ethyl ester (S1-1) (mefenpyr(-diethyl)), and related compounds as described in WO-A-91/07874;

^S1b ) dichlorophenylpyrazolecarboxylic acid derivatives ( ^S1b ), preferably compounds such as

1-(2,4-dichlorophenyl)-5-methylpyrazole-3-ethyl carboxylic acid ester (S1-2), 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-ethyl carboxylic acid ester (S1-3 ), 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-ethyl carboxylic acid ester (S1-4), and related compounds as described in EP-A-333 131 and EP -A-269 806;

^S1c ) 1,5-diphenylpyrazole-3-carboxylic acid derivatives ( ^S1c ), preferably compounds such as

1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-methyl carboxylic acid ester (S1-5), 1-(2-chlorophenyl)-5-phenylpyrazole-3-methyl carboxylic acid ester (S1-6), and related compounds, as described, for example, in EP-A-268554;

S1 ^d ) compounds of the triazolecarboxylic acid type (S1 ^d ), preferably compounds such as fenchlorazole(-ethyl ester), i.e. 1-(2,4-dichlorophenyl)-5-trichloromethyl-(III)-1,2,4-triazole-3-ethyl carboxylic acid ester (S1-7), and related compounds as described in EP-A-174 562 and EP-A-346 620;

S1 ^e ) compounds such as 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (S1 ^e ), preferably compounds such as 5-(2. 4-dichlorobenzyl)-2-isoxazoline-3-ethyl carboxylic acid ester (S1-8) or 5-phenyl-2-isoxazoline-3-ethyl carboxylic acid ester (S1-9) and related compounds as described in WO-A-91 /08202, or 5,5-diphenyl2-isoxazoline-carboxylic acid (S1-10) or 5,5-diphenyl-2-isoxazoline-3-ethyl carboxylic acid ester (S1-11) (isoxadifene-ethyl) or n-propyl ester (S1-12) or 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-ethyl carboxylic acid ester (S1-13), as described in patent application WO-A95/07897.

S2) Compounds of the group of 8-quinolineoxy derivatives (S2).

S2 ^a ) Compounds of the type 8-quinolineoxyacetic acid (S2 ^a ), preferably (5-chloro-8quinolineoxy)acetic acid-(1-methylhexyl)-ester (cloquintocet-mexyl) (S2-1), (5-chloro-8- quinolinoxy)acetic acid-(1,3-dimethyl-but-1-yl)-ester (S2-2), (5-chloro-8-quinolinoxy)acetic acid 4-allyl-hydroxy-butyl ester (S2-3) , (5-chloro-8-quinolinoxy)acetic acid-1-allyloxy-prop-2-yl ester (S2-4), (5-chloro-8-quinolinoxy) acetic acid ethyl ester (S2-5), (5 -chloro-8-quinolinoxy) methyl ester of acetic acid (S2-6), (5-chloro-8-quinolinoxy) allyl ester of acetic acid (S2-7), (5-chloro-8-quinolinoxy)acetic acid-2- (2-propylidene-iminoxy)-1-ethyl ester (S2-8), (5-chloro-8-quinolineoxy)acetic acid-2-oxo-prop-1-yl ester (S2-9), and related compounds, as described in EP-A-86750, EP-A-94349 and EP-A-191736 or EP-A-0492366, as well as (5-chloro-8-quinolineoxy)acetic acid (S2-10), its hydrates and salts , for example its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as described in WO-A-2002/34048;

S2 ^b ) compounds such as (5-chloro-8-quinolinoxy)malonic acid (S2 ^b ), preferably compounds such as (5-chloro-8-quinolinoxy) malonic acid diethyl ester, (5-chloro-8-quinolinoxy) diallyl malonic acid ester, (5-chloro-8-quinolinoxy) malonic acid methyl ethyl ester and related compounds as described in EP-A-0 582 198.

S3) Compounds of the dichloroacetamide type (S3), which are often used as pre-emergence protectants (soil protectants), such as, for example, dichloromide (KH-diallyl-2,2-dichloroacetamide) (S3-1),

R-29148 (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer (S3-2),

R-28725 (3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine) from Stauffer (S3-3), benoxacor (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4- benzoxazine) (S3-4),

PPG-1292 (Nallyl-N-[(1,3-dioxolan-2-yl)methyl]dichloroacetamide) from PPG Industries (S3-5),

- 9 047067

DKA-24 (Noallyl-No[(allylaminocarbonyl)methyl]dichloroacetamide) from Sagro-Chem (S3-6),

AD-67 or MON 4660 (3-dichloroacetyl-1-oxa-3-aza-spiro[4,5]decane) from Nitrokemia or Monsanto (S3-7),

TI-35 (1-dichloroacetyl-azepane) from TRI-Chemical RT (S3-8), diclonone (dicyclonone) or BAS145138, or LAB145138 (S3-9), ((RS)-1-dichloroacetyl-3,3,8a -trimethylperhydropyrrolo[1,2-a]pyrimidin-6-one) from BASF, furilazole or MON 13900 ((RS)-3-dichloroacetyl-5-(2-furyl)-2,2-dimethyloxazolidine) (S3-10) , as well as its ^)-isomer (S3-11).

S4) Compounds of the acyl sulfonamide class (S4):

S4 ^a ) N-acylsulfonamides of formula (S4 ^a ) and their salts, as described in WO-A-97/45016, o. o o .—urL · d

II // \\ ¹¹ II /~A-1 ^g 'A7tA < ^s * ^a >

Η ^χ=/ ο η in which RA ¹ means (C ₁ -C ₆ )alkyl, (C ₃ -C ₆ )cycloalkyl, where the last 2 radicals are replaced by v _A substituents from the group consisting of halogen, (C1-C ₄ )alkoxy, halo(C1-C ₆ )haloalkoxy and (C1-C ₄ )alkylthio and, in the case of cyclic radicals, also (C1-C ₄ )alkyl and (C1-C ₄ )haloalkyl;

RA ² means halogen, (C1-C ₄ )alkyl, (C1-C ₄ )alkoxy, CF ₃ ;

mA means 1 or 2;

v _D means 0, 1, 2 or 3;

S4 ^b ) compounds of the 4-(benzoylsulfamoyl)benzamides type of formula (S4 ^b ) and salts thereof, as described in WO-A-99/16744,

Rb _o

UN in which RB ¹ , RB ² independently of each other mean hydrogen, (C1- _C6 )alkyl, ( _C3 - _C6 )cycloalkyl, ( _C3 - _C6 )alkenyl, ( _C3 - _C6 ) alkynyl,

RB ³ is halogen, (C1- _C4 )alkyl, (C1- _C4 )haloalkyl or (C1- _C4 )alkoxy, and _mB is 1 or 2;

for example, those in which

R _B ¹ =cyclopropyl, R _B ² =hydrogen and (RB3) 2-OMe (cyprosulfamide, S4-1),

R _B ¹ =cyclopropyl, RB ² =hydrogen and (rb ³ )=5-C1-2-OMc (S4-2),

Rb^tuh, R _B ² =hydrogen and ^ _in ³ )=2-ОМе (S4-3),

R _in ¹ = isopropyl, R ^{in 2} = hydrogen and ^ in ³ ) = 5-C1-2-OMe (S4-4), and

R _in ¹ = isopropyl, R ^{in 2} = hydrogen and ^ in ³ ) = 2-ОМе (S4-5);

S4 ^c ) compounds of the class of benzoylsulfamoylphenylureas of the formula (S4 ^c ), as described in EP-A-365484,

in which RC ¹ , RC ² independently of each other mean hydrogen, (C1- _C8 )alkyl, ( _C3 - _C8 )cycloalkyl, ( _C3 - _C6 )alkenyl, ( _C3 - _C6 )alkynyl,

RC ³ is halogen, (C1-C ₄ )alkyl, (C1-C ₄ )alkoxy, CF ₃ , m _c is 1 or 2;

for example 1-[4-(№2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea,

1-[4-(#2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea, 1-[4-(#4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea;

S4 ^d ) compounds of the N-phenylsulfonyl terephthalamide type (S4 ^d ) and their salts, which are known, for example, from CN 101838227, |° ⁵ o o _{(S4 d)}

O -- H O ^λ -in which RD ⁴ is halogen, (C1-C ₄ )alkyl, (C1-C ₄ )alkoxy, CF ₃ , m _D is 1 or 2;

RD ⁵ means hydrogen, (C1- _C6 )alkyl, ( _C3 - _C6 )cycloalkyl, ( _C2 - _C6 )alkenyl, ( _C2 - _C6 )alkynyl, ( _C5 - _C6 )cycloalkenyl.

S5) Compounds from the class of hydroxyaromatic compounds and aromatic-aliphatic carboxylic acid derivatives (S5), for example triacetoxybenzoic acid 3,4,5-ethyl ester,

- 10 047067

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, WO-A-2OO5/O16OO1.

S6) Active substances from the class of 1,2-dihydroquinoxalin-2-ones (S6), for example 1-methyl-3-(2-thienyl)1,2-dihydroquinoxalin-2-one, 1 -methyl-3-(2- thienyl)-1,2-dihydroquinoxalin-2-thione, 1 -(2-aminoethyl)-3-(2thienyl)-1,2-dihydroquinoxalin-2-one hydrochloride, 1 -(2-methylsulfonylaminoethyl)-3 -(2-thienyl)-1,2dihydroquinoxalin-2-one, as described in WO-A-2OO5/11263O.

S7) Compounds from the class of diphenylmethoxyacetic acid derivatives (S7), for example diphenylmethoxyacetic acid methyl ester (CAS Reg. No. 41858-19-9) (S7-1), diphenylmethoxyacetic acid ethyl ester or diphenylmethoxyacetic acid as described in WO-A-98 /38856.

S8) Compounds of formula (S8) as described in WO-A-98/27O49,

where the symbols and indices have the following meanings:

RD ¹ means halogen, (C ₁ -C ₄ )alkyl, (C ₁ -C ₄ )haloalkyl, (C ₁ -C ₄ )alkoxy, (C ₁ -C ₄ )haloalkoxy,

RD ² means hydrogen or (C1-C4)alkyl,

RD ³ means hydrogen, (C1- _C8 )alkyl, ( _C2 - _C4 )alkenyl, ( _C2 - _C4 )alkynyl or aryl, where each of the above carbon-containing radicals is unsubstituted or substituted by one or more, preferably up to three , the same or different radicals from the group consisting of halogen and alkoxy; or their salts, nD means an integer from 0 to 2.

S9) Compounds from the class of 3-(5-tetrazolylcarbonyl)-2-quinolones (S9), e.g. 1,2-dihydro-4hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No. 219479 -18-2), 1,2-dihydro-4-hydroxy-1methyl-3-(5-tetrazolylcarbonyl)-2-quinolone (registration no. CAS 95855-00-8), as described in WO-A-1999/ 000020.

S10) Compounds of formula (S1O ^a ) or (S1O ^b ), as described in WO-A-2007/023719 and WO-A-2007/023764,

in which RE ¹ means halogen, (C1-C4)alkyl, methoxy, nitro, cyano, CF ₃ , OCF ₃ ,

YE, ZE independently mean O or S, nE means an integer from 0 to 4,

RE ² means (C1- _C16 )alkyl, ( _C2 - _C6 )alkenyl, ( _C3 - _C6 )cycloalkyl, aryl; benzyl, halobenzyl,

RE ³ means hydrogen or (C1-C6)alkyl.

S11) Compounds of the type of hydroxyimino compounds (S11), which are known as seed dressings, such as, for example, oxabetrinyl (^)-1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile) (S11-1), which known as a protective seed treater for millet against metolachlor damage, fluxofenim (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethanone O-(1,3-dioxolan-2-ylmethyl)oxime) ( S11-2), which is known as a seed protectant for switchgrass against metolachlor damage, and ciometrinil or CGA-43089 (^)-cyanomethoxyimino(phenyl)-acetonitrile) (S11-3), which is known as a seed protectant for millet against damage by metolachlor.

S12) Compounds from the class of isothiochromanones (S12), such as, for example, methyl [(3-oxo-1H-2benzothiopyran-4(3H)-ylidene)methoxy] acetate (CAS Reg. No. 205121-04-6) (S12- 1) and related compounds from WO-A-1998/13361.

S13) One or more compounds from the following group (S13):

naphthalic anhydride (1,8-naphthalenedicarboxylic acid anhydride) (S13-1), which is known as a protective seed treater for corn against thiocarbamate herbicide damage, phenoclorim (4,6-dichloro-2-phenylpyrimidine) (S13-2), which is known as a protectant for pretilachlor in rice crops, flurazole (benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-ethyl carboxylic acid ester) (S13-3), which is known as a protectant seed treatment for millet against damage ahlahlo

- 11 047067 rum and metolachlor,

CL 304415 (CAS Reg. No. 31541-57-8) (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4) from American Cyanamid, which is known as a protectant for corn against imidazolinone damage,

MG 191 (registration no. CAS 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia, which is known as a corn protectant,

MG 838 (reg. CAS No. 133993-74-5) (2-propenyl 1-oxa-4-azaspiro[4.5]decane-4-carbodithioate) (S13-6) from Nitrokemia, disulfoton (O,O-diethyl S- 2-ethylthioethyl phosphorothioate) (S13-7), dietholate (O,O-diethyl O-phenyl phosphorothioate) (S13-8), mephenate (4-chlorophenyl methylcarbamate) (S13-9).

S14) Compounds which, in addition to having a herbicidal effect against harmful plants, have a protective effect on agricultural crops such as rice, such as, for example, dimepiperate or MY 93 ^-1-methyl-1-phenylethyl piperidine-1-carbothioate), which is known as a rice protectant against damage by the herbicide molinate, daimuron or SK 23 (1-(1-methyl-1-phenylethyl)-3-p-tolylurea), which is known as a rice protectant against damage by the herbicide imazosulfuron, tsumiluron- 'JC 940 (3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)urea, see JP-A-60087254), which is known as a rice protectant against damage by some herbicides, methoxyphenone or NK 049 (3,3'-dimethyl-4-methoxy-benzophenone), which is known to protect rice against damage by some herbicides,

CSB (1-bromo-4-(chloromethylsulfonyl)benzene) from Kumiai (CAS Reg. No. 54091-06-4), which is known as a rice protectant against damage by certain herbicides.

S15) Compounds of formula (S15) or tautomers thereof

as described in WO-A-2008/131861 and WO-A-2008/131860, in which RH ¹ means a (C1-C ₆ )haloalkyl radical,

RH ² means hydrogen or halogen,

RH ³ , RH4 independently of each other mean hydrogen, (C1-C16)alkyl, ( _C2 -C16)alkenyl or ( _C2 -C16)alkynyl, where each of the last 3 radicals is unsubstituted or is substituted by one or more radicals from group consisting of halogen, hydroxy, 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 heterocyclyl; or (C ₃ -C ₆ )cycloalkyl, (C ₄ -C ₆ )cycloalkenyl, (C ₃ -C ₆ )cycloalkyl which is fused in one ring region with a 4-6 membered saturated or unsaturated carbocyclic ring, or (C ₄ -C ₆ )cycloalkenyl which is fused in one ring region with a 4-6 membered saturated or unsaturated carbocyclic ring, where each of the last 4 radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, hydroxy, cyano, (C1-C ₄ )alkyl, (C1-C ₄ )haloalkyl, (C1-C ₄ )alkoxy, (C1-C ₄ )haloalkoxy, (C1-C ₄ )alkylthio, (C1-C ₄ )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 heterocyclyl; or

RH ³ means (C1- _C4 )alkoxy, ( _C2 - _C4 )alkenyloxy, ( _C2 - _C6 )alkynyloxy or ( _C2 - _C4 )haloalkoxy, and

RH ⁴ means hydrogen or (C1-C ₄ )alkyl, or

RH ³ and RH ⁴ together with the directly bonded N-atom mean a 4-8 membered heterocyclic ring which may contain additional ring heteroatoms other than the N-atom, preferably up to two additional ring heteroatoms from the group consisting of N, O and S, and which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, cyano, nitro, (C1- _C4 )alkyl, (C1- _C4 )haloalkyl, (C1- _C4 )alkoxy, (C1- _C4) )haloalkoxy, and (C1- _C4 )alkylthio.

S16) Compounds which are primarily used as herbicides, but which also have a protective effect on crop plants, for example (2,4-dichlorophenoxy)acetic acid (2,4-D), (4-chlorophenoxy)acetic acid, ^^) -2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),

- 12 047067

4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), (4-chloro-o-tolyloxy)acetic acid (MCPA), 4-(4-chloro-o-tolyloxy)butyric acid, 4- (4-chlorophenoxy)butyric acid, 3,6-dichloro-2-methoxybenzoic acid (dicamba), 1-(ethoxycarbonyl)ethyl-3,6-dichloro-2-methoxybenzoate (lactidichloroethyl).

Very preferred are the protectants s) selected from the group of isoxadiphenethyl, cyprosulfamides, cloquintocet-mexyl and mefenpyr-diethyl. Particularly preferred are mefenpyr-diethyl and cloquintocet-mexyl. Mefenpyrdiethyl is highly preferred. Cereal crop protectants are highly preferred.

Suitable anionic dispersants e1), as emulsifiers, surfactants, wetting agents and dispersants, are, for example, alkali and alkaline earth metal salts or ammonium salts of sulfonates, sulfates, phosphates, ethyl carboxylic acids and mixtures thereof, such as salts of alkylsulfonic acids or alkylphosphonic acids, as well as alkylarylsulfonic or alkylarylphosphonic acids, diphenylsulfonates, alpha-olefin sulfonates, lignosulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, dodecyl- and tridecylbenzenene sulfonates, naphthalene and alkylnaphthalene sulfonates, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, ethoxylated alkylphenols, alcohols, ethoxylated alcohol or fatty acid esters. Examples of phosphates are phosphate esters. Examples of ethyl carboxylic acid ester are alkyl ethyl carboxylic acid ester, as well as carboxylated alcohol or alkyl phenol ethoxylates. Also suitable is the group of anionic emulsifiers of alkali metal salts, alkaline earth metals and ammonium salts of polystyrenesulfonic acids, salts of polyvinylsulfonic acids, salts of alkylnaphthalene sulfonic acids, salts of alkylnaphthalene-formaldehyde condensation products, salts of naphthalene sulfonic acid condensation products, phenolsulfonic acid and formaldehyde. Examples are potassium dodecyl benzene sulfonate, such as Rhodocal® 70/B (Solvay), phenyl sulfonate CA100 (Clariant), or isopropylammonium dodecyl benzene sulfonate, such as Atlox® 3300B (Croda).

Other typical representatives include, among others, phenylsulfonate CA (Ca-dodecylbenzenesulfonate), Soprophor® species (if necessary, esterified tristyrylphenol ethoxylate derivatives), Emmulsogen® 3510 (alkylated EO/PO copolymerisate), Emulsogen® EL 400 (ethoxylated castor oil ), Tween® types (fat-acylated sorbitan ethoxylates), Calsogen® AR 100 (Ca-dodecylbenzenesulfonate). Preferred are combinations of alkylated aromatic sulfonic acid salts, such as Ca phenylsulfonate and/or Calsogen® AR 100, with alkylated ethylene-propylene oxide copolymers, such as Emulsogen® 3510. Particularly preferred are combinations of dodecylbenzene sulfonic acid salts, such as Calsogen® AR 100 with an alkylated copolymerisate from ethylene and propylene oxide, such as Emulsogen® 3510.

Examples of other anionic emulsifiers e1) from the group of naphthalene sulfonates are Galoryl® MT 800 (sodium dibutyl naphthalene sulfonic acid), Morwet® IP (sodium diisopropyl naphthalene sulfonate) and Nekal® BX (alkyl naphthalene sulfonate). Examples of anionic surfactants from the group of condensation products of naphthalene sulfonates with formaldehyde are Galoryl® DT 201 (a hydroxypolymer of naphthalene sulfonic acid with formaldehyde and sodium methylphenol), Galoryl® DT 250 (a condensation product of phenol and naphthalene sulfonates), Reserve® C (a condensation product of phenol and naphthalene sulfonates), naphthalene) or Morwet® D-425, Tersperse® 2020. Preferred are 1,2 with di-butyl or diisobutyl-substituted naphthalene sulfonates, such as the products Galoryl® MT 800 (CFPINufarm) and Nekal® BX (BASF). Other common surfactants are Soprophor® 3D33, Soprophor® 4D384, Soprophor® BSU, Soprophor® CY/8 (Solvay) and Hoe® S3474 and in the form of Sapogenat® T products (Clariant), such as Sapogenat® T 100.

As nonionic dispersants e2), such as emulsifiers, wetting agents, surfactants and dispersants, the usual surfactants present in the formulations of agrochemical active substances are taken into account. For example, ethoxylated nonylphenols, decomposition products of linear or branched alcohols with ethylene oxide and/or propylene oxide, ethylene oxide-propylene oxide block copolymers, alkoxylated linear and branched, saturated and unsaturated alcohols (for example, butoxypolyethylenepropylene glycols) with closed and uncapped end groups, decomposition products of alkyl phenols fishing with ethylene oxide and/or propylene oxide, ethylene oxide-propylene oxide block copolymers, polyethylene glycols and polypropylene glycols, further fatty acid esters, polyglycol fatty acid esters, alkyl sulfonates, alkyl sulfates, aryl sulfates, ethoxylated arylalkyl phenols, such as tristyrylphenol ethoxylate with an average of 16 ethylene oxide units per molecule, further ethoxylated and propoxylated arylalkylphenols, as well as sulfated or phosphated arylalkylphenol

- 13 047067 ethoxylates or -ethoxy-and -propoxylates. Particularly preferred are tristyryl phenol alkoxylates and polyglycol fatty acid ester. Very preferred are tristyryl phenol ethoxylates, tristyryl phenol ethoxy propoxylates and castor oil polyglycol ester, respectively alone or in mixtures. For this purpose, if necessary, additives are used, such as surfactants or fatty acid esters, which help improve the biological effect. Suitable nonionic emulsifiers b2) are, for example, Soprophor® 796/P, Lucramul® CO30, Lucramul® HOT, Lucramul® PSI 100 or Synperonic® T304.

Suitable nonionic dispersants e2) may also be selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinyl alcohol, PVP-dimethylaminoethyl methacrylate copolymer, butylated PVP, vinyl chloride-vinyl acetate copolymer, and partially hydrolyzed vinyl acetate, phenolic resin, modified cellulose types such as eg Luviskol® (polyvinylpyrrolidone), Mowiol® (polyvinyl alcohol) or modified cellulose. Polyvinylpyrrolidone species are preferred, especially low molecular weight species such as Luviskol® K30 or Sokalan® K30 are preferred.

As other nonionic emulsifiers e2) from the group of di- and tri-block copolymers from alkylene oxides, for example, compounds based on ethylene and propylene oxides with an average molar mass of 200-10000, preferably 1000-4000 g are taken into account /mol, with the mass amount of polyethoxylated block varying in the range of 10-80%, such as Synperonic® PE series (Uniqema), Pluronic® PE series (BASF), VOP® 32 or Genapo^PF series (Clariant) .

For ZC formulations, carriers f) of the SC formulation can be added.

The carriers f) are preferably selected from the group consisting of minerals, carbonates, sulphates and phosphates of alkaline earth metals and earth metals, such as calcium carbonate, polymeric carbohydrates, silicic acid, (natural) skeletal silicate, such as kaolin. Common examples of suitable fillers c) are, for example, Agsorb® LVM®-GA (attapulgite), Harborlite® 300 (perlite), Collys® HV (modified starch), Omya®-chalk (calcium carbonate), Kaolin® Tec 1 (kaolin , hydrous aluminum silicate), Steamic® OOS (talc, magnesium silicate).

Further preferred for f) are natural skeletal silicates and types of calcium carbonates such as Omya®-chalk (calcium carbonate), kaolin Tes 1® (kaolin) and Harborlite® 300 (perlite), especially preferred are natural skeletal silicates such as kaolin, Tes ® 1 (kaolin, hydrous aluminum silicate) and Harborlite® 300 (perlite). Other fillers in SC formulations according to the invention are selected from the group consisting of minerals, carbonates, sulfates and phosphates of alkaline earth metals and earth metals, such as calcium carbonate, polymeric carbohydrates, skeletal silicates, such as precipitated silicic acid with low absorption capacity and natural skeletal silicates, such as kaolin. Common examples of suitable fillers c) are, for example, Agsorb® LVM®-GA (attapulgite), Harborlite® 300 (perlite), Collys® HV (modified starch), Omya®-chalk (calcium carbonate), Kaolin® Tec 1 (kaolin , hydrous aluminum silicate), Steamic® OOS (talc, magnesium silicate). Suitable ones are, for example, modified natural silicates such as chemically modified bentonite, hectorite, attapulgite, montmorillonite, smectite or other silicate minerals such as Bentone® (Elements), Attagel® (Engelhard), Agsorb® (Oil-Dri Corporation) or Hectorite® (Akzo Nobel) or Van Gel series (R.T. Vanderbilt).

Particularly preferred are carriers c) selected from the group having a base capable of absorbing moisture well, with an absorption capacity of at least 200 g of dibutyl phthalate per 100 g of carrier material (specific surface area of solid particles determined by the BET method, according to ISO 9277). such as synthetic precipitated silicic acid with high absorption capacity (Sipernat® types) as well as pyrogenic silicic acid (Aerosil® types).

The capsule suspension concentrates according to the invention are excellent for applying the agrochemical active ingredients contained to plants and/or their habitat. They ensure the release of active components in appropriately required quantities over a long period of time.

In practice, the capsule suspension concentrates according to the invention can be used either in pure form or after preliminary dilution with water. In this case, application occurs using conventional methods, such as watering, spraying or spraying.

Consumption rates for capsule suspension concentrates according to the invention can vary over a wide range. They depend on the respective agrochemical active ingredients and their content in the microcapsule formulations.

A further subject of the invention is the use of a capsule suspension concentrate according to the invention or a ZC formulation according to the invention as a herbicide in cereal crops and rapeseed in the pre-emergence period and also in the post-emergence period.

The preferred application of the capsule suspension concentrates according to the invention is as a herbicide in cereal crops and rapeseed, very preferably in winter cereals and during the pre-emergence period, as well as during the post-emergence period. Therefore, it is preferable

- 14 047067 can be used during application in the autumn immediately after sowing grain crops and immediately before or after the germination of weeds and weeds.

The capsule suspension concentrates according to the invention can be prepared in a known manner, for example in the form of mixed formulations of the individual components, if necessary with additional active substances, additives and/or customary formulation auxiliaries, which are then diluted in the usual manner with water for use, or are obtained in the form of so-called tank mixtures after a general dilution of the individual components obtained separately or partially separated with water. Time-shifted use (separate use) of separated or partially separated individual components is also possible. It is also possible to apply the individual components or capsule suspension concentrates according to the invention in several portions (sequential application), for example, a pre-emergence application followed by a post-emergence application or an early post-emergence application followed by a mid or late post-emergence application. In this case, it is preferable to use the active ingredients in appropriate combinations together or topically.

Thus, the subject of the present invention is a method for controlling unwanted plants in plant crops, characterized in that the capsule suspension concentrate according to the invention or the ZC formulation according to the invention is applied to the plants, or to the surface on which the plants grow.

Undesirable plants should be understood as all plants that grow in areas where they are undesirable. These can be, for example, harmful plants (for example, monocotyledonous or dicotyledonous weeds or undesirable crop plants).

Monocot weeds, such as the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus ), Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa ), Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum ), Phalaris (canary grass), Phleum (timothy grass), Roa (blue grass), Rottboellia (rottbelia), Sagittaria (arrowhead), Scirpus (reed), Setaria (bristle grass) and Sorghum (sorghum).

Dicotyledonous weeds, for example, the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis ), Bidens (chain), Capsella (shepherd's purse), Carduus (thistle), Cassia (cassia), Centaurea (cornflower), Chenopodium (pigweed), Cirsium (thistle), Convolvulus (convolvulus), Datura (datura), Desmodium ( Desmodium), Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Geranium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica (nettle), Veronica (speedwell), Viola (violet) and Xanthium (cocklebur).

Preferably, the capsule suspension concentrates according to the invention are used to control weeds.

The formulations according to the invention can be used in vegetable crops and especially in potatoes.

If the capsule suspension concentrates according to the invention are applied to the soil surface before sprouting, the growth of the weed sprouts is completely stopped, or the weeds grow to the cotyledon stage, but then their growth stops and they eventually die within 3-4 weeks after the start of growth.

When applying a product containing capsule suspension concentrates according to the invention to the green parts of plants during post-emergence application after treatment, a radical cessation of growth also occurs very quickly, and the weeds remain at the growth stage at which they were at the time of application, or die completely after a certain period of time, thus eliminating competition in the form of harmful weeds very early and for a long period.

Capsule suspension concentrates according to the invention are characterized by rapid application and long-lasting herbicidal effect. The named properties and advantages are necessary for practical weed control in order to prevent the appearance of undesirable competitive plants in agricultural crops and thus preserve quantitatively and qualitatively and/or

- 15 047067 increase productivity. These new products according to the invention significantly exceed the technical standard regarding the described properties.

Although the capsule suspension concentrates according to the invention have excellent herbicidal activity against mono- and dicotyledonous weeds, cultivated plants of economically important crops, for example, dicotyledonous crops such as soybeans, cotton, rapeseed, sugar beets, or cereal crops such as wheat, barley, rye, oats, millet, rice or corn, only little or no harm is caused. Therefore, the capsule suspension concentrates according to the invention are very well suited for the selective control of undesirable plant growth in crops of agricultural useful or ornamental plants.

In addition, the capsule suspension concentrates according to the invention have excellent plant growth regulating properties. They intervene and regulate plant metabolism, and this can be used to specifically influence plant components and to facilitate harvesting, such as by triggering desiccation and growth arrest. They further make it possible to generally regulate and retard unwanted vegetative growth without destroying the plant. Retarded vegetative growth plays an important role in many mono- and dicotyledonous crops; for example, this way can reduce or completely prevent losses during storage.

Due to their herbicidal and growth regulating properties, the capsule suspension concentrates according to the invention can also be used to control pests in crops of known or new plants modified by genetic engineering or conventional mutagenesis. Transgenic plants are generally distinguished by particularly advantageous properties, for example by their resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or their pathogens, such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties generally relate to the harvested crop, regarding quantity, quality, storage stability, composition and special components. Thus, transgenic plants with increased starch content or altered starch properties, or plants with a different fatty acid composition in the harvested crop are known.

Preferred is the use of capsule suspension concentrates according to the invention for economically important transgenic crops of useful and ornamental plants, for example, for cereals such as wheat, barley, rye, oats, millet, rice, rapeseed and corn. The products according to the invention can preferably be used as herbicides in industrial crops that are resistant to the phytotoxic effects of herbicides or have become resistant due to genetic engineering methods. Particularly preferred is application on wheat, barley, rye and rapeseed, preferably winter rapeseed.

When using capsule suspension concentrates according to the invention in transgenic crops, in addition to the observed results in relation to harmful plants, in other crops results that are specific to these transgenic crops often occur, for example, a changed or specially expanded range of weeds that can be suppressed, a changed quantity used , which can be used for application, preferably has good compatibility with herbicides to which transgenic crops are resistant, as well as an effect on the growth and yield of transgenic crops.

Further, the present invention also provides a method for controlling unwanted plant growth, preferably in plant crops such as cereals (e.g. wheat, barley, rye, oats, rice, corn, millet), especially preferably in monocotyledonous crops such as cereals, for example, wheat, barley, rye, oats, their crosses, such as triticale, rice, corn and millet, wherein one or more capsule suspension concentrates according to the invention are applied to harmful plants, plant parts, plant seeds or to the surface on which plants grow, for example, on a cultivated surface. Preferably, the application of capsule suspension concentrates according to the invention occurs during the pre-emergence and post-emergence periods. Particularly preferable application occurs in the pre-emergence period.

The capsule suspension concentrates according to the invention can be used as herbicides for the control of harmful plants in crops of beneficial plants in transgenic crop plants.

The invention is explained in detail using the following examples.

Examples

Substances used and their abbreviations.

The terms used in the following examples have the following meanings.

- 16 047067

Mefenpyr-diethyl Diethyl (7?6)-1-(2,4-dichlorophenyl)-5-methyl-2-pyrazoline3,5-diethyl ester of carboxylic acid, (Bayer AG), temperature 50 - 55°C, MPR Flufenacet 4'-fluoro-M-isopropyl-2-(5-trifluoromethyl-1,3,4-thiadiazol-2yloxy)acetanilide (Bayer AG), FFA Diflufenican 2',4'-difluoro-2-(a,a,a-trifluoro-n-tolyloxy)nicotinanide (Bayer AG), DFF Cloquintocet-mexyl (RS)-1-methylhexyl (5-chloroquinolin-8-yloxy)acetate (Syngenta), melting temperature range 60-70°C, CQM DCPMI 2-[(2,4-dichlorophenyl)-methyl]-4,4'-dimethyl-3- isoxazolidinone (No. C AS 81777-95-9 or IPUAC 2-(2,4dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, hereinafter called DCPMI) Morweg® D-425 naphthalene sulfonic acid-formaldehyde-sodium salt condensate (Akzo Nobel) Pluronic® PE 10500 propylene oxide-ethylene oxide-(PO-EO)-block polymer (BASF) Lemon acid polybasic organic acids Rhodopol® G xanthan derivative (Solvay) Silcolapse® 426R, 411 Silicone based defoamer (Solvay) Glycerol low freezing coolant Proxel® GXL preservative (biocide, Proxel) Solvesso® 200 ND mineral oil, ExxonMobil, naphthalene-free Desmodur® 44V20L polymers MDI, Covestro AG, functionality 2.7. HDA 1,6-hexamethylenediam, BASF

Reax 88B lignosulfonate from MeadWestVaco

Receipt example.

Example 1 (according to the invention) (CS-formulation).

14.23 g of DCPMI and 7.14 g of mefenpyr-diethyl were dissolved at 50°C in 21.4 g of Solvesso® 200 ND.

The solution was added to a mixture of 1.1 g Desmodur® 44V20L, 1.51 g Reax 88B, plus 0.2 g Silcolapse® 426R and 0.18 g Kathon® CG/ICP in 53.78 g water with 0.36 g hexamethylenediamine. Dispersed using a dispersant at 15,000 rpm for 10 minutes. The resulting reaction mixture is heated over 1 hour to 70°C and over the next 4 hours the temperature is slowly maintained at 70°C with stirring. After further cooling to room temperature, it is concentrated with 0.1 g of Rhodopol® G. This gives a microcapsule formulation containing 150 DCPMI and 75 g/l menfenpyr-diethyl with a particle size of 8.3 μm (d90).

A KS-preparative form with a density of 1.05 is formed.

Example 2 (according to the invention) (CS-formulation).

14.23 g of DCPMI and 7.14 g of cloquintocet-mexyl were dissolved at 50°C in 21.4 g of Solvesso® 200 ND.

The solution was added to a mixture of 1.1 g Desmodur® 44V20L, 1.51 g Reax 88B, plus 0.2 g Silcolapse® 426R and 0.18 g Kathon® CG/ICP in 53.78 g water with 0.36 g hexamethylenediamine. Dispersed using a dispersant at 15,000 rpm for 10 minutes. The resulting reaction mixture is heated over 1 hour to 70°C and over the next 4 hours the temperature is slowly maintained at 70°C with stirring. After further cooling to room temperature, it is concentrated with 0.1 g of Rhodopol® G. This gives a microcapsule formulation (CM) containing 150 DCPMI and 75 g/l cloquintocet-mexyl with a particle size of 8.3 μm (d90).

- 17 047067

Comparative example 1 (CS formulation).

14.23 g of DCPMI was dissolved at 50°C in 21.4 g of Solvesso® 200 ND.

The solution was added to a mixture of 1.1 g Desmodur® 44V20L, 1.51 g Reax 88B, plus 0.2 g Silcolapse® 426R and 0.18 g Kathon® CG/ICP in 60.92 g water with 0.36 g hexamethylenediamine. Dispersed using a dispersant at 15,000 rpm for 10 minutes. The resulting reaction mixture is heated over 1 hour to 70°C and over the next 4 hours the temperature is slowly maintained at 70°C with stirring. After subsequent cooling to room temperature, it is concentrated with 0.1 g of Rhodopol® G. This gives a microcapsule formulation with a DCPMI content of 150 g/l and a particle size of 8.3 μm (d90).

SC-preparative forms.

To obtain the ZC formulation according to the invention, the following SC formulations were obtained as mixing partners. They, together with the formulations according to the invention, were mixed with other formulations according to the invention.

Preparation of SA preparative forms based on a protective agent.

The preparation of a SC formulation based on a protective agent (cloquintocet-mexyl or mefenpyr-diethyl) occurs in a similar manner to BCS 15 3 070, while the protective agent is added warm as a melt to the formulation. Stir for 2-24 hours until crystals form. Then grinding occurs in a wet state, for example, using a bead mill. An organic thickener is then added.

Obtaining an aqueous suspension concentrate.

To obtain the examples listed in the table, first of all, the water is left at room temperature. Then, while stirring, add other components (in no particular order of addition). Then grinding occurs in a wet state, for example, using a bead mill. An organic thickener is then added.

Received formulations

SC-1 SC-2 SC-3 SC-4 Mefenpyr-diethyl 27.27 Cloquintosetmexil 27.27 Flufenacet 42.37 Diflufenican 42.37 Morwet® D-425 1.0 1.0 1.0 1.0 Pluronic®PE 10500 5 5 5 5 lemon acid 0.1 0.1 0.1 0.1 Aerosil® 200 0.5 0.5 0.5 0.5 Rhodopol® 23 0.2 0.2 0.2 0.2 Silcolapse® 411 0.5 0.5 0.5 0.5 Glycerol 5 5 5 5 Proxel® GXL 0.18 0.18 0.18 0.18 Total added water to 100% Density of the formulation 1.1 1.1 1D9 1.19 g/l content of active substance 300 300 500 500

Obtained ZC-preparative forms (finished preparative forms).

The corresponding formulations according to the invention are mixed with other active ingredients. Then add water to 1 liter.

- 18 047067

Example 3 4 5 Compare n.2 Compare n. 3 Type of formulation ZC ZC ZC ZC ZC Example 1 (CS 150 g/l DCPMI and 75 g/l MPR) 0.666 7l 0.666 7l 0.666 7l Comparative Example 1 (CS 150 g/l DCPMI) 0.666 7l 0.333 3 l SC-1 (MPR SC 300 g/l) 0.333 3 l 0.166 7 l SC-3 (DFF SC 500 g/l) 0.06 l SC-4 (FFA SC 500 g/l) 0.15 l 0.2 l 0.12 l 0.075 l Add water to 1 liter 0.183 3 l 0.133 3 l 0.153 3 l 0 0.425 l Total load in g/l 225 250 240 150 137.5 g/l DCPMI 100 100 100 100 50 g/l MPR 50 50 50 50 50 g/l DFF thirty 0 g/l FFA 75 100 60 0 37.5 Consumption rates for field testing in l/ha 2 2 2 2 4 g active ingredient DCPMI per ha 200 200 200 200 200 g protective agent MPR per ha 100 100 100 100 100 g active ingredient DFF per ha 60 g FFA active ingredient per ha 150 200 120 150 Stability of the formulation after 8W40°C storage decree but decree decree decree But Not decree relative humidity after 72 hours DCPMI 85% 85% 85% 85% 85%

The composition of Comparative Example 3 shows agglomerates and crystal growth in the formulation. When the product was wet sifted on a 150 micron sieve, 3% of the active substance remained.

Determination of the relative humidity of the active substance.

Spray liquid (0.5 g active ingredient/L) was added to three Teflon membranes in an open top glass box in a laboratory fume hood with a constant air flow of 1.6 m/s at 22°C and 60% relative humidity. The residue on Teflon membranes after drying after 0 and 72 h was examined using HPLC. Volatility relative to 0 h value

- 19 047067 readings. Those. a value of 85% is called relative volatility; 85% of the active substance is non-volatile and remains on the Teflon membrane.

The results in the above table show that the volatility of the protectant is not negatively affected and thus the volatility control of DCPMI remains at a very high level.

Tests in a greenhouse.

During standard experiments, seeds of various biotypes (of different origins) of weeds and weed biotypes are sown in a pot with a diameter of 8-13 cm, filled with ordinary soil (clay sand; non-sterile), and covered with a layer of soil of approximately 1 cm. The pots are then cultivated in a greenhouse ( 12-16 hours of light, daytime temperature 20-22°C, night temperature 15-18°C) until application. The pots are treated with spray liquids, mixtures/formulations according to the invention, new mixtures or individual components used on a special laboratory surface. Application in the form of WG, WP, EC or other formulations or combinations of active substances is carried out at certain stages of plant growth. The water consumption when applied by spraying was 100-600 l/ha. After treatment, the plants are again placed in greenhouses.

Approximately 3 weeks after application, an external assessment of soil and/or plant effects was carried out on a scale of 0-100% compared to the untreated control group:

0%=no significant effect compared to untreated control group;

100%=full effect compared to untreated control group.

(Note: The concept of seeds also includes vegetative forms of propagation, such as parts of rhizomes. Abbreviations used: h light = hours of light duration, g AB/ha = grams of active substance per hectare, l/ha = liter per hectare, S = sensitive, R=resistant).

1. Effect on weeds in the pre-emergence period. Seeds of various biotypes (of different origins) of weeds and weed biotypes are sown in a pot with a diameter of 8-13 cm, filled with ordinary soil (clay sand; non-sterile), and covered with a layer of soil of approximately 1 cm. The pots are then cultivated in a greenhouse (12-16 hours of light , daytime temperature 20-22°C, night temperature 15-18°C) until application. Pots at the seed/plant stage BBSN 00-10 are treated with spray liquids of mixtures/formulations according to the invention, mixtures or individual components used, such as WG, WP, EC or other formulations, on a special laboratory surface. The water consumption when applied by spraying was 100-600 l/ha. After treatment, the plants are again placed in greenhouses and, if necessary, further fertilized and irrigated.

2. Effect on weeds in the post-emergence period. Seeds of various biotypes (of different origins) of weeds and weed biotypes are sown in a pot with a diameter of 8-13 cm, filled with ordinary soil (clay sand; non-sterile), and covered with a layer of soil of approximately 1 cm. The pots are then cultivated in a greenhouse (12-16 hours of light , daytime temperature 20-22°C, night temperature 15-18°C) until application. Pots at different stages of seed/plant VSN, between 11-25, i.e. Typically, between two and three weeks after the start of cultivation, spray liquids with mixtures/formulations according to the invention, mixtures or individual components used, such as WG, WP, EC or other formulations, are treated on a special laboratory surface. The water consumption when applied by spraying was 100-600 l/ha. After treatment, the plants are again placed in greenhouses and, if necessary, further fertilized and irrigated.

3. Effect on weeds in the pre-emergence period with and without the introduction of active substances. Seeds of various biotypes (of different origins) of weeds and weed biotypes are sown in a pot with a diameter of 8-13 cm filled with ordinary soil (clay sand, non-sterile). Pots of seeds for comparison or are treated at the seed/plant stage 00-10, i.e. usually between two and three weeks after the start of cultivation, spray liquids with mixtures/formulations according to the invention, mixtures or individual components used, such as WG, WP, EC or other formulations, on a special laboratory surface, or an equivalent number of mixtures/formulations According to the invention, mixtures or separately used components, such as WG, WP, EC or other preparative forms, are introduced into the surface layer of the earth by approximately 1 cm. The water consumption during spray application was 100-600 l/ha. After treatment, the plants are again placed in greenhouses and, if necessary, further fertilized and irrigated. The pots are cultivated in a greenhouse (12-16 hours of light, daytime temperature 20-22°C, night temperature 15-18°C).

4. Selective action in the pre-emergence period. Seeds of various cultivated species (of different origins) of weeds and weed biotypes are sown in a pot with a diameter of 8-13 cm, filled with ordinary soil (clay sand, non-sterile), and covered with a layer of soil of approximately 1 cm. Then the pots are cultivated in a greenhouse (12-16 hours light, daytime temperature 20-22°C, night temperature 15-18°C) until application. Pots at the seed/plant stage BBSN 00-10 are treated with spray liquids of mixtures/formulations according to the invention, mixtures or individual components used, such as WG, WP, EC or other formulations, on a special laboratory surface. The water consumption when applied by spraying was 100-600 l/ha. After treatment, the plants are again placed in greenhouses and, if necessary, further fertilized and irrigated.

- 20 047067

5. Selective action in the post-emergence period. Seeds of various cultivated species (of different origins) of weeds and weed biotypes are sown in a pot with a diameter of 8-13 cm, filled with ordinary soil (clay sand, non-sterile), and covered with a layer of soil of approximately 1 cm. Then the pots are cultivated in a greenhouse (12-16 hours light, daytime temperature 20-22°C, night temperature 15-18°C) until application. Pots at different stages of VSN seeds/plants, 11-32, i.e. Typically, between two and four weeks after the start of cultivation, spray liquids with mixtures/formulations according to the invention, mixtures or individual components used, such as WG, WP, EC or other formulations, are treated on a special laboratory surface. The water consumption when applied by spraying was 100-600 l/ha. After treatment, the plants are again placed in greenhouses and, if necessary, further fertilized and irrigated. The pots are cultivated in a greenhouse (12-16 hours of light, daytime temperature 20-22°C, night temperature 15-18°C).

6. Effect on weeds when used before sowing. Seeds of various biotypes (of different origins) of weeds and weed biotypes are sown in a pot with a diameter of 8-13 cm filled with ordinary soil (clay sand, non-sterile). The seed pots are treated with spray liquids of mixtures/formulations according to the invention, mixtures or individual components used, such as WG, WP, EC or other formulations, on a special laboratory surface. The water consumption when applied by spraying was 100-600 l/ha. After sowing, the pots are placed in greenhouses and, if necessary, further fertilized and irrigated. The pots are cultivated in a greenhouse (12-16 hours of light, daytime temperature 20-22°C, night temperature 15-18°C).

7. Effect on weeds in the pre- and post-emergence period under different cultivation conditions. Seeds of various biotypes (of different origins) of weeds and weed biotypes are sown in a pot with a diameter of 8-13 cm, filled with ordinary soil (clay sand; non-sterile), and covered with a layer of soil of approximately 1 cm. The pots are then cultivated in a greenhouse (12-16 hours of light , daytime temperature 20-22°C, night temperature 15-18°C) until application. Pots at different stages of seeds/plants BBSN 00-25 are treated with spray liquids of mixtures/formulations according to the invention, mixtures or individual components used, such as WG, WP, EC or other formulations, on a special laboratory surface. The water consumption when applied by spraying was 100-600 l/ha. After treatment, the plants are again placed in greenhouses and, if necessary, further fertilized and irrigated. The pots are cultivated in a greenhouse (12-16 hours of light, daytime temperature 20-22°C, night temperature 15-18°C). Irrigation may vary if necessary. At the same time, separate control groups provide water differentially, from a level above PWP (continuous wilting point) and up to the level of maximum soil capacity.

8. Effect on weeds in the pre- and post-emergence period under different irrigation conditions. Seeds of various biotypes (of different origins) of weeds and weed biotypes are sown in a pot with a diameter of 8-13 cm, filled with ordinary soil (clay sand; non-sterile), and covered with a layer of soil of approximately 1 cm. The pots are then cultivated in a greenhouse (12-16 hours of light , daytime temperature 20-22°C, night temperature 15-18°C) until application. Pots at different stages of seeds/plants BBSN 00-25 are treated with spray liquids of mixtures/formulations according to the invention, mixtures or individual components used, such as WG, WP, EC or other formulations, on a special laboratory surface. The water consumption when applied by spraying was 100-600 l/ha. After treatment, the plants are again placed in greenhouses and, if necessary, further fertilized and irrigated. The pots are cultivated in a greenhouse (12-16 hours of light, daytime temperature 20-22°C, night temperature 15-18°C). At the same time, different irrigation technologies are used in separate control groups. Irrigation is carried out either differentially above or below previously established levels (modeled sprinkling).

9. Effect on weeds in the pre- and post-emergence period under different soil conditions. Seeds of various biotypes (of different origins) of weeds and weed biotypes are sown in a pot with a diameter of 8-13 cm, filled with ordinary soil and covered with a layer of soil of approximately 1 cm. To compare the herbicidal effect, plants were cultivated on various types of soil, from sandy soil to heavy clay soil and different content of organic substances. The pots are then cultivated in a greenhouse (12-16 hours of light, daytime temperature 20-22°C, night temperature 15-18°C) until application. Pots at different stages of seeds/plants BBSN 00-25 are treated with spray liquids of mixtures/formulations according to the invention, mixtures or individual components used, such as WG, WP, EC or other formulations, on a special laboratory surface. The water consumption when applied by spraying was 100-600 l/ha. After treatment, the plants are again placed in greenhouses and, if necessary, further fertilized and irrigated. The pots are cultivated in a greenhouse (12-16 hours of light, daytime temperature 20-22°C, night temperature 15-18°C).

10. Effect on weeds in the pre- and post-emergence period to control resistant weeds/weeds. Seeds of different biotypes (of different origins) of weeds and weed biotypes with different mechanisms of resistance to different mechanisms of action are sown in a pot with a diameter of 8-13 cm filled with ordinary soil (clay sand, LSI; pH 7.4; % C org. 2.2) and cover with a layer of soil of about 1 cm. Then the pots are cultivated in a greenhouse (12-16 hours of light, daytime temperature about 23°C,

- 21 047067 night temperature about 15°C) before application. Pots at different stages of seeds/plants BBSN 00-25 are treated with spray liquids of mixtures/formulations according to the invention, mixtures or individual components used, such as WG, WP, EC or other formulations, on a special laboratory surface. The water consumption during spray application was 300 l/ha. After treatment, the plants are again placed in greenhouses and, if necessary, further fertilized and irrigated. The pots are cultivated in a greenhouse (12-16 hours of light, daytime temperature about 23°C, night temperature about 15°C).

11. Effect on weeds and selectivity of crops in the pre- and post-emergence period under different sowing conditions. Seeds of various biotypes (of different origin) and cultivated species (origin) of weeds and weed biotypes are sown in a pot with a diameter of 8-13 cm filled with ordinary soil and covered with a layer of soil of approximately 0-5 cm. Then the pots are cultivated in a greenhouse (12-16 hours light, daytime temperature 20-22°C, night temperature 15-18°C) until application. Pots at different stages of seeds/plants BBSN 00-25 are treated with spray liquids of mixtures/formulations according to the invention, mixtures or individual components used, such as WG, WP, EC or other formulations, on a special laboratory surface. The water consumption when applied by spraying was 100-600 l/ha. After treatment, the plants are again placed in greenhouses and, if necessary, further fertilized and irrigated. The pots are cultivated in a greenhouse (12-16 hours of light, daytime temperature 20-22°C, night temperature 15-18°C).

12. Effect on weeds in the pre- and post-emergence period at different soil pH values. Seeds of various biotypes (of different origins) of weeds and weed biotypes are sown in a pot with a diameter of 8-13 cm, filled with ordinary soil and covered with a layer of soil of approximately 1 cm. To compare the herbicidal effect, plants were cultivated on different types of soil, on ordinary soil (clay sand) with different values of pH 7.4 and pH 8.4. For a higher pH value, lime was mixed into the soil accordingly. The pots are then cultivated in a greenhouse (12-16 hours of light, daytime temperature 20-22°C, night temperature 15-18°C) until application. Pots at different stages of seeds/plants BBSN 00-10 are treated with spray liquids of mixtures/formulations according to the invention, mixtures or individual components used, such as WG, WP, EC or other formulations, on a special laboratory surface. The water consumption when applied by spraying was 100-600 l/ha. After treatment, the plants are again placed in greenhouses and, if necessary, further fertilized and irrigated. The pots are cultivated in a greenhouse (12-16 hours of light, daytime temperature 20-22°C, night temperature 15-18°C).

Results obtained in a greenhouse.

Accordingly, Composition 1 (MPR protectant in capsule) as well as Comparative Composition 1 (MPR protectant outside capsule) were compared with each other. The usual rate of application on the field is at 200 g a.v./ha DCPMI, as well as 100 g a.v./ha mefenpyr-diethyl. The application window was the early pre-emergence period (BBSN 11). In order to produce maximum harm, consumption rates were increased to factor 2 in the greenhouse._________________________________________

Formulations used Consumption rates Damage on winter wheat in % Damage to barley in % Comparative example 1 100 tDCPMIh 50 g MPR/ha 0 0 Example 1 100 tDCPMIh 50 g MPR/ha 0 0 Comparative example 1 200 g DCPMI and 100 rMPR/ra 0 0 Example 1 200 g DCPMI and 100 rMPR/ra 0 0 Comparative example 1 400 g DCPMI and 200 rMPR/ra 0 0 Example 1 400 g DCPMI and 200 rMPR/ra 0 0

The formulations according to the invention of the herbicidal active substance show a very high effect, with little damage. Surprisingly, no differences could be found, although a protectant (CS) was present in the examples in the delayed-release formulation.

- 22 047067

Field test.

During field tests in natural conditions, during normal field preparation and with natural or artificial infestation of harmful plants, before or after sowing crops or before or after germination of harmful plants, apply the product according to the invention, the new mixtures or individual components and give a visual assessment after 4 weeks to 8 months after treatment compared to untreated fragments (small plots of land). At the same time, damage to cultivated plants and the effect against harmful plants, as well as other results of the corresponding subject of experiment, are recorded in percentage terms.

b) Results.

The following abbreviations were used.

ВВСН=ВВСН-code provides information about the morphological stage of plant development. The abbreviation officially means the Federal Office of Biology, the Office for the Protection of Plant Varieties and the Chemical Industry. The value VSN 00-10 indicates the stages of seed germination before appearing on the surface. The value of VSN 11-25 indicates the stages of leaf development before the appearance of shoots (the corresponding number of sprouts or lateral shoots).

PE=application before planting on soil; VSN of seeds/plants 00-10.

PO=application after emergence to green parts of plants; VSN plants 11-25.

HRAC=international 'Herbicide Resistance Action Committee', which categorizes authorized active substances according to their mechanism of action (syn. 'Mode of Action'; MoA).

HRAC group A = acetyl-coenzyme A-carboxylase inhibitors (MoA: ACCase).

HRAC group B = acetolactate synthase inhibitors (MoA: ALS).

AB=active active substance (relative to 100% of the active substance; syn. a.v. (English: a.i..)).

Dosage g AB/ha=consumption rate in grams of active substance per hectare.

To designate the mousetail foxtail biotype (botanical name: Alopecurus myosuroides; EPPO code or former Bayer code: ALOMY), use the EPPO code with the additional designation:

ALOMY_DEU12053 indicates a biotype with increased metabolic ALS resistance (EMR) without Target Site Resistance (TSR) to ALS.

ALOMY_DEU12061 indicates a biotype with increased metabolic ACCase resistance (EMR) without Target Site Resistance (TSR) to ACCase.

ALOMY_R35 denotes a biotype that is sensitive to herbicides with an ALS or ACCase mechanism of action (syn. 'Mode of Action'; MoA).

The actions of herbicidal formulations according to the invention meet the requirements and, thus, solve the problem of improving the profile of the use of the herbicidal active substance 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-3-isoxazolidinone (also obtaining a universal application of the solution relative to the required consumption rate at a constant to increasing efficiency).

In general, the herbicidal results of the product according to the invention, compared with mixtures of the prior art or separately used components, have a better effect on economically important mono- and dicotyledonous pests, the synergistic herbicidal effects were calculated using the Colby-Formel formula (cf. S.R. Colby; Weeds, 15 (1967), 20-22).

Field test of herbicidal effectiveness of aqueous dispersions.

Way. The standard field application in autumn is 200 l/ha of spray liquid with the addition of 150 g of flufenacet, 200 g of DCPMI and 100 g of mefenpyr-diethyl per hectare. We assessed herbicidal effectiveness on foxtail foxtail (Alopecurus myosuroides; ALOMY), phytotoxicity on cultivated plants of winter barley and winter wheat; as well as damage to neighboring crops (tree plantations, sugar beets, broccoli). Conducted an external assessment of effect on a scale of 0-100% compared with the untreated control group: 0%=no significant effect compared with the untreated control group; 100%=full effect compared to untreated control group.

Field test results - early post-emergence period, VSN 11

Example Herbicidal effectiveness against ALOMY Phytotoxicity to... Winter wheat Example 3 good (80%) insignificant (5%) Comparative example 3 good (80%) insignificant (5%)

- 23 047067

The assessment was carried out at the end of March (application at the end of September). The formulations according to the invention show a very high effect without causing damage. They could not establish differences between the formulations, although here the protective agent is also released slowly.

Claims (12)

1. Capsule suspension concentrate for the control of unwanted plants in plant crops, containing A) granular dispersed phase, which is a capsule containing a) a reaction product of at least one compound with isocyanate-reactive groups a1) and an isocyanate mixture a2), b) active substance, s) a protective agent s) dissolved in an organic, water-insoluble solvent L), wherein the protective agent s) is selected from the group consisting of isoxadifen-ethyl, cyprosulfonamides, cloquintocet-mexyl and mefenpyr-diethyl, and B) a liquid aqueous phase, wherein the particles of the dispersed phase A) have an average particle size of 1-50 μm. 2. Capsule suspension concentrate according to claim 1, characterized in that it additionally contains one or more additives c). 3. Capsule suspension concentrate according to claim 1 or 2, characterized in that it additionally contains at least one protective colloid c1). 4. Capsule suspension concentrate according to one of the preceding paragraphs, characterized in that it additionally contains at least one non-encapsulated active substance z). 5. Capsule suspension concentrate according to one of the preceding paragraphs, characterized in that the active substance b) is selected from the group including anilofos, acephate, benfluralin, bifenthrin, bupyrimate, butralin, chloroacetic acid, cyfluthrin, cinmethylin, cypermethrin, demeton^-methylsulfone, dimethamethrin, dimethoate, dioxabenzophos, diphenylamine, dithiopyr, dodemorphacetate, esfenvalerate, ethalfluralin, etofumesate, phenazaquin, phenytropan, fenoxycarb, fenuron-TSA, fenvalerate, fluoroglycophen-ethyl, flupyradifuron, flurazole, flurochloridone-meptyl, , flusilazole, furalaxyl, haloxyfop- ethyl, haloxyfop-methyl, imazalil, ioxynyl octanoate, isoprothiolane, metalaxyl, methomyl, metoprothrin, monocrotophos, nitrapyrine, nitrotal-isopropyl, penconazole, pendimethalin, permethrin, propamocarb hydrochloride, propaquizafop, pyrazophos, quizalofop-Rtefuril, resmethrin, acetic acid, tetramethrin , thiophanox, triflumizole, pyridafenthione, 2-phenylphenol, dimethylvinphos, beta-cypermethrin, famfur, clodinafop-propargyl, triazamate, tebufenpyrad, pyrimidifen, aldrin, bromophos, dialifos, pyriminobac-methyl, benzoylprop, benzoylpropethyl, binapacryl, camphechlor, chlorphenetol, chlorphen prop , chlorphenprop-methyl, chlorfoxime, crufomate, ciometrinil, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane, dimethylane, dinobuton, fenson, fentiaprop, fentiaprop-ethyl, fluenethyl, glyodine, 2-isovalerylindan-1 ,3-dione, methoxyphenone, 2-methoxyethylmercuric chloride, nitrophen, indanophane, acequinocyl, ipsdienol with (b)-cis-verbenol. phenoxanil, pyraclostrobin, trifloxystrobin, cyflufenamide, gamma-cyhalothrin, proquinazide, 2,6-diisopropylnaphthalene, isothianyl and 2-[(2,4-dichlorophenyl)methyl]-4,4'-dimethyl-3-isoxazolidinone (DCPMI). 6. Capsule suspension concentrate according to one of the preceding claims, characterized in that the active substance b) is DCPMI. 7. A method for producing a capsule suspension concentrate according to claims 1-6, characterized in that at step (1) the protective agent s), dissolved in an organic, water-insoluble solvent L), is mixed with an isocyanate mixture a2), and the active substance b is additionally added ), dissolved in an organic, water-insoluble solvent L); the solution thus obtained is then emulsified in water in step (2); and the thus obtained emulsion E is mixed in step (3) with a compound with isocyanate-reactive groups a1). 8. ZC-preparative form for controlling unwanted plants in plant crops, containing a capsule suspension concentrate according to one of claims 1-6 and at least one suspension concentrate (SC) containing one or more active substances z); at least one or more thickeners c); one or more anionic emulsifiers e1); and/or one or more nonionic emulsifiers e2). 9. ZC-formulation according to claim 8, characterized in that it contains at least one additional protective agent. 10. ZC-formulation according to claim 8 or 9, characterized in that the active substance z) is selected from the group including flufenacet, prosulfocarb, pendimethalin, diflufenican, aclonifen, meth - 24 047067 ribuzine, pyroxasulfone, propoxycarbazone, thiencarbazone-methyl, fenoxaprop, bromoxynil, halauxifen-methyl, 2,4-D, MCPA. 11. Use of a capsule suspension concentrate according to claims 1-6 or a ZC-preparation form according to one of claims 8-10 as a herbicide in grain crops and rapeseed in the pre-emergence period, as well as in the post-emergence period. 12. A method for controlling unwanted plants in plant crops, characterized in that the capsule suspension concentrate according to one of claims 1 to 6 or the ZC formulation according to one of claims 8 to 10 is applied to the plants or to the surface on which the plants grow .