Aqueous capsule suspension concentrates based on polyurea shell materials containing multifunctional aminocarboxylates

Abstract

The present invention relates to an aqueous capsule suspension concentrate based on a polyurea shell material containing multifunctional aminocarboxylates, a method for preparing the same and its use as an agricultural chemical formulation providing improved biodegradability.

Description

[0001] The present invention relates to an aqueous capsule suspension concentrate based on a polyurea shell material containing multifunctional aminocarboxylates, a method for preparing the same and its use as an agricultural chemical formulation providing improved biodegradability.

[0002] Microcapsules are spherical objects consisting of a core and a wall material surrounding the core, wherein the core can in principle be a solid, liquid or gas component surrounded by a solid wall material. For many applications, the wall is formed by a polymer material. The volume average diameter of the microcapsules is usually 1 to 1000 μm.

[0003] A variety of shell materials are known for producing the wall of microcapsules. The shell can be composed of natural, semi-synthetic or synthetic materials. Natural shell materials are, for example, gum arabic, agar, agarose, maltodextrin, alginic acid or its salts (e.g., sodium alginate or calcium alginate), fats and fatty acids, hexadecanol, collagen, chitosan, lecithin, gelatin, albumin, shellac, polysaccharides (e.g., starch or dextran), polypeptides, protein hydrolysates, sucrose and waxes. Semi-synthetic shell materials are especially chemically modified celluloses, in particular cellulose esters and cellulose ethers, for example cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose, and starch derivatives, in particular starch ethers and starch esters. Synthetic shell materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol, polyvinyl pyrrolidone or polyureas.

[0004] Depending on the type of shell material and the production method, in each case microcapsules are formed having different properties, such as diameter, size distribution and physical and / or chemical properties.

[0005] Polyurea core-shell microcapsules obtained by reaction of at least one diisocyanate and at least one polyamine are known in the art, for example from WO 2011 / 161229 or WO 2011 / 160733. According to WO 2011 / 161229 or WO 2011 / 160733, polyurea microcapsules are prepared in the presence of polyvinylpyrrolidone (PVP) as protective colloid.

[0006] The development of biodegradable microcapsules is mainly carried out for drug delivery and in vivo release applications. As the environmental aspects of polymers begin to be discussed in the public, and efforts are made to reduce environmental pollution, the interest in biodegradable capsules has increased.

[0007] The closest prior art is WO 2017 / 089116 and WO 2017 / 089117, using polyester-modified polyisocyanates cured with amines. The application does not provide further data on biodegradability; however, it is known that polyesters hydrolyze after a period of time in the environment. A disadvantage of this application is that the polyisocyanate must be modified with a polyester. This often results in more unstable capsules due to delamination during curing. In addition, if new polyisocyanates are used in the encapsulation process, new modified esters are required, increasing the complexity of the formulator's toolbox. Another disadvantage is the increased viscosity of the modified polyisocyanates, leading to further mixing and metering problems during production. Often, these isocyanates must be heated to provide a lower viscosity. However, the stability of isocyanates decreases with increasing temperature.

[0008] It would be easier for a formulation chemist to use a polyamine containing an ester group inside the main chain, no free carboxylic acid and at least two NH2 groups at the end of the chain. However, it is known that this chemical substance will polymerize, cyclize or decompose with itself, because the NH2 group is highly reactive and will react with the ester group. Therefore, as also described in WO2017 / 089116 and 2017 / 089117, only lysine or amino acids are known to be available so far, while this chemical substance will allow new formulations of biodegradable polymers with improved properties. In the unpublished EP18181480.7, Nouryon found a new method for preparing polyamine esters containing this amine described by compound IV as described below on an industrial scale.

[0009] Therefore, the object of the present invention is to provide microcapsules, in particular for encapsulating active ingredients, and agricultural chemical preparations comprising said microcapsules, said microcapsules having:

[0010] Small particle (microcapsule) size and narrow particle size distribution;

[0011] Good fastening and mechanical stability of microcapsules;

[0012] Can be sprayed in dispersion form;

[0013] Partially made of biodegradable building blocks.

[0014] The above mentioned problems are overcome by the capsule suspension concentrate (CS) according to the present invention, wherein the capsules are made of a polymer, preferably a polyurea, polyurethane or polyamide polymer, containing an amine functional ester of formula IV as a monomer.

[0015] Thus, in general, the present invention relates to polymers comprising an amine-functional ester of formula IV as a monomer, wherein the polymer is preferably used in agrochemical formulations, wherein the polymer comprises

[0016] a) at least one polyisocyanate containing at least 2 isocyanate groups, and

[0017] b) at least one ester group-containing compound of the formula IV and optionally further isocyanate-reactive compounds b) different from IV.

[0018] The present invention therefore relates to microcapsules which comprise in their polymer shell a polymer having a monomer which is an amine-functional ester of the formula IV, wherein the capsules are preferably used in agrochemical formulations.

[0019] The present invention relates to microcapsules comprising a capsule core and a polymer shell, wherein the shell comprises in polymerized form:

[0020] a) at least one polyisocyanate containing at least 2 isocyanate groups, and

[0021] b) at least one compound of the formula IV containing an ester group and optionally further isocyanate-reactive compounds different from IV,

[0022] It forms a partially biodegradable shell.

[0023] The present invention also relates to a microcapsule dispersion comprising microcapsules, wherein the capsule core essentially contains at least one component which is soluble in an organic solvent, preferably, the one component being an agrochemical active ingredient.

[0024] Furthermore, the microcapsule preparation is preferably present as a capsule suspension concentrate (CS) in water.

[0025] Furthermore, the invention relates to an agrochemical formulation comprising microcapsules having the active ingredient in their core, wherein the formulation is preferably an aqueous capsule suspension concentrate.

[0026] If not stated otherwise, in the present invention, the particle size is determined according to the CIPAC (CIPAC=Collaborative International Pesticides Analytical Council; www.cipac.org) method MT 187 as d50 or d90=active ingredient particle size (laser light scattering of 50% or 90% of all volume particles). The median particle size refers to the d50 value.

[0027] The median particle size d50 of the particles (microcapsules) of CS is generally 1 to 50 μm, preferably 1 to 20 μm, most preferably 3 to 15 μm.

[0028] The invention also relates to microcapsules obtainable by the process according to the invention.

[0029] The invention also relates to the use of microcapsules according to the invention or obtained by the process according to the invention in personal care compositions, or home care compositions, or compositions for industrial or institutional or hospital applications, or material protection compositions, or pharmaceutical compositions, or plant protection compositions.

[0030] The invention also relates to the use of the microcapsules according to the invention or obtained by the process according to the invention in cosmetic compositions, hygienic compositions, compositions for industrial or institutional or hospital cleaning or disinfection, laundry detergents, fabric softeners, dishwashing liquids, household cleaners, industrial cleaners, oil recovery, adhesives, coatings or construction or agricultural formulations.

[0031] Thus, in one embodiment, the present invention relates to microcapsules consisting of a polymer consisting of monomers a) and b), wherein

[0032] a) is at least one polyisocyanate containing at least 2 isocyanate groups; and

[0033] b) is at least one compound of formula IV containing an ester group.

[0034] Thus, in one embodiment, the present invention relates to microcapsules consisting of a polymer consisting of monomers a) and b), wherein

[0035] a) is at least one polyisocyanate containing at least 2 isocyanate groups; and

[0036] b) is at least one compound of the formula IV containing ester groups and optionally further isocyanate-reactive compounds different from IV.

[0037] Furthermore, in another embodiment, the present invention relates to microcapsules comprising a capsule core and a polymer shell, wherein the shell comprises in polymerized form:

[0038] a) at least one polyisocyanate containing at least 2 isocyanate groups; and

[0039] b) at least one compound of the formula IV containing an ester group and optionally further isocyanate-reactive compounds different from IV,

[0040] It forms a partially biodegradable shell.

[0041] Furthermore, in another embodiment, the present invention relates to microcapsules comprising a capsule core and a polymer shell, wherein the shell comprises in polymerized form:

[0042] a) at least one polyisocyanate containing at least 2 isocyanate groups; and

[0043] b) at least one compound of the formula IV containing an ester group and optionally further isocyanate-reactive compounds different from IV,

[0044] It forms a partially biodegradable shell, and

[0045] At least one active ingredient is contained in the capsule core.

[0046] Therefore, in another embodiment, the present invention relates to a polymer obtained by reacting monomers a) and b), wherein

[0047] a) is at least one polyisocyanate containing at least 2 isocyanate groups; and

[0048] b) is at least one compound of formula IV containing an ester group.

[0049] In a specific embodiment, the present invention relates to a microcapsule formulation comprising the following components:

[0050] a): at least one isocyanate,

[0051] b): at least one compound of formula IV,

[0052] c): at least one active ingredient,

[0053] d): optionally a water-immiscible solvent,

[0054] e): optionally at least one emulsifier and / or dispersant,

[0055] f): at least one protective colloid,

[0056] g): optionally other additives,

[0057] i) water to volume,

[0058] Components a) and b) form the shell of the microcapsules.

[0059] In one embodiment, component b) comprises a compound according to formula IV and a further isocyanate-reactive compound b) different from the compound of formula IV.

[0060] In one embodiment, at least one component selected from d), e) and g) is essential.

[0061] In another embodiment, at least two components selected from d), e) and g) are necessary.

[0062] In another embodiment, components d), e) and g) are essential.

[0063] The microcapsules according to the present invention have the following advantages:

[0064] Small particle size and narrow particle size distribution;

[0065] Good fastening and mechanical stability;

[0066] ·Sprayable;

[0067] Partially made of biodegradable building blocks.

[0068] In addition, microcapsules and formulations containing them can provide controlled release of active ingredients.

[0069] The terms "biodegradation" or "biodegradability" are synonymous and, in the sense of the present invention, mean that when exposed to environmental action, after an appropriate and demonstrable period of time, the polymer decomposes. The degradation mechanism may be hydrolysis and / or oxidation and is mainly based on exposure to microorganisms such as bacteria, yeasts, fungi and algae. An example of a method for determining biodegradability is to mix the polymer with compost and store it for a specific time. According to ASTM D5338, ASTM D6400, EN13432 and DIN V54900, as an example, during the composting process, air without CO2 is passed through the mature compost and the compost is subjected to a defined temperature program. Biodegradability is defined herein by the ratio of the net amount of CO2 released by the sample (after deducting the amount of CO2 released by the compost without the sample) to the maximum possible amount of CO2 released by the sample (calculated from the carbon content of the sample). Even after a few days of composting, biodegradable polymers generally show significant signs of degradation, such as mold growth, splitting and perforation. Alternative methods are described in OECD 301 - 307. The test can be performed under aerobic or anaerobic conditions.

[0070] In another method of determining biodegradability, the polymer is incubated with a certain amount of a suitable enzyme for a defined period of time at a certain temperature, and then the concentration of organic degradation products dissolved in the incubation medium is determined. As an example, similar to Y. Tokiwa et al., American Chemical Society Symposium 1990, Chapter 12, "Biodegradation of Synthetic Polymers Containing Ester Bonds", the polymer can be incubated for several hours at 30-37°C with a predetermined amount of lipase (e.g. from Rhizopus arrhizus, Rhizopus delemar, Achromobacter sp. or Candida cylindracea), and the DOC value (dissolved organic carbon) of the reaction mixture free of insoluble components can then be measured.

[0071] Preferably, the material undergoes hydrolysis in the environment. The invention likewise provides a process for preparing a capsule suspension concentrate according to the invention, characterized in that the active ingredient c) optionally dissolved in an organic, water-immiscible solvent d) is mixed with an isocyanate mixture a) and optionally with an organic solvent and / or e) an emulsifier and / or dispersant. The solution thus prepared is then emulsified in water containing a protective colloid f), optionally with further additives g). In the process, the isocyanate a) is reacted with b) a compound IV, wherein b) is added to the water before the emulsification or b) is added after the emulsification step. Further additives g) may optionally be added.

[0072] For the preparation of the CS according to the invention, any device which generates strong shear forces commonly used for such purposes may be used. Examples include rotor-stator mixers and jet dispersers.

[0073] In the implementation of the method according to the invention, the ratio of the NCO groups from component a) to the NCO reactive groups from component b) can be varied within a specific range. Typically, 0.8 to 1.5 equivalents of the amine or alcohol component are used per 1 mol of isocyanate. Preferably, the amounts of isocyanate and amine or alcohol are selected so that there are equimolar amounts of isocyanate groups and amino or hydroxyl groups.

[0074] In carrying out the process according to the invention, the reaction temperature can be varied within a certain range.

[0075] In the emulsification step, the method according to the present invention is generally carried out at a temperature of -10 to 80°C, preferably 0 to 50°C, more preferably 2 to 40°C, most preferably 2 to 30°C.

[0076] The final curing of the polymer shell forming the microcapsules is generally carried out at a temperature of -10 to +80°C, preferably 0 to 80°C, typically 0 to 80°C, preferably 10 to 75°C.

[0077] The wall thickness of the capsule of the capsule suspension concentrate according to the present invention is 0.001 to 4 μm, preferably 0.01 to 2 μm, most preferably 0.01 to 1 μm, wherein the wall thickness is preferably determined by calculation based on the amount of active ingredient, the average particle size of the active ingredient and the amount of polymer shell material. The calculation can be performed according to J Pharm Sci, 62, 1973, 452.

[0078] In the reaction of a) with b), the sum of the number-average functionality X of the isocyanate groups and the isocyanate-reactive groups is 2≤X≤6, preferably 2≤X≤4.5, more preferably 2.0≤X≤3.5, most preferably 2.2≤X≤2.8.

[0079] The "number average functionality X" feature in the process according to the invention is explained as follows. The higher functionality compounds are important here, and the result of subtracting 2 from the lower functionality compounds is added to the higher functionality compounds. For example, if the (average) functionality of a) is 2.1 and the (average) functionality of b) is 2.6: 2.1-2=0.1. This difference is added to 2.6: 2.6+0.1=2.7. The number average functionality is therefore 2.7. Alternatively, if a) is 2.7 and ab) is 2.3, the number average functionality is 2.7+2.3-2=3.0.

[0080] The capsule suspension concentrates according to the invention have many advantages. For example, they are able to release the active ingredient in the amount required in each case over a long period of time. It is also advantageous that the plant compatibility of the active ingredients present is improved and the volatility and thus the damage to neighboring crops is reduced. In addition, the acute toxicity of the active ingredients is reduced, so that the deployment of the microcapsule preparation is problem-free for the operator even without any major safety precautions.

[0081] Compound IV is defined as follows:

[0082] Nouryon has found in EP 18181480.7 that a process for preparing amine-functional esters of aminocarboxylic acids and polyols (formula IV) can be carried out by metering polyols and aminocarboxylic acids (cyclic amides thereof) in a precise molar ratio of about n mol of aminocarboxylic acid per mole of polyol containing n hydroxyl groups, so that the polyol does not have to be distilled off, and that, moreover, when the process is carried out in this way, it is possible to carry out the reaction in the absence of solvents or with limited amounts of solvents by means of a plurality of Bronsted-Lowry acids ( -Lowry acids) to catalyze (transesterification) esterification reactions.

[0083]

[0084] Esters of aminocarboxylic acids according to formula IV can be prepared by an improved process comprising reacting a polyol of formula (I) with an aminocarboxylic acid of formula II or its cyclic amide of formula III in the presence of a Bronsted-Lowry acid at a temperature of 60 to 200°C.

[0085] HO-(A)-OH (I)

[0086] wherein A is a carbon chain having 2 to 36 carbon atoms, which may be aliphatic (straight or branched, saturated or unsaturated) or aromatic, or CH2CH(OH)CH2, CH2C(CH2OH)2CH2, CH2C(CH2 H)(CH3)CH2, CH2C(CH2OH)(CH2CH3)CH2, p-tetrahydrofuran, erythritol or an ester of a dicarboxylic acid or tricarboxylic acid with ethylene glycol or propylene glycol, and wherein A may optionally be alkoxylated with one or more alkylene oxide units or reacted with one or more hydroxycarboxylic acids,

[0087]

[0088] wherein m is an integer of 1-8 in formula II and an integer of 3-8 in formula III, each R is independently hydrogen or C1-C4 alkyl or CH2CH2COOH or CH2COOH or (CH2)4NH2,

[0089] wherein the ratio of the total molar amount of the aminocarboxylic acid or its cyclic amide to the molar amount of the polyol is n:0.8 to n:1.5, wherein n is the total number of hydroxyl groups on the polyol, and wherein the Brønsted-Lowry acid is not added to the reaction mixture until at least 50% of the total amount of the polyol and the aminocarboxylic acid or its cyclic amide has been metered in.

[0090] In a preferred embodiment, the Bronsted-Lowry acid is sulfuric acid.

[0091] By this reaction, amine-functional esters of aminocarboxylic acids can be obtained.

[0092] In many embodiments, the compound (IV) obtainable by the method of the present invention may be encompassed by the following structure:

[0093]

[0094] where k is a value from 1 to 3, and

[0095] wherein R is independently hydrogen or C1-C4 alkyl or CH2CH2COOH or CH2COOH or (CH2)4HN2, and

[0096] wherein A is a carbon chain having 2 to 36 carbon atoms, which may be aliphatic (straight or branched, saturated or unsaturated) or aromatic, or CH2CH(OH)CH2, CH2C(CH2OH)2CH2, CH2C(CH2 H)(CH3)CH2, CH2C(CH2OH)(CH2CH3)CH2, p-tetrahydrofuran, erythritol or an ester of a dicarboxylic acid or tricarboxylic acid with ethylene glycol or propylene glycol, and wherein A may optionally be alkoxylated with one or more alkylene oxide units or reacted with one or more hydroxycarboxylic acids as defined above,

[0097] and wherein each m, if from formula II, is an integer from 1 to 8, preferably from 1 to 8, and if from formula III, is an integer from 3 to 8,

[0098] and X is an anion obtainable by deprotonating a Bronsted-Lowry acid.

[0099] If the above selection of A is followed, in case the group A contains further hydroxy substituents, these can be converted into groups in which the proton of the OH group is replaced by a group of formula (V)

[0100]

[0101] wherein k, each R is independently, m and X are as defined above.

[0102] The compound obtainable by the process of the present invention may contain 0 to 30 mol % of the compound of the following formula (VI), based on the total moles of compound (IV),

[0103]

[0104] wherein k, each R independently, A, m and X are as defined above. Preferably, the amount of the compound of formula VI is 1 mol% to 20 mol%, even more preferably 2 mol% to 15 mol%, most preferably 5 mol% to 10 mol%, based on the total amount of compound IV.

[0105] The polyols that can be used in the process are compounds of the formula HO-A-OH (I) containing at least two hydroxyl groups, wherein A is a carbon chain having 2 to 36 carbon atoms, which can be aliphatic (straight or branched, saturated or unsaturated) or aromatic, or CH2CH(OH)CH2, CH2C(CH2OH)2CH2, CH2C(CH2OH)(CH3)CH2, CH2C(CH2OH)(CH2CH3)CH2, tetrahydrofuran, erythritol or esters of di(tri)carboxylic acids with ethylene glycol or propylene glycol, optionally alkoxylated with one or more alkylene oxide units or reacted with one or more hydroxycarboxylic acids.

[0106] Examples of alkoxylated polyols are

[0107] HO-(CH2-CH(R1)-O)p-CH2-CH(R1)-(O-CH2-CH(R1))p-OH,

[0108] HO-(CH2-CH(R1)-O)p-CH2-CH=CH-CH2-(O-CH2-CH(R1))p-OH,

[0109] HO-(CH2-CH(R1)-O)p-CH2-CH(CH3)2-CH2-(O-CH2-CH(R1))p-OH、

[0110] HO-(CH2-CH(R1)-O)p-C6H4-(O-CH2-CH(R1))p-OH、

[0111] HO-(CH2-CH(R1)-O)p-CH2-C6H4-CH2-(O-CH2-CH(R1))p-OH、

[0112] HO-(CH2-CH(R1)-O)p-C6H 10 -(O-CH2-CH(R1))p-OH、

[0113] HO-(CH2-CH(R1)-O)p-CH2-C6H 10 -CH2-(O-CH2-CH(R1))p-OH、

[0114] HO-(CH2-CH(R1)-O)p-CH2-(CH2)n-CH2-(O-CH2-CH(R1))p-OH、

[0115] HO-(CH2-CH(R1)-O)p-CH2-CH2-CH2-CH2-(O-CH2-CH2-CH2-CH2)p-(O-CH2-CH(R1))p-OH、

[0116] HO-(CH2-CH(R1)-O)p-(CH2)i-CH((CH2)jCH3)-CH((CH2)jCH3)-(CH2)i-(O-CH2-CH(R1))p-OH、

[0117] HO-(CH2-CH(R1)-O)p-CH2-(CH(O-CH2-CH(R1))p-OH))d-CH2-(O-CH2-CH(R1))p-OH、

[0118] HO-(CH2-CH(R1)-O)p-CH2-C(CH2-(O-CH2-CH(R1))p-OH)2-CH2-(O-CH2-CH(R1))p-OH、

[0119] HO-(CH2-CH(R1)-O)p-CH2-C(CH2-(O-CH2-CH(R1))p-OH)(CH3)-CH2-(O-CH2-CH(R1))p-OH、

[0120] HO-(CH2-CH(R1)-O)p-CH2-C(CH2-(O-CH2-CH(R1))p-OH)(CH2CH3)-CH2-(O-CH2-CH(R1))p-OH, wherein each p is independently an integer from 0 to 25, as long as one p in the structure is at least 1, n is 1 to 10, i+j=16, d=1-4, and each R1 is independently a hydrogen atom or a C1-C2 alkyl group.

[0121] Examples of polyols of the alcohol class reacted with the hydroxycarboxylic acid are compounds of the formula:

[0122] HO-(CH(Z)-C(O)-O)p-CH2-CH(R1)-(OC(O)-CH(Z))p-OH, HO-(CH(Z)-C(O)-O)p-CH2-CH=CH-CH2-(OC(O)-CH(Z))p-OH, HO-(CH(Z)-C(O)-O)p-CH2-CH(CH3)2-CH 2-(OC(O)-CH(Z))p-OH、HO-(CH(Z)-C(O)-O)p-C6H4-(OC(O)-CH(Z))p-OH、HO-(C H(Z)-C(O)-O)p-CH2-C6H4-CH2-(OC(O)-CH(Z))p-OH, HO-(CH(Z)-C(O)-O)p-C6H 10 -(OC(O)-CH(Z))p-OH、HO-(CH(Z)-C(O)-O)p-CH2-C6H 10-CH2-(OC(O)-CH(Z))p-OH,HO-(CH(Z)-C(O)-O)p-CH2-(CH2)n-CH2-(OC(O)-CH(Z))p-OH,HO-(C H(Z)-C(O)-O)p-CH2-CH2-CH2-CH2-(O-CH2-CH2-CH2-CH2)p-(OC(O)-CH(Z))p-OH、HO-(CH(Z)-C (O)-O)p-(CH2)i-CH((CH2)jCH3)-CH((CH2)jCH3)-(CH2)i-(OC(O)-CH(Z))p-OH、HO-(CH(Z)-C( O)-O)p-CH2-(CH(OC(O)-CH(Z))p-OH))d-CH2-(OC(O)-CH(Z))p-OH, HO-(CH(Z)-C(O)-O)p-CH2- C(CH2-(OC(O)-CH(Z))p-OH)2-CH2-(OC(O)-CH(Z))p-OH, HO-(CH(Z)-C(O)-O)p-CH2-C(CH2-(OC (O)-CH(Z))p-OH)(CH3)-CH2-(OC(O)-CH(Z))p-OH、HO-(CH(Z)-C(O)-O)p-CH2-C(CH2-(OC(O)-C H(Z))p-OH)(CH2CH3)-CH2-(OC(O)-CH(Z))p-OH, HO-(CH(Z)-C(O)-O)p-CH2(CH2)k-CH(R1)-(OC (O)-CH(Z))p-OH, HO(CH(Z)-C(O)-O)p-CH2-(CH(OC(O)-CH(Z)-OH)p)e-CH2-(OC(O)-CH(Z))pOH,

[0123] Wherein each p is independently an integer of 0-25, as long as at least one p in the structure is at least 1, and each R1 is independently a hydrogen atom or a C1-C2 alkyl group, k is 0-10, if k>0, then R1 is hydrogen, Z is hydrogen or CH3, and e=1-4.

[0124] Examples of polyols of esters of dicarboxylic acids or tricarboxylic acids with ethylene glycol or propylene glycol are compounds of the formula: HO(CH2CH(R1)-O)pC(O)-CH2-(C(OH)(C(O)(O-CH(R1)-CH2)pOH)d-(CH2)kC(O)(O-CH(R1)-CH2)pOH,

[0125] Wherein each p is independently an integer of 0-25, as long as at least one p in the structure is at least 1, and each R1 is independently a hydrogen atom or a C1-C2 alkyl group, d=0-1, when d=1, k=1; when d=0, k=0-10.

[0126] The most preferred polyols are selected from ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, glycerol, polytetrahydrofuran, pentaerythritol, trimethylolpropane, trimethylolethane, diethylene succinate, dimerized fatty alcohols, 1,6-hexanediol, 1,4-butylene glycol, 1,8-octanediol, 1,10-decanediol, erythritol, optionally alkoxylated or reacted with hydroxycarboxylic acids. When polyethylene glycol, polypropylene glycol or polybutylene glycol are used, they preferably contain 2 to 10 ethylene oxide, propylene oxide or butylene oxide units, even more preferably 2 to 6 units.

[0127] Mixtures of two or more polyols may also be used.

[0128] Preferred aminocarboxylic acids of the formula II are glycine, alanine, valine, leucine, isoleucine, lysine, aspartic acid and glutamic acid, more preferably glycine or alanine.

[0129] Further preferred aminocarboxylic acids of formula II are selected from 6-aminocaproic acid, 4-aminobutyric acid.

[0130] In a preferred embodiment, a cyclic amide of formula III is used in the process of the present invention. More preferably, in formula III, m is 3, 4, 5 or 6. Most preferred are cyclic amides of 6-aminocaproic acid and 4-aminobutyric acid.

[0131] It should be noted that mixtures of aminocarboxylic acids and / or cyclic amides can also be used in the process.

[0132] Preferred amine functional esters of formula (IV) include

[0133]

[0134]

[0135]

[0136] Compared to many commercially available amine-functional compounds containing at least two amine groups, the compounds of formula (IV), (VI) have been determined to have improved biodegradability and / or chemical degradability, which increases the environmental profile of any application in which they are used. In applications where diamines / polyamines are currently used, for example in the preparation of polymers containing diamine monomers, they can be used as alternatives with better degradability characteristics. Such polymers include polyureas, polyepoxides and polyamide polymers, and it is desirable to make such polymers biodegradable. In addition, they can be used as building blocks, wherein the amines are further modified to prepare imide-functional monomers or (meth)acrylamide-functional monomers.

[0137] In a preferred embodiment, the compounds of formula (IV), (VI) are readily biodegradable.

[0138] In a preferred embodiment of the inventive method, aminocarboxylic acid is used in the form of its cyclic amide (Formula III). The advantage of carrying out the transesterification of the cyclic amide of aminocarboxylic acid rather than the esterification of aminocarboxylic acid or its salt is that it is easier to control the amount of water in the method. When carrying out the transesterification, there is no net water formation. When carrying out the esterification, more water will be formed, and the water content of this increase may cause side reactions, such as hydrolysis reactions particularly under acidic pH, in which the product formed decomposes again in the starting compound. In addition, when attempting to remove water from the reaction mixture, reactants, most mainly polyols, may form azeotropes with water and also lose.

[0139] In the process of the present invention, the aminocarboxylic acid of formula (III) or its cyclic amide derivative and the polyol are preferably used in the following molar ratio, the molar ratio of the total aminocarboxylic acid and / or cyclic amide of formula (III) to the polyol is preferably n:0.8 to n:1.3, more preferably n:0.9 to n:1.1, wherein n represents the number of hydroxyl groups on the polyol, and most preferably the two compounds are used in substantially equimolar amounts of about 1 mole of aminocarboxylic acid per hydroxyl group.

[0140] In a preferred embodiment, the molar amount of water during the process is from 0 to 10 mol %, more preferably from 0.01 to 5 mol %, most preferably from 0.1 to 2 mol %, based on the total moles of polyol.

[0141] After the reaction is complete, the product may optionally (to reduce viscosity) be diluted with water and / or an organic polar solvent. Preferred organic solvents are glycolic solvents, such as propylene glycol, triethylene glycol, ethylene glycol, 2-methoxyethanol, glycerol or isopropanol.

[0142] The Bronsted-Lowry acid is preferably used as a concentrated (ie 20 to 100 wt %) aqueous solution and metered portionwise into the reaction mixture containing all of the aminocarboxylic acid or its cyclic amide and the polyol in order to control the exothermic effect of the reaction.

[0143] Bronsted-Lowry acid is not an aminocarboxylic acid. Bronsted-Lowry acid is preferably an acid with a pKa of -10 to 3. Bronsted-Lowry acid is even more preferably an inorganic acid, even more preferably it is sulfuric acid, phosphoric acid or a hydrohalic acid, and most preferably it is sulfuric acid, because hydrohalic acids such as HCl result in solid products in embodiments, and phosphoric acid results in lower conversions. In addition, both HCl and H3PO4 in liquid form can be obtained as solutions with considerable water (HCl 37% concentration, H3PO4 85% concentration), while H2SO4 can be obtained in a substantially water-free form (such as a 95-98% concentrated solution). Therefore, the use of H2SO4 allows the product to be obtained in liquid form with a high conversion (>90%), and in addition, there is no need to evaporate water.

[0144] In a preferred embodiment, X is an anion derived from an inorganic Bronsted-Lowry acid, more preferably a halide, sulfate, hydrogensulfate, hydrogenphosphate, dihydrogenphosphate or phosphate anion. Most preferably, X is a sulfate or hydrogensulfate anion.

[0145] The process can be carried out under reduced pressure, but is preferably carried out under atmospheric pressure.

[0146] Optionally, the product may be neutralized to a pH of 3-7 by a base. The product may be purified by methods available to those skilled in the art. However, due to the low by-product content, it may also be used, for example as a surfactant, without further processing or purification steps.

[0147] The process is particularly advantageous for polyols having a boiling point of up to 220° C., or for polyols that can form azeotropes with water having a boiling point below 220° C. In contrast to prior art processes, in the process of the present invention, when such polyols are used, they are not stripped out of the reaction mixture when the water of reaction is removed, since such water is not formed in the process of the present invention and therefore does not need to be removed. Many polyols that can be used in the process of the present invention have boiling points within this range (particularly smaller polyols or polyols containing some branching in their structure).

[0148] The process is preferably carried out at a temperature of 60 to 150°C, more preferably 80 to 145°C, most preferably 110 to 140°C.

[0149] Compounds b) which can be additionally mixed with compound IV as useful alternatives for further isocyanate-reactive groups b) and which are optionally additionally added include aliphatic, aromatic, cyclic and cycloaliphatic primary and secondary diamines, and also polyamines. Examples include ethylenediamine (1,2), diethylenetriamine, monoisopropylamine, 4-aminopyridine (4-AP), n-propylamine, polyaziridines based on ethyleneimine or propyleneimine, triethylenetetramine (TETA), tetraethylenepentamine, 2,4,4′-triaminodiphenyl ether, bis(hexamethylene)triamine, ethylenediamine (EDA), trimethylenedipiperidine (TMDP), guanidine carbonate (GUCA), phenylenediamine, toluenediamine, pentamethylenehexamine, 2,4-diamino-6-methyl-1,3,5-triazine, 1,2-diaminocyclohexane, 4,4′-diamino

[0063] The following are some examples of the present invention: 1,2-diaminonaphthalene isophorone diamine, diaminopropane, diaminobutane, piperazine, aminoethylene piperazine (AEP), poly(propylene glycol) bis(2-aminopropyl ether) or o,o′-bis(2-aminopropyl)polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol, hexamethylene diamine, bis(3-aminopropyl)amine, bis(2-methylaminoethyl)methylamine, 1,4-diaminocyclohexane, 3-amino-1-methylaminopropane, N-methylbis(3-aminopropyl)amine, 1,4-diamino-n-butane and 1,6-diamino-n-hexane.

[0150] Useful compounds having isocyanate-reactive groups b) likewise include primary and secondary, aliphatic and aromatic diols and polyols. Examples include: ethylene glycol, propylene glycol (1,2), propylene glycol (1,3), butanediol (1,4), pentanediol (1,5), hexanediol (1,6), glycerol and diethylene glycol. Glycerol and propane-1,2-diol are preferably used.

[0151] Compounds having isocyanate-reactive groups b) also include amino alcohols. Examples include triethanolamine, monoethanolamine, triisopropanolamine, diisopropylamine, N-methylethanolamine, N-methyldiethanolamine.

[0152] In one embodiment, water is used as isocyanate-reactive component b). It reacts in situ with the isocyanate (poly / di) to give the amine (poly / di). It is likewise possible to use blends of b).

[0153] Isocyanate mixtures a) are mixtures of mono-, di- and / or polyisocyanates, or reaction products of isocyanate mixtures. Suitable compounds a) are, for example, butene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, isomeric bis(4,4′-isocyanatocyclohexyl)methane (H12-MDI) and mixtures thereof with any isomeric content, cyclohexylene 1,4-diisocyanate, 4-isocyanatomethyloctane 1,8-diisocyanate (nonane triisocyanate), phenylene 1,4-diisocyanate, 4-isocyanatomethyloctane 1,8-diisocyanate (nonane triisocyanate), 1,6-diisocyanate ( ... , 4-diisocyanate, toluene 2,4- and / or 2,6-diisocyanate (TDI), naphthylene 1,5-diisocyanate, diphenylmethane 2,2′- and / or 2,4′- and / or 4,4′-diisocyanate (MDI), 1,3- and / or 1,4-bis(2-isocyanatoprop-2-yl)benzene (TMXDI), 1,3-bis(isocyanatomethyl)benzene (XDI), 2,6-diisocyanatohexanoic acid alkyl esters having an alkyl group of 1 to 8 carbon atoms (lysine diisocyanate) and mixtures thereof. Compounds containing modified structures such as allophanate, uretdione, carbamate, isocyanurate, biuret, iminooxadiazinedione or oxadiazinedione structures and based on the diisocyanates mentioned are also suitable units for component a2), as are polycyclic compounds, for example polymeric MDI (pMDI, for example PAPI-27 from Dow or VIZOL® from Covestro AG) 44V20 products) and combinations of the above.

[0154] Preference is given to modifications having an isocyanate (NCO) functionality of 2 to 6, preferably 2.0 to 4.5, more preferably 2.3 to 4.2, most preferably 2.3 to 3.8. An NCO functionality of 2.4 to 2.8 is particularly preferred.

[0155] It is preferred to use a diisocyanate selected from HDI, IPDI, H12-MDI, TDI and MDI for modification. TDI and MDI and their derivatives are particularly preferred. Particularly preferred MDI is polymeric MDI, such as PAPI-27 used in a blend with TDI. The preferred NCO content of the isocyanate or polyisocyanate or blend is 3% to 50% by weight, more preferably 10% to 40% by weight, more preferably 15% to 35% by weight, and most preferably 18% to 30% by weight. The isocyanate groups can also exist in a partially or completely blocked form before they react with the isocyanate-reactive groups, so that they cannot react with the isocyanate-reactive groups immediately. This ensures that the reaction does not occur until a specific temperature (blocking temperature) is reached. Typical blocking agents can be found in the prior art and are selected so that they are removed from the isocyanate groups again at a temperature of 60 to 220° C. according to the substance, and then react only with the isocyanate-reactive groups. There are end-capping agents which are incorporated into the polyurethane, and there are also those which remain in the polyurethane as solvent or plasticizer or escape from the polyurethane as gas. Sometimes the expression "end-capped NCO value" is used. When the expression "NCO value" is used in the present invention, this always refers to the uncapped NCO value. Usually the degree of blocking is up to <0.5%. Examples of typical end-capping agents are caprolactam, methyl ethyl ketoxime, pyrazoles such as 3,5-dimethyl-1,2-pyrazole or 1,-pyrazole, triazoles such as 1,2,4-triazole, diisopropylamine, diethyl malonate, diethylamine, phenol and its derivatives and imidazole.

[0156] Component a) can also be used in the form of a mixture of the abovementioned compounds or in the form of a prepolymer. In this case, for example, a compound containing isocyanate groups and having an NCO content of 3% to 50% by weight is reacted with a compound containing isocyanate-reactive groups and having an OH value of 10 mg KOH / g to 150 mg KOH / g.

[0157] Useful organic solvents d) include all customary organic solvents which, on the one hand, have low miscibility with water and, on the other hand, dissolve the active agrochemical ingredients used with good solubility. In the context of the present invention, low miscibility is understood to mean a miscibility with water of less than 1% by weight. Preferred examples include aliphatic and aromatic, optionally halogenated hydrocarbons such as toluene, xylene, 100, 100ND, 150, 150ND or 200, 200ND (mineral oil), tetrachloromethane, chloroform, dichloromethane and dichloroethane, as well as esters such as ethyl acetate and alkanecarboxamides such as N,N-dimethyloctanamide and N,N-dimethyldecanamide. In addition, there are vegetable oils and modified oils (for example by methylation, ethylation and hydrogenation and hydration) based on, for example, rapeseed oil, corn kernel oil, coconut oil, etc. Particular preference is given to using mineral oils, very particular preference to using solvents based on dialkylnaphthalenes (for example diisopropylnaphthalene) and 1-methylnaphthalene, 2-methylnaphthalene and mixtures of naphthalene (for example 200ND product, CAS No.: 64742-94-5).

[0158] Useful emulsifiers e) include standard surface-active substances present in the formulation of active agricultural chemical ingredients. Examples include ethoxylated nonylphenols, polyglycol ethers of linear alcohols, reaction products of alkylphenols with ethylene oxide and / or propylene oxide, and fatty acid esters, alkyl sulfonates, alkyl sulfates and aryl sulfates. The emulsifier can be added to the oil phase and / or the aqueous phase. Preferably, the emulsifier is added to the aqueous phase.

[0159] Suitable anionic dispersants e), such as emulsifiers, surfactants, wetting agents and dispersants, are, for example, alkali metal, alkaline earth metal or ammonium salts of sulfonic acid, sulfuric acid, phosphoric acid, carboxylic acid and mixtures thereof, for example salts of alkylsulfonic acid or alkylphosphoric acid and alkylarylsulfonic acid or alkylarylphosphoric acid, diphenylsulfonates, α-olefinsulfonates, ligninsulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecylbenzene and tridecylbenzene, sulfonates of naphthalene and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, sulfates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols or sulfates of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkylcarboxylates and carboxylated alcohol ethoxylates or alkylphenol ethoxylates. Likewise suitable anionic emulsifiers are the alkali metal, alkaline earth metal and ammonium salts of polystyrenesulfonic acid, polyvinylsulfonates, alkylnaphthalenesulfonates, salts of alkylnaphthalenesulfonic acid-formaldehyde condensation products, salts of condensation products of naphthalenesulfonic acid, phenolsulfonic acid and formaldehyde. Examples are calcium dodecylbenzenesulfonate such as 70 / B (Solvay), Phenylsulfonate CA100 (Clariant) or isopropylammonium dodecylbenzenesulfonate such as 3300B (Croda). Alternatively, a Breakthru additive such as a polyether-modified trisiloxane may be added.

[0160] Other typical representatives include Phenylsulfonat CA (calcium dodecylbenzenesulfonate), Products (optionally esterified derivatives of tristyrylphenol ethoxylates), 3510 (alkylated EO / PO copolymer), EL 400 (ethoxylated castor oil), Products (Fat acylated sorbitan ethoxylates), AR 100 (calcium dodecylbenzenesulfonate). Preferred are salts of alkylated aromatic sulfonic acids such as calcium phenylsulfonate and / or Alkylated copolymers of AR 100 with ethylene oxide and propylene oxide such as 3510 combination. Particularly preferred dodecylbenzene sulfonate such as Alkylated copolymers of AR 100 with ethylene oxide and propylene oxide such as A combination of 3510.

[0161] Examples of further anionic emulsifiers e) from the group consisting of naphthalenesulfonates are MT 800(Sodium dibutylnaphthalenesulfonate), IP (sodium diisopropylnaphthalene sulfonate) and BX (alkyl naphthalene sulfonate). Examples of anionic surfactants derived from condensates of naphthalene sulfonates with formaldehyde are DT 201 (naphthalenesulfonic acid hydroxy polymer with formaldehyde and methylphenol sodium salt), DT 250 (condensation product of phenol sulfonate and naphthalene sulfonate), C (condensation product of phenolsulfonate and naphthalenesulfonate) or D-425, 2020. Preferred are 1,2-dibutyl or 1,2-diisobutyl substituted naphthalenesulfonates, such as products such as MT 800 (CFPI-Nufarm) and BX (BASF). Other typical surfactants are 3D33, 4D384, BSU, CY / 8 (Solvay) and S3474, and T product (Clariant) form, e.g. T100.

[0162] Useful nonionic dispersants e) are, for example, emulsifiers, wetting agents, surfactants and dispersants, including the standard surface-active substances present in the formulations of active agrochemical ingredients. Examples include ethoxylated nonylphenols, reaction products of linear or branched alcohols with ethylene oxide and / or propylene oxide, ethylene oxide-propylene oxide block copolymers, end-capped and non-end-capped alkoxylated linear and branched, saturated and unsaturated alcohols (e.g. butoxypolyethylene glycol-polypropylene glycol), reaction products of alkylphenols with ethylene oxide and / or propylene oxide, ethylene oxide-propylene oxide block copolymers, polyethylene glycols and polypropylene glycols, and also fatty acid esters, fatty acid polyglycol ether esters, alkyl sulfonates, alkyl sulfates, aryl sulfates, ethoxylated aryl alkylphenols, e.g. tristyrylphenol ethoxylates having an average of 16 ethylene oxide units per molecule, and ethoxylated and propoxylated aryl alkylphenols, and sulfated and phosphated aryl alkylphenol ethoxylates or ethoxylated and propoxylated. Particular preference is given to tristyrylphenol alkoxylates and fatty acid polyglycol ether esters. Very particular preference is given to tristyrylphenol ethoxylates, tristyrylphenol ethoxypropoxylates and castor oil polyglycol ether esters, in each case alone or in the form of a mixture. Additives are additionally useful, such as surfactants or esters of fatty acids, which contribute to improving the biological efficacy. Suitable nonionic emulsifiers b2) are, for example 796 / P, CO30 HOT, PSI 100 or T304.

[0163] Suitable nonionic dispersants e) may likewise be selected from polyvinylpyrrolidone (PVP), polyvinyl alcohol, copolymers of PVP and dimethylaminoethyl methacrylate, butylated PVP, copolymers of vinyl chloride and vinyl acetate and partially hydrolyzed vinyl acetate, phenolic resins, modified cellulose types such as (Polyvinylpyrrolidone), (polyvinyl alcohol) or modified cellulose. Polyvinyl pyrrolidone type is preferred, and low molecular weight type is particularly preferred, such as K30 or K30.

[0164] Useful further nonionic emulsifiers e) from the group of di- and triblock copolymers of alkylene oxides are, for example, compounds based on ethylene oxide and propylene oxide having an average molar mass of 200 to 10 000 g / mol, preferably 1000 to 4000 g / mol, in which the mass proportion of polyethoxylated blocks varies between 10% and 80%, for example PE series (Uniqema), PE series (BASF), 32 or PF Series (Clariant).

[0165] Useful protective colloids f) include all substances usually used for this purpose. Preferred examples include natural and synthetic water-soluble polymers, such as gelatin, starch and cellulose derivatives, especially cellulose esters and cellulose ethers, such as methylcellulose, and also polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, lignin sulfonates (e.g. NA, 88 25S), modified naphthalene sulfonate (e.g. Morwet D-425), polyvinyl pyrrolidone and polyacrylamide. Particularly preferred are polyvinyl alcohol, partially hydrolyzed polyvinyl acetate and lignin sulfonate. Most preferred are polyvinyl alcohol and / or lignin sulfonate.

[0166] Useful other additives g) include

[0167] - Organic thickeners and inorganic thickeners. Useful organic thickeners include organic natural or biotechnologically modified or organic synthetic thickeners. Typical synthetic thickeners are (Croda) or or Series (Elementis). These are usually based on acrylates. Typical organic thickeners are based on xanthan gum or cellulose (e.g. hydroxyethyl cellulose or carboxymethyl cellulose) or combinations thereof. Further typical representatives are based on cellulose or lignin. Preference is given to using naturally modified thickeners based on xanthan gum. Typical representatives are, for example (Solvay) and (Kelco Corp.), and (Cargill). Silica and attapulgite are also preferred.

[0168] - preservatives, which include all substances usually present in crop protection compositions for this purpose. Examples include SPX(Thor) and GXL (Lonza).

[0169] - Defoamers, which include all substances which can usually be used for this purpose in crop protection compositions. Preference is given to silane derivatives, such as polydimethylsiloxane and magnesium stearate. Typical products are used 484 (Solvay, silicone emulsion) and SAG1571 (Momentive).

[0170] - Substances used as cold stabilizers may be all those substances which can usually be used for this purpose in crop protection compositions. Examples include urea, glycerol and propylene glycol.

[0171] - pH stabilizers and neutralizers, which include conventional acids and bases. Examples include phosphoric acid, citric acid, sodium hydroxide solution, and aqueous ammonia solution.

[0172] - a suitable carrier material which is selected from highly absorbent carriers having an absorption capacity of at least 200 g of dibutyl phthalate per 100 g of carrier material.

[0173] Preferred highly absorbent carriers g) are silica, e.g. products (highly absorbent synthetic precipitated silica) and fumed silica ( product). Precipitated silica is preferred.

[0174] % to 40% by weight, more preferably 10 to 20% by weight, the proportion of organic solvents d) is generally 0 to 90% by weight, preferably 10 to 60% by weight, more preferably 20 to 40% by weight, most preferably 25 to 40% by weight, the proportion of protective colloids f) is generally 0.1 to 5% by weight, preferably 0.2 to 3% by weight, more preferably 0.3 to 1.5% by weight, and the proportion of additives g) is generally 0.1 to 15% by weight, preferably 0.3 to 10% by weight, more preferably 0.4 to 3% by weight, all based on the total weight of the agrochemical preparation.

[0175] With regard to the above-mentioned proportions of the individual components, it is clear to the person skilled in the art that the preferred ranges for the individual components can be freely combined with one another, and these combinations of different preferred ranges for the individual components are therefore also regarded as disclosed.

[0176] However, unless stated otherwise, the same level of preferred ranges, ie all preferred or more preferred ranges, are particularly preferred and the specific disclosure is not intended to replace these general combinations but to add to them.

[0177] The same applies to further statements of preferred ranges elsewhere in the specification.

[0178] In a preferred embodiment, the ratio of a) to b) is from 0.1% to 8% by weight,

[0179] The proportion of active agrochemical ingredients c) is 1% to 50% by weight,

[0180] The proportion of organic solvent d) is 0% to 60% by weight,

[0181] The proportion of protective colloid f) is 0.1% to 5% by weight,

[0182] And the proportion of additive g) is 0.1% to 15% by weight.

[0183] In a further preferred embodiment, the ratio of a) to b) is from 0.1% to 8% by weight,

[0184] The proportion of active agrochemical ingredients c) is 1% to 50% by weight,

[0185] The proportion of organic solvent d) is 0% to 40% by weight,

[0186] The proportion of protective colloid f) is 0.1% to 5% by weight,

[0187] And the proportion of additive g) is 0.1% to 15% by weight.

[0188] In an even further preferred embodiment, the ratio of a) to b) is from 0.1% to 8% by weight,

[0189] The proportion of active agrochemical ingredients c) is 1% to 50% by weight,

[0190] The proportion of organic solvent d) is 0% to 40% by weight,

[0191] The proportion of protective colloid f) is 0.1% to 5% by weight,

[0192] And the proportion of additive g) is 0.1% to 15% by weight.

[0193] In another embodiment, the ratio of a) to b) is from 0.1% to 8% by weight,

[0194] The proportion of active agrochemical ingredients c) is 1% to 50% by weight,

[0195] The proportion of organic solvent d) is 0% to 90% by weight,

[0196] The proportion of protective colloid f) is 0.1% to 5% by weight,

[0197] And the proportion of additive g) is 0.1% to 15% by weight.

[0198] In another embodiment, the ratio of a) to b) is from 0.2% to 4.5% by weight,

[0199] The proportion of active agrochemical ingredients c) is 5% to 40% by weight,

[0200] The proportion of organic solvent d) is 0% to 60% by weight,

[0201] The proportion of protective colloid f) is 0.2% to 3% by weight,

[0202] And the proportion of additive g) is 0.3% to 10% by weight.

[0203] In another preferred embodiment, the ratio of a) to b) is from 0.2% to 4.5% by weight,

[0204] The proportion of active agrochemical ingredients c) is 10% to 20% by weight,

[0205] The proportion of organic solvent d) is 0% to 40% by weight,

[0206] The proportion of protective colloid f) is 0.3% to 1.5% by weight,

[0207] And the proportion of additive g) is 0.4% to 3% by weight.

[0208] In another embodiment, the ratio of a) to b) is from 0.3% to 2.5% by weight,

[0209] The proportion of active agrochemical ingredients c) is 10% to 20% by weight,

[0210] The proportion of organic solvent d) is 0% to 40% by weight,

[0211] The proportion of protective colloid f) is 0.3% to 1.5% by weight,

[0212] And the proportion of additive g) is 0.4% to 3% by weight.

[0213] In another embodiment, the ratio of a) to b) is from 0.3% to 2.5% by weight,

[0214] The proportion of active agrochemical ingredients c) is 10% to 20% by weight,

[0215] The proportion of organic solvent d) is 0% to 40% by weight,

[0216] The proportion of protective colloid f) is 0.3% to 1.5% by weight,

[0217] And the proportion of additive g) is 0.4% to 3% by weight.

[0218] Wherein in the foregoing, water was added to volume.

[0219] However, water is preferably present in 20-60 wt%, more preferably 30-50 wt%, most preferably 35-50 wt%.

[0220] Preferably, the ratio of active agrochemical ingredient c) to isocyanate mixture a) is from 7:1 to 40:1, preferably from 8:1 to 20:1, more preferably from 9:1 to 18:1.

[0221] The ratio of isocyanate-reactive groups b) to isocyanate mixture c) is from 0 to 1.2, preferably from 0 to 1.1, more preferably from 0.8 to 1.1, more preferably from 0.9 to 1.1, most preferably from 0.95 to 1.05.

[0222] In addition, the organic solvent d) in the aforementioned embodiment is preferably mineral oil, and further preferably a dialkylnaphthalene-based solvent (e.g., diisopropylnaphthalene), or a mixture of 1-methylnaphthalene, 2-methylnaphthalene and naphthalene (e.g., 200 ND product, CAS number: 64742-94-5), where 1-methylnaphthalene, 2-methylnaphthalene and a mixture of naphthalene are very particularly preferred as solvents. If the active ingredient c) is liquid at room temperature, preferably no solvent is used, for example in the case of clomazone or acetochlor. In a preferred embodiment, the active ingredient can serve as solvent d) for further active ingredients c) which can be solid at room temperature.

[0223] The active ingredient c) may be any agrochemically active compound, in particular a herbicide, insecticide or fungicide or a mixture thereof.

[0224] The active compounds identified herein by their common names are known and described, for example, in the Pesticide Manual ("The Pesticide Manual" 16th edition, British Crop Protection Council 2012), or can be found on the Internet (e.g. http: / / www.alanwood.net / pesticides). The classification is based on the current FRAC, HRAC, IRAC mode of action classification scheme at the time of filing this patent application.

[0225] Preferred active herbicidal ingredients c) are aclonifen, aminopyralid, benzofenap, bifenox, bromoxynil, bromoxynil butyrate, potassium heptanoate and potassium octanoate, butachlor, bixlozone, clomazone, clopyralid, 2,4-D, and also the following commonly used forms: 2,4-D-butoxy ester (2,4-D-b utotyl), 2,4-D-butyl ester, 2,4-D-dimethylammonium, 2,4-D-diamine (2,4-D-diethanolammonium), 2,4-D-ethyl ester, 2,4-D-2-ethylhexyl ester, 2,4-D-isobutyl ester, 2,4-D-isooctyl ester, 2,4-D-isopropyl ester, 2,4-D-isopropylammonium, 2,4-D-sodium, 2,4-D-triisopropanolammonium, 2,4-D-triethanolamine (2,4-D-triethanolammonium), diflufenican, 2-[(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, cinmethylin, dimethachlor, dimethenamid, dimethenamide-P, ethoxysulfuron, fenoxaprop, fenoxaprop-P, penoxaprop-ethyl, fenoxaprop-P-ethyl, fenquinotrione, fentrazamide, florasulam, flufenacet enacet), fluroxypyr, fluroxypyr-meptyl, foramsulfuron, halauxifen-methyl, iodosulfuron, iodosulfuron-methyl-sodium, isoxaflutole, MCPA (4-chloro-2-methylphenoxy)acetic acid, also including the following common forms: MCPA-butoxy ester, MCPA-dimethylammonium, MCPA-isooctyl ester, MCPA-sodium, MCPA-potassium, MCPA-2-ethylhexyl ester, mefenacet,mesosulfuron, mesosulfuron-methyl, metazachlor, metolachlor, S-metolachlor, metosulam, metribuzin, naproxenamide, nicosulfuron, oxadiargyl, oxadiazon, pendimethalin, pethoxamid, picloram, propoxazolone ycarbazone), propoxycarbazone-sodium, propyzamid, prosulfocarb, pyrasulfotole, pyroxasulfone, pyroxsulam, quinmerac, tefuryltrione, tembotrione, thiencarbazone, thiencarbazone-methyl, triafamone. ,

[0226] Preferred safeners to be included in ingredient c are the following safeners designated as component s):

[0227] s1) a compound selected from the group consisting of heterocyclic carboxylic acid derivatives:

[0228] s1 a ) dichlorophenylpyrazoline-3-carboxylic acid type compound (S1a), preferably a compound such as

[0229] 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid, ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate (S1-1) ("mefenpyr-diethyl"), and related compounds as described in WO-A-91 / 07874;

[0230] s1 b) derivatives of dichlorophenylpyrazolecarboxylic acid (S1b), preferably compounds such as 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylic acid ethyl ester (S1-2), 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylic acid ethyl ester (S1-3), 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylic acid ethyl ester (S1-4) and related compounds as described in EP-A-333131131 and EP-A-269806;

[0231] s1 c ) derivatives of 1,5-diphenylpyrazole-3-carboxylic acid (S1c), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-5), methyl 1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-6), and related compounds as described, for example, in EP-A-268554;

[0232] s1 d ) triazole carboxylic acid type compounds (S1d), preferably compounds such as fenchlorazole (ethylester), i.e. 1-(2,4-dichlorophenyl)-5-trichloromethyl-1H-1,2,4-triazole-3-carboxylic acid ethyl ester (S1-7), and related compounds as described in EP-A-174562 and EP-A-346620;

[0233] s1 e )5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid type compounds (S1e), preferably compounds such as 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylic acid ethyl ester (S1-8) or 5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-9), and related compounds as described in WO-A-91 / 08202, or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid 5,5-diphenyl-2-isoxazoline-3-carboxylic acid n-propyl ester (S1-12) or 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-13), as described in patent application WO-A-95 / 07897.

[0234] s2) A compound selected from 8-quinolyloxy derivatives (S2):

[0235] s2 a )8-quinolinyloxyacetic acid type compound (S2 a), preferably 1-methylhexyl (5-chloro-8-quinolinyloxy) acetate ("cloquintocet-mexyl") (S2-1), 1,3-dimethylbutan-1-yl (5-chloro-8-quinolinyloxy) acetate (S2-2), 4-allyloxybutyl (5-chloro-8-quinolinyloxy) acetate (S2-3), 1-allyloxypropan-2-yl (5-chloro-8-quinolinyloxy) acetate (S2-4), ethyl (5-chloro-8-quinolinyloxy) acetate (S2-5), methyl 5-chloro-8-quinolinyloxy acetate (S2-6), allyl (5-chloro-8-quinolinyloxy) acetate (S2-7), (5-chloro-8-quinolinyloxy) acetate (S2-8), methyl 5-chloro-8-quinolinyloxy acetate (S2-9), methyl 5-chloro-8-quinolinyloxy acetate (S2-10), methyl 5-chloro-8-quinolinyloxy acetate (S2-11), methyl 5-chloro-8-quinolinyloxy acetate (S2-12), methyl 5-chloro-8-quinolinyloxy acetate (S2-13), methyl 5-chloro-8-quinolinyloxy acetate (S2-14), methyl 5-chloro-8-quinolinyloxy acetate (S2-15), methyl 5-chloro-8-quinolinyloxy acetate (S2-16), methyl 5-chloro-8-quinolinyloxy acetate (S2-17), methyl 5-chloro-8-quinolinyloxy acetate (S2-18), methyl 5-chloro-8-quinolinyloxy acetate (S2-19), methyl 5-chloro-8-quinolinyloxy acetate (S2-23), methyl 5-chloro-8-quinolinyloxy acetate (S2-24), methyl 5-chloro-8-quinolinyloxy acetate (S2-25), methyl 5-chloro- 2-(2-propylideneiminoxy)-1-ethyl (5-chloro-8-quinolinyloxy)acetate (S2-8), 2-oxopropyl-1-yl (5-chloro-8-quinolinyloxy)acetate (S2-9), and related compounds as described in EP-A-86750, EP-A-94349 and EP-A-191736 or EP-A-0492366, and (5-chloro-8-quinolinyloxy)acetic acid (S2-10), and hydrates and salts thereof, for example, lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, iron salts, ammonium salts, quaternary ammonium salts, sulfonium salts or phosphonium salts thereof, as described in WO-A-2002 / 34048;

[0236] s2 b )(5-chloro-8-quinolyloxy)malonate type compounds (S2b), preferably compounds such as diethyl (5-chloro-8-quinolyloxy)malonate, diallyl (5-chloro-8-quinolyloxy)malonate, methyl ethyl (5-chloro-8-quinolyloxy)malonate, and related compounds as described in EP-A-0582198.

[0237] s3) Active ingredients of the dichloroacetamide type (S3), which are usually used as pre-emergence safeners (soil-acting safeners), e.g.

[0238] "dichlormid" (N,N-diallyl-2,2-dichloroacetamide) (S3-1),

[0239] "R-29148" from Stauffer (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) (S3-2),

[0240] "R-28725" from Stauffer (3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine) (S3-3),

[0241] "benoxacor" (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4),

[0242] "PPG-1292" (N-allyl-N-[(1,3-dioxolan-2-yl)methyl]dichloroacetamide) (S3-5) from PPG Industries,

[0243] "DKA-24" (N-allyl-N-[(allylaminocarbonyl)methyl]dichloroacetamide) (S3-6) from Sagro-Chem,

[0244] "AD-67" or "MON 4660" (3-dichloroacetyl-1-oxa-3-azaspiro[4.5]decane) from Nitrokemia or Monsanto (S3-7),

[0245] "TI-35" (1-dichloroacetylazepane) (S3-8) from TRI-Chemical RT,

[0246] "Diclonon" (Dicyclonon) or "BAS145138" or "LAB145138" (S3-9),

[0247] ((RS)-1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[1,2-a]pyrimidin-6-one) from BASF,

[0248] "Furilazole" or "MON 13900" ((RS)-3-dichloroacetyl-5-(2-furyl)-2,2-dimethyloxazolidine) (S3-10), and its (R) isomer (S3-11).

[0249] s4) Compounds from the class of acylsulfonamides (S4):

[0250] s4 a ) formula (S4 a ) and their salts, as described in WO-A-97 / 45016,

[0251]

[0252] in

[0253] R A 1 is (C1-C6)-alkyl, (C3-C6)-cycloalkyl, wherein the latter two groups are selected from the following v AThe cyclic groups may be substituted by halogen, (C1-C4)-alkoxy, (C1-C6)-haloalkoxy and (C1-C4)-alkylthio groups, and for cyclic groups, may also be substituted by (C1-C4)-alkyl and (C1-C4)-haloalkyl groups;

[0254] R A 2 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, CF3;

[0255] m A is 1 or 2;

[0256] vA is 0, 1, 2, or 3;

[0257] s4 b ) a 4-(benzoylsulfamoyl)benzamide compound of formula (S4b) and a salt thereof, as described in WO-A-99 / 16744,

[0258]

[0259] in

[0260] R B 1 , R B 2 are independently hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C3-C6)-alkenyl, (C3-C6)-alkynyl,

[0261] R B 3 is halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl or (C1-C4)-alkoxy, and

[0262] m B is 1 or 2,

[0263] For example, the following compounds,

[0264] R B 1 = cyclopropyl, R B 2 =Hydrogen and (R B 3 )=2-OMe("cyprosulfamide", S4-1),

[0265] R B 1 = cyclopropyl, R B 2 =Hydrogen and (R B 3)=5-Cl-2-OMe(S4-2),

[0266] R B 1 =Ethyl, R B 2 =Hydrogen and (R B 3 )=2-OMe(S4-3),

[0267] R B 1 = isopropyl, R B 2 =Hydrogen and (R B 3 )=5-Cl-2-OMe(S4-4), and

[0268] R B 1 = isopropyl, R B 2 =Hydrogen and (R B 3 )=2-OMe(S4-5);

[0269] s4 c ) comes from formula (S4 c ) of the benzoylsulfamoylphenylurea class, as described in EP-A-365484,

[0270]

[0271] in

[0272] R C 1 , R C 2 are independently hydrogen, (C1-C8)-alkyl, (C3-C8)-cycloalkyl, (C3-C6)-alkenyl, (C3-C6)-alkynyl,

[0273] R C 3 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, CF3, and

[0274] m C is 1 or 2;

[0275] For example

[0276] 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea,

[0277] 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea,

[0278] 1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea;

[0279] s4 d ) N-phenylsulfonyl terephthalamide-type compounds of formula (S4d) and salts thereof, which are known from, for example, CN101838227,

[0280]

[0281] in

[0282] R D 4 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, CF3;

[0283] m D is 1 or 2;

[0284] R D 5 is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl or (C5-C6)-cycloalkenyl.

[0285] s5) Active ingredients (S5) from the class of hydroxyaromatic compounds and aromatic-aliphatic carboxylic acid derivatives, for example ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicylic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid, as described in WO-A-2004 / 084631, WO-A-2005 / 015994, WO-A-2005 / 016001.

[0286] s6) Active ingredients from the class of 1,2-dihydroquinoxaline-2-ones (S6), for example 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxaline-2-one, 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxaline-2-thione, 1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxaline-2-one hydrochloride, 1-(2-methylsulfonylaminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxaline-2-one, as described in WO-A-2005 / 112630.

[0287] s7) Compounds from the class of the diphenylmethoxyacetic acid derivatives (S7), for example methyl diphenylmethoxyacetate (CAS Reg. No. 41858-19-9) (S7-1), ethyl diphenylmethoxyacetate or diphenylmethoxyacetic acid, as described in WO-A-98 / 38856.

[0288] s8) A compound of formula (S8), as described in WO-A-98 / 27049,

[0289]

[0290] The symbols and subscripts are defined as follows:

[0291] R D 1 is halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy,

[0292] R D 2 is hydrogen or (C1-C4)-alkyl,

[0293] R D 3 is hydrogen, (C1-C8)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl or aryl, wherein each of the aforementioned carbon-containing radicals is unsubstituted or substituted by one or more, preferably up to 3, identical or different radicals selected from halogen and alkoxy; or a salt thereof,

[0294] n D An integer from 0 to 2.

[0295] s9) active ingredients from the class of 3-(5-tetrazolylcarbonyl)-2-quinolones (S9), for example 1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No. 219479-18-2), 1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No. 95855-00-8), as described in WO-A-199 / 000020;

[0296] s10) Compound of formula (S10a) or (S10b)

[0297] As described in WO-A-2007 / 023719 and WO-A-2007 / 023764

[0298]

[0299] in

[0300] R E 1 Halogen, (C1-C4)-alkyl, methoxy, nitro, cyano, CF3, OCF3

[0301] Y E , Z E are independently O or S,

[0302] n E is an integer from 0 to 4,

[0303] R E 2 is (C1-C 16 )-alkyl, (C2-C6)-alkenyl, (C3-C6)-cycloalkyl, aryl, benzyl, halogenated benzyl,

[0304] R E 3 is hydrogen or (C1-C6)-alkyl.

[0305] s11) Active ingredients of the oxyimino compound type (S11), which are known as seed dressings, for example

[0306] "oxabetrinil" ((Z)-1,3-dioxol-2-ylmethoxyimino(phenyl)acetonitrile) (S11-1), which is known as a seed dressing safener for millet / sorghum against damage by metolachlor,

[0307] "fluxofenim" (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethanone O-(1,3-dioxol-2-ylmethyl)oxime) (S11-2), which is known as a seed dressing safener for millet / sorghum against damage by isopropylamine, and

[0308] "Cyometrinil" or "CGA-43089" ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3), which is known as a seed dressing safener for millet / sorghum against damage by metolachlor.

[0309] s12) Active ingredients from the class of isothiochromanones (S12), for example methyl [(3-oxo-1H-2-benzothiopyran-4(3H)-ylidene)methoxy]acetate (CAS Reg. No. 205121-04-6) (S12-1) and related compounds from WO-A-1998 / 13361.

[0310] s13) one or more compounds of group (S13):

[0311] "Naphthalic anhydride" (1,8-naphthalene dicarboxylic anhydride) (S13-1), which is known as a seed dressing safener for corn against damage by thiocarbamate herbicides,

[0312] "fenclorim" (4,6-dichloro-2-phenylpyrimidine) (S13-2), known as safener for pretilachlor in sown rice,

[0313] "flurazole" (benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (S13-3), known as a seed dressing safener for millet / sorghum against alachlor and isopropylamine damage,

[0314] "CL 304415" from American Cyanamid (CAS Reg. No. 31541-57-8) (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4), which is known as a safener for corn against damage by imidazolinones,

[0315] "MG 191" from Nitrokemia (CAS Reg. No. 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5), which is known as a safener for corn,

[0316] "MG 838" from Nitrokemia (CAS Reg. No. 133993-74-5) (2-propenyl-1-oxa-4-azaspiro[4.5]decane-4-carbodithioate) (S13-6),

[0317] "disulfoton" ("disulfoton") (S-2-ethylthioethyl dithiophosphoric acid O,O-diethyl ester) (S13-7),

[0318] "dietholate" (O-phenylthiophosphoric acid O,O-diethyl ester) (S13-8),

[0319] "mephenate" (4-chlorophenyl methylcarbamate) (S13-9).

[0320] s14) Active ingredients which, in addition to their herbicidal action on weeds, also act as safeners for crop plants such as rice, e.g.

[0321] "dimepiperate" or "MY-93" (S-1-methyl 1-phenylethylpiperidin-1-carbothioate), which is known as a safener for rice against damage by the herbicide cypermethrin,

[0322] "Methiocarb" or "SK 23" (1-(1-methyl-1-phenylethyl)-3-p-tolylurea), which is known as a safener for rice against damage by the herbicide pyrazosulfuron-methyl,

[0323] "benzyluron" = "JC-940" (3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)urea, see JP-A-60087254), which is known as a safener for rice against damage by some herbicides,

[0324] "Methoxyphenone" or "NK 049" (3,3'-dimethyl-4-methoxybenzophenone), which is known as a safener for rice against damage by some herbicides,

[0325] "CSB" (1-bromo-4-(chloromethylsulfonyl)benzene) (CAS Reg. No. 54091-06-4) from Kumiai, which is known as a safener against damage by some herbicides in rice.

[0326] s15) A compound of formula (S15) or a tautomer thereof

[0327]

[0328] As described in WO-A-2008 / 131861 and WO-A-2008 / 131860

[0329] in

[0330] R H 1 is a (C1-C6)-haloalkyl group, and

[0331] R H 2 is hydrogen or a halogen, and

[0332] R H 3 , R H 4 are each independently hydrogen, (C1-C 16 )-alkyl, (C2-C 16 )-alkenyl or (C2-C 16 )-alkynyl,

[0333] wherein each of the last three groups is unsubstituted or substituted by one or more groups selected from the 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,

[0334] or (C3-C6)-cycloalkyl, (C4-C6)-cycloalkenyl, (C3-C6)-cycloalkyl fused to one side of the ring to form a 4- to 6-membered saturated or unsaturated carbocyclic ring, or (C4-C6)-cycloalkenyl fused to one side of the ring to form a 4- to 6-membered saturated or unsaturated carbocyclic ring,

[0335] wherein each of the last four groups is unsubstituted or substituted by one or more groups selected from the group consisting of halogen, hydroxy, cyano, (C1-C4) alkyl, (C1-C4) haloalkyl, (C1-C4) alkoxy, (C1-C4) haloalkoxy, (C1-C4) alkylthio, (C1-C4) alkylamino, di[(C1-C4) alkyl]amino, [(C1-C4) alkoxy]carbonyl, [(C1-C4) haloalkoxy]carbonyl, unsubstituted or substituted (C3-C6) cycloalkyl, unsubstituted or substituted phenyl and unsubstituted or substituted heterocyclyl,

[0336] or

[0337] R H 3 is (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C6)-alkynyloxy or (C2-C4)-haloalkoxy, and

[0338] R H 4 is hydrogen or (C1-C4)-alkyl, or

[0339] R H 3 and R H 4 Together with the directly bonded nitrogen atom, it is a four- to eight-membered heterocyclic ring which, in addition to the nitrogen atom, may also contain further ring heteroatoms, preferably up to two further ring heteroatoms selected from N, O and S, and which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy and (C1-C4)-alkylthio.

[0340] s16) Active ingredients which are primarily used as herbicides but which also act as safeners for crop plants, e.g.

[0341] (2,4-dichlorophenoxy)acetic acid (2,4-D), (4-chlorophenoxy)acetic acid, (R, S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop), 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), 3,6-dichloro-2-methoxybenzoic acid 1-(ethoxycarbonyl)ethyl ester (lactidichlor-ethyl).

[0342] Preferred safeners s) are selected from the group consisting of isoxadifen, cyproconazole, cloquintocet-mexyl and mefenpyr-butyl. Particular preference is given to mefenpyr-butyl and mefenpyr-butyl. Very particular preference is given to mefenpyr-butyl.

[0343] Particularly preferred are active herbicidal ingredients c) selected from the group consisting of:

[0344] Flufenacet, bensulfuron, pendimethalin, difluanid, bensulfuron, metribuzin, sulfamethoxam, propoxychlor, ureasulfuron-butyl, oxadiazine, bromoxynil, fluazifop-methyl, 2,4-D, MCPA.

[0345] Very particular preference is given to the active herbicidal ingredients c) flufenacet, pyraclostrobin, diflufenicol.

[0346] Particular preference is also given to mixtures of one or more active herbicidal ingredients c) selected from:

[0347] Flufenacet and pethosulf; Flufenacet and aclofenac; Flufenacet and metribuzin; Flufenacet and fluclopyralid; Benthiocarb and flufenacet; Benthiocarb and aclofenac; Benthiocarb and metribuzin; Benthiocarb and flufenacet; Benthiocarb and flufenacet; Pendimethalin and flufenacet; Pendimethalin and aclofenac; Pendimethalin and metribuzin; Pendimethalin and flufenacet; Methribuzin and flufenacet; Flufenacet and flufenacet; Flufenacet and flufenacet; Flufenacet and flufenacet; Flufenacet and flufenacet; Flufenican; metribuzin and fenpyralid, fluazifop-methyl and fenpyralid; sulfonepyralid and diflufenican; fenpyralid and diflufenican; sulfonepyralid and difenpyralid; sulfonepyralid and difenpyralid; sulfonepyralid and fenpyralid; sulfonepyralid and metribuzin; sulfonepyralid and flufenacet; sulfonepyralid and diflufenican; sulfonepyralid and fenpyralid; flufenacet and metribuzin; sulfonepyralid and flufenacet; sulfonepyralid and diflufenican or flufenacet and sulfonepyralid and dilflufenican (dilflufenican); fenpyralid and diflufenican and flufenacet; metribuzin and diflufenican and flufenacet.

[0348] The mixture is most preferably selected from: flufenacet and diflufenac; flufenacet and pyraclostrobin; beniflox and diflufenac; metribuzin and diflufenac; flufenacet and beniflox; flufenacet and metribuzin; flufenacet and pyraclostrobin and diflufenac; beniflox and diflufenac and flufenacet; metribuzin and diflufenac and flufenacet; metribuzin and diflufenac and flufenacet.

[0349] The active herbicidal ingredients c) mentioned and mixtures thereof can likewise be used together with a safener selected from isoxadifen, cyprosulfamide, clofenac-butyl and mefenpyr-butyl.

[0350] Most preferably, the mixture comprising c) and s) is selected from: 2-[(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), cypermethrin, flufenacet, diflufenicol and pyraclostrobin; flufenacet and diflufenicol and pyraclostrobin; benifloxylidene and diflufenicol and pyraclostrobin; sulfonepyraclostrobin and pyraclostrobin.

[0351] Examples of fungicides as compound c) are:

[0352] 1) Inhibitors of ergosterol biosynthesis, for example (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamid, (1.005) fenpropidin, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquinconazole, (1.009) flutriafol, (1.010) imazalil, (1.011) imazalil sulfate sulfate), (1.012) ipconazole, (1.013) metconazole, (1.014) myclobutanil, (1.015) paclobutrazol, (1.016) prochloraz, (1.017) propiconazole, (1.018) prothioconazole, (1.019) pyrisoxazole, (1.020) spiroxamine, (1.021) tebuconazole, (1.022) tetraconazole, (1.023) triadimenol, (1.024) tridemorph, (1.025) trimethoate riticonazole), (1.026) (1R, 2S, 5S) -5- (4-chlorobenzyl) -2- (chloromethyl) -2-methyl-1- (1H-1, 2, 4-triazol-1-ylmethyl) cyclopentanol, (1.027) (1S, 2R, 5R) -5- (4-chlorobenzyl) -2- (chloromethyl) -2-methyl-1- (1H-1, 2, 4-triazol-1-ylmethyl) cyclopentanol, (1.028) (2R) -2- (1-chlorocyclopropyl) -4- [( 1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.029) (2R)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.030) (2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.041)031) (2S) -2- (1-chlorocyclopropyl) -4- [(1R) -2,2-dichlorocyclopropyl] -1- (1H-1,2,4-triazol-1-yl) butan-2-ol, (1.032) (2S) -2- (1-chlorocyclopropyl) -4- [(1S) -2,2-dichlorocyclopropyl] -1- (1H-1,2,4-triazol-1-yl) butan-2-ol, (1.033) (2S) -2- [4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl] -1- (1H-1,2,4-triazol-1-yl) propan-2-ol, (1.034) (R) - [3- (4-chloro-2-fluorophenyl) -5- (2,4-difluorophenyl) -1,2-oxazol-4-yl] (pyridine -3-yl)methanol, (1.035) (S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.036) [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.037) 1-({(2R,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4-triazole, (1.038) 1-({(2S,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl- 1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.041) 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate -yl thiocyanate, (1.042) 2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.043) 2-[(2R,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.044) 2-[(2R,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.046) 2-[(2R,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.047)045) 2-[(2R,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.046) 2-[(2S,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.047) 2-[(2S,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.04 8) 2-[(2S,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.049) 2-[(2S,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.050) 2-[1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.051) 2-[2-chloro-4-(2 ,4-dichlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.052) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.053) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.054) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)pentan-2-ol, (1.055) Mefentrifluconazole ), (1.056) 2-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.057) 2-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.058) 2-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.059) 5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.060) 5-(allylsulfanyl)-1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-1H-1,2,4-triazole, (1.061) 5-(allylsulfanyl)-1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-1H-1,2,4-triazole, (1.062) 5-(allylsulfanyl)-1-{[rel(2R,3S)-3-(2- N'-(2,5-dimethyl-4-{[3-(1,1,2,2-tetrafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.064) N'-(2,5-dimethyl-4-{[3-(2,2,2-trifluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.065) N'-(2,5-dimethyl-4-{[3-(2,2,3,3-tetrafluoropropoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methyliminocarboxamide , (1.066) N′-(2,5-dimethyl-4-{[3-(pentafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.067) N′-(2,5-dimethyl-4-{3-[(1,1,2,2-tetrafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.068) N′-(2,5-dimethyl-4-{3-[(2,2,2-trifluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.069) N′-(2,5-dimethyl-4-{3-[(2,2,3,3-tetrafluoropropyl)sulfanyl]phenoxy}phenyl )-N-ethyl-N-methyliminocarboxamide, (1.070) N′-(2,5-dimethyl-4-{3-[(pentafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.071) N′-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methyliminocarboxamide, (1.072) N′-(4-{[3-(difluoromethoxy)phenyl]sulfanyl}-2,5-dimethylphenyl)-N-ethyl-N-methyliminocarboxamide, (1.073) N′-(4-{3-[(difluoromethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methyliminocarboxamide, (1.074) N′-(4-{3-[(difluoromethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methyliminocarboxamide, (1.076)074) N′-[5-bromo-6-(2,3-dihydro-1H-inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methyliminocarboxamide, (1.075) N′-{4-[(4,5-dichloro-1,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methyliminocarboxamide, (1.076) N′-{5-bromo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.0 77) N′-{5-bromo-6-[(1S)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.078) N′-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.079) N′-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.080) N′ -{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.081) ipfentrifluconazole, (1.082) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.083) 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridinyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (1.084) 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridinyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (1.085) 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile and (1.086) 4-[[6-[rac-(2R)-2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile.

[0353] 2) Inhibitors of respiratory complex I or II, for example (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr, (2.009) isofetamid, (2.010) pyrazolone isopyrazam (trans epimeric enantiomers 1R, 4S, 9S), (2.011) pyraclostrobin (trans epimeric enantiomers 1S, 4R, 9R), (2.012) pyraclostrobin (trans epimeric racemates 1RS, 4SR, 9SR), (2.013) pyraclostrobin (mixture of cis epimeric racemates 1RS, 4SR, 9RS and trans epimeric racemates 1RS, 4SR, 9SR), (2.014) pyraclostrobin (cis epimeric enantiomers 1R, 4S, 9R), (2.015) pyraclostrobin (cis epimeric enantiomers 1S, 4R, 9S), (2.016) pyraclostrobin (cis epimeric enantiomers 1S, 4R, 9S), (2.022) 1,3-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.023) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.024) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.025) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.026) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.027) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.028) 1,3-dimethyl- 1H-pyrazole-4-carboxamide, (2.024) 1,3-dimethyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.025) 1-methyl-3-(trifluoromethyl)-N-[2′-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.026) 2-fluoro-6-(trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)benzamide, (2.027) 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.028) 1-methyl-3-(trifluoromethyl)-N-[2′-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.029) 1-methyl-3-(trifluoromethyl)-N-[2′-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.030)028) inpyrfluxam, (2.029) 3-(difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.030) fluindapyr, (2.031) 3-(difluoromethyl)-N-[(3R)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.032) 3-(difluoromethyl)-N-[(3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide formamide, (2.033) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine, (2.034) N-(2-cyclopentyl-5-fluorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.035) N-(2-tert-butyl-5-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.036) N-(2-tert-butylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.037) N-(5- chloro-2-ethylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.038) isoflucypram, (2.039) N-[(1R,4S)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.040) N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.0 41) N-[1-(2,4-dichlorophenyl)-1-methoxyprop-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.042) N-[2-chloro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.043) N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.044) N-[5-chloro-2-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.045) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[5-methyl-2-(trifluoromethyl)benzyl]-1H-pyrazole-4-carboxamide, (2.046) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-fluoro-6-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.047) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, ( 2.048) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.049) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.050) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(5-fluoro-2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.051) N-cyclopropyl 1-methyl-1H-pyrazole-4-carboxamide, (2.052) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-fluorobenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.053) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.054) N-cyclopropyl- N-(2-cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.055) N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.056) N-cyclopropyl-N-(2-cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.057) pyrapropoyne. .

[0354] 3) Inhibitors of respiratory complex III, such as (3.001) ametoctradin, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) coumethoxystrobin, (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxazole adone), (3.010) fenamidone, (3.011) flufenoxystrobin, (3.012) fluoxastrobin, (3.013) kresoxim-methyl, (3.014) metominostrobin, (3.015) orysastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyrame tostrobin), (3.019) pyraoxystrobin, (3.020) trifloxystrobin, (3.021) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylvinyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylacetamide, (3.022) (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.023) (2R)-2-{2-[ (3.024) (2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.025) fenpicoxamid, (3.026) mandestrobin, (3.027) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-formamido-2-hydroxybenzamide, (3.028) (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.029) (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.030) (2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.031) (2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.032) (3.033)029) methyl {5-[3-(2,4-dimethylphenyl)-1H-pyrazol-1-yl]-2-methylbenzyl}carbamate, (3.030) metyltetraprole, (3.031) florylpicoxamid. .

[0355] 4) Inhibitors of mitosis and cell division, for example (4.001) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate-methyl, (4.008) zoxamide, (4.009) 3-chloro-4-(2,6-difluorophenyl)-6-methyl- 5-phenylpyridazine, (4.010) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (4.011) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine, (4.012) 4-(2-bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.013) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.014) 4-(2-bromo-4-fluorophenyl)-N-(2-bromophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.015) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.016) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.017) 4-(2-bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.018) 4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.019) 4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H- Pyrazole-5-amine, (4.020) 4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.021) 4-(2-chloro-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.022) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (4.023) N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.024) N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.025)025) N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine. .

[0356] 5) Compounds capable of multi-site action, such as (5.001) Bordeaux mixture, (5.002) captafol, (5.003) captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper oxychloride, oxychloride), (5.009) copper sulfate (2+), (5.010) dithianon, (5.011) dodine, (5.012) folpet, (5.013) mancozeb, (5.014) maneb, (5.015) metiram, (5.016) metiram zinc zinc), (5.017) oxine-copper, (5.018) propineb, (5.019) sulfur and sulfur preparations including calcium polysulfide, (5.020) thiram, (5.021) zineb, (5.022) ziram, (5.023) 6-ethyl-5,7-dioxo-6,7-dihydro-5H-pyrrolo[3′,4′:5,6][1,4]dithiino[2,3-c][1,2]thiazole-3-carbonitrile.

[0357] 6) Compounds capable of inducing host defense, such as (6.001) acibenzolar-S-methyl, (6.002) isotianil, (6.003) probenazole, and (6.004) tiadinil.

[0358] 7) Inhibitors of amino acid and / or protein biosynthesis, for example (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil, (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinolone.

[0359] 8) Inhibitors of ATP production, for example (8.001) silthiofam.

[0360] 9) Inhibitors of cell wall synthesis, for example (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamid, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one.

[0361] 10) Inhibitors of lipid and membrane synthesis, for example (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl.

[0362] 11) Melanin biosynthesis inhibitors, for example (11.001) tricyclazole, (11.002) tolprocarb.

[0363] 12) Nucleic acid synthesis inhibitors, for example (12.001) benalaxyl, (12.002) kiralaxyl, (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam).

[0364] 13) Signal transduction inhibitors, for example (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazid, (13.005) quinoxyfen, (13.006) vinclozolin.

[0365] 14) Compounds that can act as uncouplers, for example (14.001) fluazinam, (14.002) meptyldinocap.

[0366] 15) Other fungicides, such as (15.001) abscisic acid, (15.002) benthiazole, (15.003) bethoxazin, (15.004) capsimycin, (15.005) carvone, (15.006) chinomethionat, (15.007) cufraneb, (15.008) cyflufenamid, (15.0 09) cymoxanil, (15.010) cyprosulfamide, (15.011) flutianil, (15.012) fosetyl-aluminium, (15.013) fosetyl-calcium, (15.014) fosetyl-sodium, (15.015) methyl isothiocyanate, (15.016) metrafenone, (15.017) mildiomycin, (15.018) natamycin, (15.019) nickel dimethyl dithiocarbamate dimethyldithiocarbamate), (15.020) nitrothal-isopropyl, (15.021) oxamocarb, (15.022) oxathiapiprolin, (15.023) oxyfenthiin, (15.024) pentachlorophenol and its salts, (15.025) phosphorous acid and its salts, (15.026) propamocarb-fosetylate, (15.027) fenpyraclostrobin pyriofenone (chlazafenone), (15.028) tebufloquin, (15.029) tecloftalam, (15.030) tolnifanide, (15.031) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.032) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.033) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.034) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.035) 1-(4-{4-[(5R)-5032) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.033) 2-(6-benzylpyridin-2-yl)quinazoline, (15.034) dipymetitrone, (15.035) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1 -yl]ethanone, (15.036) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.037) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.038) 2-[6-(3-fluoro-4-methoxy 2-{(5S)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.040) 2-{(5S)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.041) Ipflufenoquinoline, (1 5.042) 2-{2-fluoro-6-[(8-fluoro-2-methylquinolin-3-yl)oxy]phenyl}propan-2-ol, (15.043) fluoxapiprolin, (15.044) 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenyl methanesulfonate, (15.045) 2-phenylphenol and its salts, (15.046) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.047) quinofumelin, (15.048)048) 4-amino-5-fluoropyrimidin-2-ol (tautomeric form: 4-amino-5-fluoropyrimidin-2(1H)-one), (15.049) 4-oxo-4-[(2-phenylethyl)amino]butyric acid, (15.050) 5-amino-1,3,4-thiadiazole-2-thiol, (15.051) 5-chloro-N′-phenyl-N′-(prop-2-yn-1-yl)thiophene-2-sulfonylhydrazide, (15.052) 5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4-amine, (15.053) 5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine, (15.054) 9-fluoro-2,2-dimethyl-5-(quinolin-3-yl)-2,3-dihydro-1 , 4-benzoxazepine, (15.055) but-3-yn-1-yl {6-[({[(Z)-(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.056) (2Z)-3-amino-2-cyano-3-phenylacrylate, (15.057) phenazine-1-carboxylic acid, (15.058) propyl 3,4,5-trihydroxybenzoate, (15.059) quinolin-8-ol, (15.060) quinolin-8-ol sulfate (2:1), (15.061) {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate} tert-butyl carbamate, (15.062) 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one, (15.063) aminopyrifen, (15.064) (N′-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methyliminocarboxamide), (15.065) (N′-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methyliminocarboxamide), (15.066) (2-{2-[(7,8-difluoro-2-methylquinolin-3-yl)oxy]-6-fluorophenyl}propan-2-ol), (15.067) (5- bromo-1-(5,6-dimethylpyridin-3-yl)-3,3-dimethyl-3,4-dihydroisoquinoline), (15.068) (3-(4,4-difluoro-5,5-dimethyl-4,5-dihydrothieno[2,3-c]pyridin-7-yl)quinoline), (15.069) (1-(4,5-dimethyl-1H-benzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline), (15.070) 8-fluoro-3-(5-fluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinolone, (15.071) 8-fluoro-3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinolone, (15.072) 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)-8-fluoroquinoline, (15.073) (N-methyl-N-phenyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide), (15.074) (methyl {4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}carbamate), (15.075) (N-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}cyclopropanecarboxamide), (15.076) N-methyl-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, ( 15.077) N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.078) N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.079) N-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]-cyclopropanecarboxamide, (15.080) N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.081) 2,2-difluoro-N-methyl-2-[4-[5- 1,2,4-oxadiazol-3-yl]phenyl]-acetamide, (15.082) N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]acetamide, (15.083) N-[(E)-N-methoxy-C-methyl-carbonimidoyl]-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-benzamide, (15.084) N-[(Z)-N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.085) N -allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]-methyl]propionamide, (15.086) 4,4-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.087) N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-benzenecarbothioamide, (15.088) 5-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.089) N-((2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-3,3,3-trifluoro-propionamide, (15.090) 1-methoxy-1-methyl-3-[[4-[5-(trifluoromethyl}-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.091) 1,1-diethyl-3-[[4-[5-(trifluoromethyl}-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.092) N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide, (15.093) N-methoxy-N-[[4-[5 -(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, (15.094) 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.095) N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl)cyclopropanecarboxamide, (15.096) N,2-dimethoxy-N-[[4-[5-(trifluoromethyl}-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.097) N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.098) 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.099) 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.100) 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.101) 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.102) 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.103) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.104) 3,3-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.105) 1-[[3-fluoro-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]azepan-2-one, (15.106)106) 4,4-dimethyl-2-[[4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.107) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.108) (1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one ethyl]benzyl}-1H-pyrazol-4-yl)acetate, (15.109) N,N-dimethyl-1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-1,2,4-triazol-3-amine, (15.110) N-{2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}butanamide, (15.111) N-(1-methylcyclopropyl)-1- )-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.112) N-(2,4-difluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.113) 1-(5,6-dimethylpyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.114) 1-(6-(difluoromethyl)- )-5-methyl-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.115) 1-(5-(fluoromethyl)-6-methylpyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline and (15.116) 1-(6-(difluoromethyl)-5-methoxypyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline.

[0367] All specified compounds of groups (1) to (15) as described above can be present in the form of free compounds or, if their functional groups permit, in the form of their agrochemically active salts.

[0368] Examples of insecticides as compounds c) are:

[0369] (1) an acetylcholinesterase (AChE) inhibitor, preferably a carbamate selected from the group consisting of alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, arb), isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC and xylylcarb; or an organophosphate selected from acephate, azamethiphos, ethyl azinphos-methyl (azinphos-ethyl), azinphos-methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate dimethoate), dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothiophosphoryl) salicylate, isoxathion,Malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl imiphos-methyl), profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, triclorfon and vamidothion.

[0370] (2) GABA-gated chloride channel blockers, preferably cyclopentadiene-organochlorines selected from chlordane and endosulfan, or phenylpyrazoles (fiproles) selected from ethiprole and fipronil.

[0371] (3) Sodium channel modulators, preferably pyrethroids, selected from acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin s-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin , β-cyhalothrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [(1R)-trans-isomer], deltamethrin, empenthrin [(EZ)-(1R)-isomer], esfenvalerate, etof enprox), fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, momfluorothrin, permethrin, phenothrin [(1R )-trans-isomer], prallethrin, pyrethrins (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)-isomer], tralomethrin and transfluthrin, or DDT or methoxychlor.

[0372] (4) Competitive modulators of nicotinic acetylcholine receptors (nAChR), preferably neonicotinoids selected from acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam, or nicotine, or sulfoximines selected from sulfoxaflor, or butenolids selected from nupyradifurone, or mesoionics selected from triflumezopyrim.

[0373] (5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators, preferably spinosyns, selected from spinetoram and spinosad.

[0374] (6) Glutamate-gated chloride channel (GluCl) allosteric modulators, preferably avermectins / milbemycins, selected from abamectin, emamectin benzoate, lepimectin and milbemectin.

[0375] (7) Juvenile hormone mimetics, preferably selected from the following juvenile hormone analogs: hydroprene, kinoprene and methoprene, or fenoxycarb or pyriproxyfen.

[0376] (8) Various non-specific (multi-site) inhibitors, preferably alkyl halides selected from methyl bromide and other alkyl halides; or chloropicrine or sulfuryl fluoride or borax or tartar emetic, or methyl isocyanate generators selected from diazomet and metam.

[0377] (9) A chord organ TRPV channel modulator selected from pymetrozine and pyrifluquinazone.

[0378] (10) A mite growth inhibitor selected from the group consisting of clofentezine, hexythiazox, diflovidazin and etoxazole.

[0379] (11) An insect intestinal membrane microbial disruptor, which is selected from Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis and Bacillus thuringiensis plant protein, and the Bacillus thuringiensis subspecies is selected from Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb and Cry34Ab1 / 35Ab1.

[0380] (12) Mitochondrial ATP synthase inhibitors, preferably ATP disruptors selected from diafenthiuron; or organotin compounds selected from azocyclotin, cyhexatin and fenbutatinoxide; or propargite or tetradifon.

[0381] (13) An uncoupler of oxidative phosphorylation by interrupting the proton gradient, selected from chlorfenapyr, DNOC and sulfluramid.

[0382] (14) A nicotinic acetylcholine receptor channel blocker selected from the group consisting of bensultap, cartap hydrochloride, thiocylam and thiosultap-sodium.

[0383] (15) A type O chitin biosynthesis inhibitor selected from the group consisting of bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron.

[0384] (16) A type 1 chitin biosynthesis inhibitor selected from buprofezin.

[0385] (17) Molting disruptors (especially for Diptera, i.e. two-winged insects), selected from cyromazine.

[0386] (18) An ecdysone receptor agonist selected from the group consisting of chromafenozide, halofenozide, methoxyfenozide and tebufenozide.

[0387] (19) An octopamine receptor agonist selected from amitraz.

[0388] (20) A mitochondrial complex III electron transport inhibitor selected from the group consisting of hydramethylnone, acequinocyl and fluacrypyrim.

[0389] (21) Mitochondrial complex I electron transport inhibitors, preferably METI miticides, selected from fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad, or rotenone (Derris).

[0390] (22) A voltage-dependent sodium channel blocker selected from indoxacarb and metaflumizone.

[0391] (23) Acetyl-CoA carboxylase inhibitors, preferably tetronic acid and tetramic acid derivatives selected from spirodiclofen, spiromesifen and spirotetramat.

[0392] (24) Mitochondrial complex IV electron transport inhibitors, preferably phosphides selected from aluminum phosphide, calcium phosphide, phosphine and zinc phosphide, or cyanides selected from calcium cyanide, potassium cyanide and sodium cyanide.

[0393] (25) Mitochondrial complex II electron transport inhibitors, preferably β-ketonitrile derivatives selected from cyenopyrafen and cyflumetofen, and carboxanilides selected from pyflubumide.

[0394] (28) A ryanodine receptor modulator, preferably a diamide selected from the group consisting of chlorantraniliprole, cyantraniliprole and flubendiamide.

[0395] (29) A chord organ modulator (with an unclear target site) selected from flonicamid.

[0396] (30) Other active compounds selected from the group consisting of Acynonapyr, Afidopyropen, Afoxolaner, Azadirachtin, Benclothiaz, Benzoximate, Benzpyrimoxan, Bifenazate, Broflanilide, Bromopropylate, Chinomethionat, Chloroprallethrin, Cryolite, Cyclofenac Cyclaniliprole, Cycloxaprid, Cyhalodiamide, Dicloromezotiaz, Dicofol, Dimpropyridaz, Epsilon-Metofluthrin, Epsilon-Momfluthrin, Flometoquin, Fluazaindolizine, Fluensulfone, Flufenerim, Flufenoxystrobin, Flufiprole, Fluhexafon, Fluopyram, Flupyrimin, Fluralaner, Fluxametamide, Fufenozide, Guadipyr, Heptafluthrin, Imidaclothiz, Iprodione, Isocycloseram, Kappa-Bifenthrin, Kappa-Tefluthrin, Lotilaner, Meperfluthrin, Oxazosulfyl , Paichongding, Pyridalyl, Pyrifluquinazon, Pyriminostrobin, Spirobudiclofen, Spiropyridine Ethyl Ester, Tetramethylfluthrin, Tetraniliprole, Tetrachlorantraniliprole, Tigolaner, Tioxazafen, Thiofluoximate, Methyl Iodide; In addition,Preparations based on Bacillus firmus (I-1582, BioNeem, Votivo), and the following compounds: 1-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine (known from WO2006 / 043635) (CAS 885026-50-6), {1′-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]-5-fluorospiro[indole-3,4′-piperidinyl]-1(2H)-yl}(2-chloropyridin-4-yl)methanone (known from WO2003 / 106457) (CAS 637360-23-7), 2-chloro-N-[2-{1-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]piperidin-4-yl}-4-(trifluoromethyl)phenyl]isonicotinamide (known from WO2006 / 003494) (CAS 872999-66-1), 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-methoxy-1,8-diazaspiro[4.5]dec-3-en-2-one (known from WO2010052161) (CAS 1225292-17-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl carbonate (known from EP2647626) (CAS 1440516-42-6), 4-(but-2-yn-1-yloxy)-6-(3,5-dimethylpiperidin-1-yl)-5-fluoropyrimidine (known from WO2004 / 099160) (CAS 792914-58-0), PF1364 (known from JP2010 / 018586) (CAS 1204776-60-2), (3E)-3-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-1,1,1-trifluoro-propan-2-one (known from WO2013 / 144213) (CAS 1461743-15-6), N-[3-(benzylcarbamoyl)-4-chlorophenyl]-1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide (known from WO2010 / 051926) (CAS 1226889-14-0), 5-bromo-4-chloro-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-2-(3-chloro-2-pyridyl)pyrazole-3-carboxamide (known from CN103232431) (CAS 1449220-44-3), 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxo-3-thietanyl)-benzamide, 4-[5-(3,4-[(5S)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(trans-1-oxo-3-thietanyl)-benzamide and 4-[(5S)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxo-3-thietanyl)benzamide (known from WO 2013 / 050317 A1) (CAS 1332628-83-7), N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propionamide, (+)-N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propionamide and (-)-N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propionamide (known from WO 2013 / 162715 A2, WO 2013 / 162716 A2, US 2014 / 0213448 A1) (CAS 1477923-37-7), 5-[[(2E)-3-chloro-2-propen-1-yl]amino]-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile (known from CN 101337937 A) (CAS 1105672-77-2), 3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)thiomethyl]phenyl]-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide (Liudaibenjiaxuanan, known from CN 103109816 A) (CAS 1232543-85-9), N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridyl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide (known from WO 2012 / 034403 A1) (CAS 1268277-22-0), N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide (known from WO 2011 / 085575 A1) (CAS 1233882-22-8), 4-[3-[2,6-dichloro-4-[(3,3-(trifluoromethyl)phenyl)-1-(3-(trifluoromethyl)phenyl)-2-( ... 1232543-85-9), 3-(2,2-dichlorovinyl)-2,2-dimethyl-4-(1H-benzimidazol-2-yl)phenyl-cyclopropanecarboxylate (known from CN103524422 A) (CAS 1542271-46-4), (4aS)-7-chloro-2,5-dihydro-2-[[(methoxycarbonyl)[4-[(trifluoromethyl)thio]phenyl]amino]carbonyl]-indeno[1,2-e][1,3,4]oxadiazine-4a(3H)-carboxylic acid methyl ester (known from CN102391261 A) (CAS 1370358-69-2), 6-deoxy-3-O-ethyl-2,4-di-O-methyl-, 1-[N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1H-1,2,4-triazol-3-yl]phenyl]carbamate]-aL-pyranose (known from US 2014 / 0275503 A1) (CAS 1181213-14-8), 8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (CAS 1253850-56-4), (8-trans)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (CAS 933798-27-7), (8-cis)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (known from WO 2007040280 A1, WO2007040282 A1) (CAS 934001-66-8), N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)thio]-propionamide (known from WO 2015 / 058021 A1, WO 2015 / 058028 A1) (CAS 1477919-27-9) and N-[4-(aminothiomethyl)-2-methyl-6-[(methylamino)carbonyl]phenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide (known from CN 103265527 A) (CAS 1452877-50-7), 5-(1,3-dioxane-2-yl)-4-[[4-(trifluoromethyl)phenyl]methoxy]pyrimidine (known from WO 2013 / 115391 A1) (CAS 1449021-97-9), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-1,8-diazaspiro[4.5]decane-2,4-dione (known from WO 2014 / 187846 A1) (CAS 1638765-58-8), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl-carbonic acid ethyl ester (known from WO 2010 / 066780 A1, WO 2011151146 A1) (CAS 1229023-00-0), 4-[(5S)-5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[(4R)-2-ethyl-3-oxy-4-isoxazolidinyl]-2-methyl-benzamide (known from WO 2011 / 067272, WO2013 / 050302) (CAS 1309959-62-3). ,

[0397] Biological products: Biological spores can be added to the formulation or can also be encapsulated.

[0398] The capsule suspension concentrates according to the invention are extremely suitable for applying the active agricultural chemical ingredients present to plants and / or their habitat. They ensure that the active ingredients are released in the corresponding desired amount over a relatively long period of time.

[0399] The capsule suspension concentrates according to the invention can be used in practice as such or after dilution with water. Application is carried out by customary methods, ie for example by pouring or spraying.

[0400] The application rate of the capsule suspension concentrate of the present invention can be varied within a relatively wide range and is guided by the active agricultural chemical ingredient and its content in the microcapsule preparation.

[0401] The preferred use of the capsule suspension concentrate of the invention is as a herbicide in cereals and rapeseed, most preferably in winter barley, and in this case in the pre-emergence method and the post-emergence method. Thus, it is preferably used in autumn applications shortly after sowing of cereals and shortly before or shortly after germination of weeds, in particular grass weeds.

[0402] The capsule suspension concentrate of the present invention can be prepared by known methods, for example, as each component, optionally with other active ingredients, additives and / or conventional formulation adjuvants, then diluted with water in a conventional manner, or by diluting the components prepared separately or partially separately with water as a bucket mix. It is also possible to use each component (separate application) prepared separately or partially separately at different times. It is also possible to apply each component of the present invention or the capsule suspension concentrate (sequential application) in multiple parts, for example, by applying before emergence, then applying after emergence, or by applying in the early stage after emergence, then applying in the mid-term or late stage after emergence. It is preferred to combine or immediately apply the active ingredient in the corresponding combination continuously.

[0403] The present invention therefore also provides a method for controlling unwanted plants in plant crops, characterized in that the capsule suspension concentrate according to the invention is applied to the plants (eg harmful plants such as monocotyledonous or dicotyledonous weeds or unwanted crop plants) or to the area where the plants grow.

[0404] Unwanted plants are understood to mean all plants which grow in unwanted locations. These may be, for example, harmful plants (for example monocotyledonous or dicotyledonous weeds or unwanted crop plants).

[0405] Monocotyledonous weeds from, for example, the genera Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrost is, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, and Sorghum.

[0406] Dicotyledonous weeds from, for example, the following genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium , Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Linde rnia), Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.

[0407] Preferably, the capsule suspension concentrate according to the invention is used to control weeds of the species Alopecurus spp. Huds (or black grass).

[0408] The invention also provides for the use of the capsule suspension concentrates according to the invention for controlling undesirable vegetation, preferably in crops of useful plants.

[0409] If the capsule suspension concentrate of the present invention is applied to the soil surface before germination, weed seedlings are completely prevented from emerging from the soil, or the weeds grow until they reach the cotyledon stage, but then they stop growing and eventually die completely after three to four weeks.

[0410] When the capsule suspension concentrate according to the invention is applied to the green parts of the plants after emergence, growth is also rapidly arrested within a very short time after the treatment and the weed plants remain at the growth stage at the time of application or die completely after a certain time, thus eliminating weed competition that is harmful to the crop plants very early and in a permanent manner.

[0411] The capsule suspension concentrates of the invention are distinguished by rapid onset of action and long duration of herbicidal action. Said properties and advantages are useful in practical weed control to keep crops free of unwanted competing plants and thus to ensure and / or increase yields in terms of quality and quantity. In view of the properties described, these novel compositions clearly exceed the state of the art in this field.

[0412] Although the capsule suspension concentrates of the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, there is only insignificant damage, if any, to crop plants of economically important crops, for example dicotyledonous crop species such as soybean, cotton, rapeseed, sugar beet or gramineous crops such as wheat, barley, rye, oats, millet / sorghum, rice or corn. For these reasons, the capsule suspension concentrates of the invention are very suitable for the selective control of unwanted vegetation in agriculturally useful plants or ornamental plants.

[0413] In addition, the capsule suspension concentrates of the compounds according to the invention have excellent growth-regulatory properties in crop plants. They intervene in the metabolism of the plant itself by means of regulatory effects and can therefore be used for controlled influence of plant components and for promoting harvest, for example by inducing dehydration and dwarfing growth. In addition, they are also suitable for general control and inhibition of unwanted plant growth without killing the plant in the process. The inhibition of vegetative growth plays an important role for many monocotyledonous and dicotyledonous crops, since, for example, lodging can be reduced or completely prevented.

[0414] By virtue of its herbicidal and plant growth regulating properties, the capsule suspension concentrate of the present invention can also be used to control harmful plants in known or yet to be developed genetically modified plant crops. Typically, transgenic plants are characterized by particularly advantageous properties, such as resistance to certain pesticides (particularly certain herbicides), resistance to plant diseases or pathogens of plant diseases (e.g. certain insects or microorganisms such as fungi, bacteria or viruses). Other specific properties relate, for example, to the quantity, quality, storage, composition and specific ingredients of the harvested material. For example, there are known transgenic plants with increased starch content or altered starch quality, or those with different fatty acid compositions in the harvested material.

[0415] Preference is given to the use of the capsule suspension concentrates of the invention in transgenic crops of economically important beneficial and ornamental plants, for example grass crops such as wheat, barley, rye, oats, millet / sorghum, rice, rape and corn. Preferably, the composition of the invention can be used as a herbicide in crops of beneficial plants which are resistant to the phytotoxic effects of herbicides or have been rendered resistant by genetic engineering. Particular preference is given to wheat, barley, rye and rape, preferably winter rape.

[0416] When the capsule suspension concentrate of the present invention is used in transgenic crops, not only the effects on harmful plants observed in other crops will occur, but also the specific effects for application in specific transgenic crops will generally occur, such as an altered or particularly broadened weed spectrum that can be controlled, an altered application rate that can be used for application, preferably good compatibility with herbicides that are resistant to transgenic crops, and an influence on the growth and yield of transgenic crop plants.

[0417] The present invention also provides a method for controlling unwanted plant growth, preferably in crop plants such as cereals (e.g. wheat, barley, rye, oats, rice, corn, millet / sorghum), more preferably in monocotyledonous crops (e.g. cereals, for example wheat, barley, rye, oats, their hybrids such as triticale, rice, corn and millet / sorghum), wherein one or more capsule suspension concentrates according to the invention are applied to harmful plants, plant parts, plant seeds or to the area where the plants grow, for example the area under cultivation. Preferably, the capsule suspension concentrate according to the invention is applied before and after emergence. More preferably, before emergence.

[0418] Therefore, the present invention also provides the use of the capsule suspension concentrate of the present invention for controlling harmful plants in transgenic crop plants.

[0419] The present invention also preferably provides for the use of the capsule suspension concentrate according to the invention for treating plants whose seeds have been treated with a safener.

[0420] Insecticides:

[0421] The capsule suspension concentrates of the invention can preferably be used as insecticides. They are active against normally sensitive and resistant species and against all or some developmental stages. The above-mentioned pests include:

[0422] Pests from the phylum Arthropoda, in particular the class Arachnida, for example Acarus spp. (for example Acarus siro), Aceria kuko, Aceria sheldoni, Aculops spp., Aculus spp. (for example Aculus fockeui, Aculus schlechtendali), Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp. (for example Brevipalpus phoenicis), Bryobia graminum), Bryobia praetiosa, Centruroides spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp. (e.g., Eotetranychu shicoriae), Epitrimerus pyri, Eutetranychus spp. (e.g., Eutetranychus banksi), Eriophyes spp. (e.g., Eriophyes pyri), Glycyphagus domesticus), Halotydeus destructor, Hemitarsonemus spp. (e.g. Hemitarsonemus latus (=Polyphagotarsonemus latus)), Hyalomma spp., Ixodes spp., Latrodectus spp., Loxosceles spp.), Neutrombicula autumnnalis, Nuphersa spp., Oligonychus spp. (e.g. Oligonychus coffeae, Oligonychus coniferarum, Oligonychus ilicis, Oligonychus indicus, Oligonychus mangiferus, Oligonychus pratensis, Oligonychus punicae, Oligonychus yothersi), Ornithodorus spp., Ornithonyssus spp., Panonychus spp. (e.g. Panonychus citri (= Metatetranychus spp.), citri), Panonychus ulmi (= Metatetranychus ulmi), Phyllocoptruta oleivora, Platytetranychus multidigituli, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Steneotarsonemus spp., Steneotarsonemus spinki, Tarsonemus spp. (e.g. Tarsonemus confusus, Tarsonemus pallidus), Tetranychus spp.) (e.g., Tetranychus canadensis, Tetranychus cinnabarinus, Tetranychus turkestani, Tetranychus urticae), Trombicula alfreddugesi, Vaejovis spp., Vasates lycopersici;

[0423] Pests from the class Chilopoda, such as Geophilus spp. and Scutigera spp.;

[0424] Pests from the order Collembola or class Collembola, for example, Onychiurus sarmatus and Sminthurus viridis;

[0425] Pests from the class Diplopoda, such as Blaniulus guttulatus;

[0426] pests from the class Insecta, for example from the order Blattodea, for example Blatta orientalis, Blattella asahinai, Blattella germanica, Leucophaea maderae, Loboptera decipiens, Neostylopyga rhombifolia, Panchlora spp., Parcoblatta spp., Periplaneta spp. (for example Periplaneta americana, Periplaneta australasiae), Pycnoscelus surinamensis, Supella longipalpa;

[0427] Pests from the order of the Coleoptera, for example Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Aethinatumida, Agelasta alni, Agrilus spp. (for example Agrilus planipennis, Agrilus coxalis, Agrilus bilineatus, Agrilus anxius), Agriotes spp. (for example Agriotes linneatus, Agriotes mancus, Alphitobius diaperinus, Amphimallon solstitialis, Anobium punctatum), Anoplophora spp. (e.g. Anoplophora glabripennis), Anthonomus spp. (e.g. Anthonomus grandis), Anthrenus spp., Apion spp., Apogonia spp., Atomaria spp. (e.g. Atomaria linearis), Attagenus spp., Baris caerulescens, Bruchidius obtectus, Bruchus spp. (e.g. Bruchus pisorum, Bruchus rufimanus), Cassida spp., Cerotoma trifurcata), Ceutorrhynchus spp. (e.g. Ceutorrhynchus assimilis, Ceutorrhynchus quadridens, Ceutorrhynchus rapae), Chaetocnema spp.) (e.g. Chaetocnema confinis, Chaetocnema denticulata, Chaetocnema ectypa), Cleonus mendicus, Conoderus spp., Cosmopolites spp. (e.g. Cosmopolites sordidus), Costelytra zealandica, Ctenicera spp., Curculio spp. (e.g. Curculio caryae, Curculio caryatrypes, Curculio obtusus, Curculio sayi), Cryptolestes ferrugineus, Cryptolestes pusillus, Cryptorhynchus lapathi, Cryptorhynchus mangiferae, Cylindrocopturus spp.), Cylindrocopturus adspersus, Cylindrocopturus furnissi, Dendroctonus spp. (e.g. Dendroctonus ponderosae), Dermestes spp., Diabrotica spp. (e.g. Diabrotica balteata, Diabrotica barberi, Diabrotica undecimpunctata howardi, Diabrotica undecimpunctata undecimpunctata, Diabrotica virgifera avirgifera, Diabrotica virgifera zeae), Dichocrocis spp., Dicladispa armigera, Diloboderus spp.), Epicaerus, Epilachna spp.) (e.g. Epilachna borealis, Epilachna varivestis), Epitrix spp. (e.g. Epitrix cucumeris, Epitrix fuscula, Epitrix hirtipennis, Epitrix subcrinita, Epitrix tuberis), Faustinus spp., Gibbium psylloides, Gnathocerus cornutus, Hellulaundalis, Heteronychus arator, Heteronyx spp., Hylamorpha elegans, Hylotrupes bajulus, Hypera postica), Hypothenemus spp. (e.g. Hypothenemus hampei, Hypothenemus obscurus, Hypothenemus pubescens), Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp., Leptinotarsa ​​decemlineata, Leucoptera spp. (e.g. Leucoptera coffee leafminer), Limonius ectypus, Lissorhoptrus oryzophilus), Listronotus (=Hyperodes) spp., Lixus spp., Luperodes spp., Luperomorpha xanthodera, Lyctus spp., Megacyllene spp. (e.g. Megacyllene robiniae), Megascelis spp., Melanotus spp.) (e.g. Melanotus longulus oregonensis), Meligethesaeneus, Melolontha spp. (e.g. Melolontha melolontha), Migdolus spp., Monochamus spp., Naupactus xanthographus, Necrobia spp., Neogalerucella spp., Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorhynchus spp. (e.g. Otiorhynchus cribricollis, Otiorhynchus ligustici, Otiorhynchus ovatus), Otiorhynchus rugosostriarus, Otiorhynchus sulcatus), Oulema spp. (e.g. Oulema melanopus, Oulema oryzae), Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Phyllophaga helleri, Phyllotreta spp. (e.g. Phyllotreta armoraciae, Phyllotreta pusilla, Phyllotreta ramosa, Phyllotreta striolata), Popillia japonica, Premnotrypes spp.), Prostephanus truncatus, Psylliodes spp. (e.g. Psylliodes affinis, Psylliodes chrysocephala, Psylliodes punctulata), Ptinus spp.), Rhizobius ventralis, Rhizopertha dominica, Rhynchophorus spp., Rhynchophorus ferrugineus, Rhynchophorus palmarum, Scolytus spp. (e.g. Scolytus multistriatus), Sinoxylon perforans, Sitophilus spp. (e.g. Sitophilus granarius, Sitophilus linearis, Sitophilus oryzae, Sitophilus zeamais), Sphenophorus spp., Stegobium paniceum, Sternechus spp.) (e.g., Sternechus paludatus), Symphyletes, Tanymecus spp. (e.g., Tanymecus dilaticollis, Tanymecus indicus, Tanymecus palliatus), Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp. (e.g., Tribolium audax, Tribolium castaneum, Tribolium confusum), Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp. (e.g., Zabrus tenebrioides);

[0428] Pests from the order Dermaptera, for example, Anisolabis maritime, Forficula auricularia, Labidura riparia;

[0429] Pests from the order of Diptera, for example Aedes spp. (e.g. Aedes aegypti, Aedes albopictus, Aedes sticticus, Aedes vexans), Agromyza spp. (e.g. Agromyza frontella, Agromyza parvicornis), Anastrepha spp., Anopheles spp. (e.g. Anopheles quadrimaculatus, Anopheles gambiae), Asphondylia spp., Bactrocera spp. (e.g. Bactrocera cucurbitae, Bactrocera citrifolia), dorsalis, Bactrocera oleae), Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chironomus spp., Chrysomya spp., Chrysops spp., Chrysozona pluvialis, Cochliomya spp., Contarinia spp. (e.g. Contarinia johnsoni, Contarinia nasturtii, Contarinia pyrivora, Contarinia schulzi, Contarinia sorghum sorghicola), Contarinia tritici), Cordylobia anthropophaga, Cricotopus sylvestris, Culex spp. (e.g. Culex pipiens, Culex quinquefasciatus), Culicoides spp., Culiseta spp.), Cuterebra spp., Dacus oleae, Dasineura spp. (e.g. Dasineura brassicae), Delia spp. (e.g. Delia antiqua, Delia coarctata, Delia florilega, Delia platura, Delia radicum), Dermatobia hominis, Drosophila spp. (e.g. Drosphila melanogaster, Drosophila uzukii), Echinocnemus spp., Euleia heraclei, Fannia spp., Gasterophilus spp., Glossina spp.), Haematopota spp., Hydrellia spp., Hydrellia griseola, Hylemya spp., Hippobosca spp., Hypoderma spp., Liriomyza spp. (e.g. Liriomyza brassicae, Liriomyza huidobrensis, Liriomyza sativae), Lucilia spp. (e.g. Lucilia cuprina), Lutzomyia spp., Mansonia spp., Musca spp. (e.g. Musca domestica, Musca domestica vicina), Oestrus spp., Oscinella frit, Paratanytarsus spp., Paralauterborniella subcincta, Pegomya spp. or Pegomyia spp.) (e.g. Pegomya betae, Pegomya hyoscyami, Pegomya rubivora), Phlebotomus spp., Phorbia spp., Phormia spp., Piophila casei, Platyparea poeciloptera, Prodiplosis spp., Psila rosae, Rhagoletis spp. (e.g. Rhagoletis cingulata, Rhagoletis completeta, Rhagoletis fausta, Rhagoletis indifferens, Rhagoletis mendax, Rhagoletis pomonella), Sarcophaga spp. spp.), Simulium spp. (e.g. Simulium meridionale), Stomoxys spp., Tabanus spp., Tetanops spp., Tipula spp. (e.g. Tipula paludosa, Tipula simplex), Toxotrypana curvicauda;

[0430] Pests from the order of the Hemiptera, for example Acizziaacaciaebaileyanae, Acizzia dodonaeae, Acizzia uncatoides, Acridaturrita, Acyrthosipon spp., for example Acyrthosiphon pisum, Acrogonia spp., Aeneolamia spp., Agonascena spp., Aleurocanthus spp., Aleyrodes proletella, Aleurolobus barodensis, Aleurothrixus floccosus, Allocaridara malayensis, Amrasca spp. (for example Amrasca bigutulla, Amrascadevastans), Anuraphis cardui, Aonidiella spp. (e.g. Aonidiella aurantii, Aonidiella citrina, Aonidiella inornata), Aphanostigma piri, Aphis spp. (e.g. Aphis citricola, Aphis craccivora, Aphis fabae, Aphis forbesi, Aphis glycines, Aphis gossypii, Aphis hederae, Aphis illinoisensis, Aphis spp. middletoni), buckthorn potato aphid (Aphisnasturtii), oleander aphid (Aphis nerii), apple aphid (Aphis pomi), spiraea aphid (Aphisspiraecola), viburnum aphid (Aphis viburniphila), grape leafhopper (Arboridia apicalis), Arytainilla spp., Aspidiella spp., Aspidiotus spp.) (e.g. Aspidiotus nerii), Atanus spp., Aulacorthum solani, Bemisia tabaci, Blastopsylla occidentalis, Boreoglycaspis melaeucae, Brachycaudus helichrysi, Brachycolus spp., Brevicoryne brassieae, Cacopsylla spp. (e.g. Cacopsyllapyricola), Calligypona marginata, Capulinia spp., Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii), Chionaspis tegalensis, Chlorita onukii, Chondracris rosea, Chromaphis juglandicola, Chrysomphalus aonidum, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp. (e.g. Coccus hesperidum, Coccus longulus, Coccus pseudomagnoliarum, Coccus viridis), Cryptomyzus ribis, Cryptonossa spp., Ctenarytaina spp. spp.), Dalbulus spp., Dialeurodeschittendeni, Dialeurodes citri, Diaphorina citri, Diaaspis spp., Diuraphis spp., Doralis spp., Drosicha spp., Dysaphis spp.) (e.g., Dysaphis apiifolia, Dysaphis plantaginea, Dysaphis tulipae), Dysmicoccus spp., Empoasca spp. (e.g., Empoasca abrupta, Empoasca fabae, Empoasca maligna, Empoasca solana, Empoasca stevensi, Eriosoma spp. (e.g., Eriosoma americanum, Eriosoma lanigerum, Eriosoma pyricola), Erythroneura spp.), Eucalyptolyma, Euphyllura spp., Euscelisbilobatus, Ferrisia spp., Fiorinia spp., Furcaspis oceanica, Geococcus coffeae, Glycaspis spp., Heteropsylla cubana, Heteropsylla spinulosa, Homalodiscacoagulata, Hyalopterus arundinis, Hyalopterus pruni, Icerya spp. (e.g. Icerya purchasi), Idiocerus spp., Idioscopus spp.), Laodelphax striatellus, Lecanium spp. (e.g. Lecanium corni (= Parthenolecanium corni)), Lepidosaphes spp. (e.g. Lepidosaphes ulmi), Lipaphis erysimi, Lopholeucaspis japonica, Lycorma delicatula, Macrosiphum spp.) (e.g., Macrosiphum euphorbiae, Macrosiphum lilii, Macrosiphum rosae), Macrosteles facifrons, Mahanarva spp., Melanaphis sacchari, Metcalfiella spp., Metcalfapruinosa, Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp. (e.g., Myzus ascalonicus, Myzus cerasi, Myzus ligustri, Myzus ornatus, Myzus persicae, Myzus nicotianae), Nasonovia spp. ribisnigri), Neomaskellia spp., Nephotettix spp. (e.g. Nephotettix cincticeps, Nephotettix nigropictus), Nettigoniclla spectra, Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Oxyachinensis, Pachypsylla spp., Parabemisia myricae, Paratrioza spp. (e.g. Paratrioza cockerelli), Parlatoria spp., Pemphigus spp. (e.g. Pemphigus bursarius, Pemphigus cockerelli), populivenae), Peregrinus maidis, Perkinsiella spp., Phenacoccus spp.) (e.g., Phenacoccusmadeirensis), Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp. (e.g., Phylloxera devastatrix, Phylloxeranotabilis), Pinnaspis aspidistrae, Planococcus spp. (e.g., Planococcus citri), Prosopidopsylla flava, Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp. (e.g., Pseudococcus calceolariae, Pseudococcus comstocki), long-tailed mealybug (Pseudococcus longispinus), true grape mealybug (Pseudococcus maritimus), dark mealybug (Pseudococcus viburni), Psyllopsis spp., Psylla spp. (e.g., boxwood psylla (Psylla buxi), apple psylla (Psylla mali), pear psylla (Psylla pyri)), Pteromalus spp., Pulvinaria spp., Pyrilla spp., Quadraspidiotus spp. (e.g., walnut psylla (Quadraspidiotusjuglansregiae), birch psylla (Quadraspidiotus ostreaeformis), pear psylla (Quadraspidiotus perniciosus)), Quesada gigas, Rastrococcus spp., Rhopalosiphum spp. (e.g. Rhopalosiphum maidis, Rhopalosiphum oxyacanthae, Rhopalosiphum padi, Rhopalosiphum rufiabdominale), Saissetia spp.) (e.g., Saissetia coffeae, Saissetia miranda, Saissetia neglecta, Saissetia oleae), Scaphoideus titanus, Schizaphis graminum, Selenaspidus articulatus, Sipha flava, Sitobion avenae, Sogata spp., Sogatellafurcifera, Sogatodes spp., Stictocephala festina, Siphoninus phillyreae, Tenalaphara malayensis, Tetragonocephela spp., Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp. (e.g. Toxoptera aurantii, Toxoptera citricidus), Trialeurodes vaporariorum, Trioza spp. (e.g. Triozadiospyri), Typhlocyba spp., Unaspis spp., Viteus vitifolii, Zygina spp.;

[0431] Pests from the order Heteroptera, for example Aelia spp., Anasa tristis, Antestiopsis spp., Boisea spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp. (for example Cimex adjunctus, Cimex hemipterus, Cimex lectularius, Cimex pilosellus), Collaria spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp. (e.g. Euschistus heros, Euschistus servus, Euschistus tristigmus, Euschistus variolarius), Eurydema spp., Eurygaster spp., Halyomorpha halys, Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptocorisa varicornis, Leptoglossus occidentalis, Leptoglossus phyllopus), Lygocoris spp. (e.g. Lygocoris pabulinus), Lygus spp. (e.g. Lygus elisus, Lygus hesperus, Lygus lineolaris), Macropes excavatus, Megacopta cribraria, Miridae, Monalonionatratum, Nezara spp.) (e.g., Nezara viridula), Nysius spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp. (e.g., Piezodorus guildinii), Psallus spp., Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatomas spp.;

[0432] Pests from the order of the Hymenoptera, for example Acromyrmex spp., Athalia spp. (e.g. Athalia rosae), Atta spp., Camponotus spp., Dolichovespula spp., Diprion spp. (e.g. Diprion similis), Hoplocampa spp. (e.g. Hoplocampa cookei, Hoplocampa testudinea), Lasius spp., Linepithema (Iridiomyrmex) humile, Monomorium pharaonis, Paratrechina spp.), Paravespula spp., Plagiolepis spp., Sirex spp. (e.g. Sirex noctilio), Solenopsis invicta, Tapinoma spp., Technomyrmex albipes, Urocerus spp., Vespa spp. (e.g. Vespa crabro), Wasmannia auropunctata, Xeris spp.;

[0433] Pests from the order Isopoda, such as Armadillidium vulgare, Oniscus asellus and Porcellio scaber;

[0434] Pests from the order of Isoptera, for example, Coptotermes spp. (e.g. Coptotermes formosanus), Cornitermes cumulans, Cryptotermes spp., Incisitermes spp., Kalotermes spp., Microtermes obesi, Nasutitermes spp., Odontotermes spp., Porotermes spp., Reticulitermes spp. (e.g. Reticulitermes flavipes, Reticulitermes hesperus);

[0435] Pests from the order of the Lepidoptera, for example Achroia grisella, Acronicta major, Adoxophyes spp. (e.g. Adoxophyesorana), Aedia leucomelas, Agrotis spp. (e.g. Agrotissegetum, Agrotis ipsilon), Alabama spp. (e.g. Alabama argillacea), Amyelois transitella, Anarsia spp., Anticarsia spp. (e.g. Anticarsia gemmatalis), Argyroploces spp., Autographa spp., Barathra brassicae, Blastodacna atra, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp., Caloptilia theivora, Capua reticulana, Carpocapsapomonella, Carposina niponensis, Cheimatobia brumata, Chilo spp. (e.g. Chilo plejadellus, Chilo suppressalis), Choreutis pariana, Choristoneura spp., Chrysodeixischalcites, Clysia ambiguella), Cnaphalocerus, Cnaphalocrocis medinalis, Cnephasia spp., Conopomorpha, Conotrachelus spp., Copitarsia, Cydia spp.) (e.g., Cydianigricana, Cydia pomonella), Dalaca noctuides, Diaphania spp., Diparopsis spp., Diatraea saccharalis, Dioryctria spp. (e.g., Dioryctria zimmermani), Earias spp., Ecdytolophaaurantium, Elasmopalpus lignosellus, Eldanas accharina, Ephestia spp. (e.g., Ephestia elutella, Ephestia kuehniella), Epinotia spp.), Epiphyas postvittana, Erannis spp., Erschoviella musculana, Etiella spp., Eudocima spp., Eulia spp., Eupocilia ambiguella, Euproctis spp. (e.g., Euproctis chrysorrhoea), Euxoa spp., Feltia spp., Galleria mellonella, Gracillaria spp., Grapholitha spp. (e.g., Grapholita molesta, Grapholita molesta, prunivora), Hedylepta spp., Helicoverpa spp. (e.g., Helicoverpa armigera, Helicoverpa zea), Heliothis spp. (e.g., Heliothis virescens), Hofmannophilapsedudospretella, Homoeosoma spp., Homona spp.), apple nest moth (Hyponomeuta padella), persimmon moth (Kakivoria flavofasciata), Lampides spp., Laphygma spp., pear borer (Laspeyresia molesta), Leucinodes orbonalis, Leucoptera spp. (e.g., coffee leafminer (Leucoptera cofferella)), Lithocolletis spp. (e.g., apple leafminer (Lithocolletis blancardella)), Lithophane antennata, Lobesia spp. (e.g., grape leafminer (Lobesia botrana)), Loxagrotis albicosta, Lymantria spp. (e.g., gypsy moth (Lymantria dispar)), Lyonetia spp.) (e.g., Lyonetia clerkella), Malacosoma neustria, Marucatestulalis, Mamestra brassicae, Melanitis leda, Mocis spp., Monopis obviella, Mythimna separata, Nemapogon cloacellus, Nymphula spp., Oiketicus spp., Omphisa spp., Operophtera spp., Oria spp., Orthaga spp., Ostrinia spp. (e.g., Ostrinia nubilalis), Panolis flammea, Parnara spp.), Pectinophora spp. (e.g., Pectinophora gossypiella), Perileucoptera, Phthorimaea spp.) (e.g. potato moth (Phthorimaea operculella)), citrus leafminer (Phyllocnistis citrella), Phyllonorycter spp. (e.g. Phyllonorycter blancardella, Phyllonorycter crataegella), Pieris spp. (e.g. Pieris rapae), Platynota stultana, Plodia interpunctella, Plusia spp., Plutella xylostella (= Plutella maculipennis), Podesia spp. (e.g. Podesia syringae), Prays spp., Prodenia spp., Protoparce spp., Pseudaletia spp. (e.g. Pseudaletia unipuncta), soybean cutworm (Pseudoplusia includens), corn borer (Pyrausta nubilalis), Rachiplusia nu, Schoenobius spp. (e.g. Schoenobius bipunctifer), Scirpophaga spp. (e.g. Scirpophaga innotata), yellow cutworm (Scotia segetum), Sesamia spp. (e.g. Sesamia inferens), Sparganothis spp., Spodoptera spp. (e.g. Spodoptera eradiana, Spodoptera exigua, Spodoptera frugiperda, Spodoptera praefica), Stathmopoda spp.), Stenoma spp., Stomopteryx subsecivella, Synanthedon spp., Tecia solanivora, Thaumetopoea spp.), Thermesia gemmatalis, Tinea cloacella, Tinea pellionella, Tineola bisselliella, Tortrix spp., Trichophaga tapetzella, Trichoplusia spp., such as Trichoplusia ni, Tryporyza incertulas, Tuta absoluta, Virachola spp.;

[0436] Pests from the order Orthoptera or the suborder Saltatoria, for example Acheta domesticus, Dichroplus spp., Gryllotalpa spp. (e.g. Gryllotalpa gryllotalpa), Hieroglyphus spp., Locusta spp. (e.g. Locusta migratoria), Melanoplus spp. (e.g. Melanoplus devastator), Paratlanticus ussuriensis, Schistocerca gregaria;

[0437] Pests from the order of the Phthiraptera, for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloxera vastatrix, Phthirus pubis, Trichodectes spp.;

[0438] Pests from the order Psocoptera, for example, Lepinotus spp., Liposcelis spp.;

[0439] Pests from the order Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp. (e.g. Ctenocephalides canis, Ctenocephalides felis), Pulex irritans, Tunga penetrans, Xenopsylla cheopis;

[0440] Pests from the order of the Thysanoptera, for example Anaphothrips obscurus, Baliothrips biformis, Chaetanaphothrips leeuweni, Drepanothrips reuteri, Enneothrips flavens, Frankliniella spp. (for example Frankliniella fusca, Frankliniella occidentalis, Frankliniella schultzei, Frankliniella tritici, Frankliniella vaccinii, Frankliniella williamsi), Haplothrips spp., Heliothrips spp.), Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamomi, Thrips spp. (e.g. Thrips palmi, Thrips tabaci);

[0441] Pests from the order Zygentoma (= Thysanura), for example, Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus, Thermobia domestica;

[0442] Pests from the class Symphyla, for example Scutigerella spp., for example Scutigerella immaculata;

[0443] Pests from the phylum Mollusca, for example from the class Bivalvia, for example Dreissena spp.,

[0444] and pests from the class Gastropoda, for example Arion spp. (e.g. Arionater rufus), Biomphalaria spp., Bulinus spp., Deroceras spp. (e.g. Deroceras laeve), Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp.;

[0445] Plant pests from the phylum Nematoda, i.e. phytoparasitic nematodes, in particular Aglenchus spp. (e.g. Aglenchus agricola), Anguina spp. (e.g. Anguina tritici), Aphelenchoides spp. (e.g. Aphelenchoides arachidis, Aphelenchoides fragariae), Belonolaimus spp. (e.g. Belonolaimus gracilis, Belonolaimus longicaudatus, Belonolaimus nortoni), Bursaphelenchus spp. (e.g. Bursaphelenchus cocophilus), Bursaphelenchus eremus, Bursaphelenchus xylophilus), Cacopaurus spp. (e.g. Cacopaurus pestis), Criconemella spp. (e.g. Criconemella curvata, Criconemella onoensis, Criconemella ornata, Criconemella rusium, Criconemella xenoplax (= Mesocriconemaxenoplax)), Criconemoides spp. (e.g. Criconemoides ferniae, Criconemoides onoense, Criconemoides ornatum), Ditylenchus spp.) (e.g., Ditylenchus dipsaci), Dolichodorus spp., Globodera spp.) (e.g., Globodera pallida, Globodera arostochiensis), Helicotylenchus spp. (e.g., Helicotylenchus dihystera), Hemicriconemoides spp., Hemicycliophora spp., Heterodera spp. (e.g., Heterodera avenae, Heterodera glycines, Heteroderaschachtii), Hirschmaniella spp., Hoplolaimus spp., Longidorus spp. (e.g., Longidorus africanus), Meloidogyne spp.) (e.g., Meloidogyne chitwoodi, Meloidogyne fallax, Meloidogyne hapla, Meloidogyne incognita), Meloinema spp., Nacobbus spp., Neotylenchus spp., Paralongidorus spp., Paraphelenchus spp., Paratrichodorus spp. (e.g., Paratrichodorus minor), Paratylenchus spp., Pratylenchus spp. (e.g., Pratylenchus penetrans penetrans), Pseudohalenchus spp., Psilenchus spp., Punctodera spp., Quinisulcius spp., Radopholus spp.) (e.g., Radopholus citrophilus, Radopholus similis), Rotylenchulus spp., Rotylenchus spp., Scutellonema spp., Subanguina spp., Trichodorus spp. (e.g., Trichodorus obtusus, Trichodorus primitivus), Tylenchorhynchus spp. (e.g., Tylenchorhynchus annulatus), Tylenchulus spp. (e.g., Tylenchulus semipenetrans), Xiphinema spp.) (e.g. standard Xiphinema index). .

[0446] Nematodes

[0447] In the present context, the term "nematodes" includes all species of the phylum Nematoda and in this context in particular parasites on plants or fungi (e.g. genera and species of the orders Aphelenchida, Meloidogyne, Tylenchida) or humans and animals (e.g. orders Trichinellida, Tylenchida, Rhabditina and Spirurida) and causing damage to these living organisms, as well as other parasitic helminths.

[0448] As described herein, nematicides in crop protection control nematodes.

[0449] The term "controlling nematodes" means killing the nematodes or preventing or retarding their development or their growth or preventing or retarding their penetration into plant tissue or their sucking of plant tissue.

[0450] In this context, the efficacy of the compounds is determined by comparing the mortality, gall formation, cyst formation, nematode density per volume of soil, nematode density per root, number of nematode eggs per volume of soil, nematode motility between plants or plant parts or treated soil treated with the capsule suspension concentrate according to the invention and untreated plants or plant parts or untreated soil (100%). Preferably, a reduction of 25-50%, particularly preferably 51-79%, very particularly preferably a reduction of 80% to 100% is achieved compared to untreated plants, plant parts or untreated soil, complete killing or complete prevention of the development and growth of nematodes. Nematode control as described herein also includes controlling the reproduction of nematodes (cyst and / or egg development). The capsule suspension concentrates according to the invention can likewise be used to keep plants or animals healthy, and they can be used therapeutically, preventively or systemically for controlling nematodes.

[0451] The person skilled in the art knows methods for determining mortality, gall formation, cyst formation, nematode density per unit soil volume, nematode density per root, number of nematode eggs per unit soil volume, nematode motility.

[0452] Use of the capsule suspension concentrate of the present invention can maintain plant health and also include reducing damage caused by nematodes and increasing harvest yields.

[0453] In the present context, the term "nematode" refers to plant nematodes, which include all nematodes that damage plants. Plant nematodes include plant parasitic nematodes and soil-borne nematodes. Plant parasitic nematodes include ectoparasites, such as Xiphinema spp., Longidorus spp., and Trichodorus spp.; hemiparasites such as Tylenchulus spp.; migratory endoparasites such as Pratylenchus spp., Radopholus spp., and Scutellonernas spp.; sedentary parasites such as Heterodera spp., Globodera spp., and Meloidogyne spp.; and stem and leaf endoparasites such as Ditylenchus spp., Aphelenchoides spp. spp.) and Hirshmaniella species. Particularly harmful root parasitic soil-borne nematodes are cyst-forming nematodes such as Heterodera or Globodera, and / or root gall nematodes of the genus Meloidogyne. Harmful species of these genera are such as Meloidogyne incognita, Heterodera glycines (soybean cyst nematode), Globodera pallida and Globodera rostochiensis (yellow potato cyst nematode), which are effectively controlled with the compounds described herein. However, the use of the compounds described herein is by no means limited to these genera or species, but is also extended to other nematodes in the same manner.

[0454] Plant nematodes include, for example, Aglenchus agricola, Anguina tritici, Aphelenchoides arachidis, Aphelenchoides fragaria, and stem and leaf endoparasites Aphelenchoides spp., Belonolaimus gracilis, Belonolaimus longicaudatus, Belonolaimus nortoni, Bursaphelenchus cocophilus, Bursaphelenchus eremus, Bursaphelenchus xylophilus and Bursaphelenchus spp., Cacopaurus pestis, Criconemella curvata, Criconemella onoensis, Criconemella ornata, Criconemella rusium, Criconemella xenoplax (= Mesocriconema xenoplax) and Criconemella spp.,

[0455] Criconemoides ferniae, Criconemoides onoense, Criconemoides ornatum and Criconemoides spp., Ditylenchus destructor, Ditylenchus dipsaci, Ditylenchus myceliophagus as well as endoparasites of stems and leaves, Ditylenchus spp., Dolichodorus heterocephalus, Globodera pallida (= Heterodera pallida), Globodera rostochiensis (yellow potato cyst nematode), Globodera solanacearum, Globodera spp. tabacum, Globoderavirginia and sedentary cyst parasites, Globodera spp., Helicotylenchus digonicus, Helicotylenchus dihystera, Helicotylenchus erythrine, Helicotylenchusmulticinctus, Helicotylenchus nannus, Helicotylenchus pseudorobustus and Helicotylenchus spp.), Hemicriconemoides, Hemicycliophora arenaria, Hemicycliophora anudata, Hemicycliophora parvana, Heterodera avenae, Heterodera cruciferae, Heterodera glycines (soybean cyst nematode), Heterodera oryzae, Heterodera schachtii, Heterodera zeae and sedentary cyst parasites, Heterodera species pp., Hirschmaniella gracilis, Hirschmaniella oryzae, Hirschmaniella spinytail spinicaudata, as well as endoparasites of stems and leaves, Hirschmaniella spp., Hoplolaimus aegyptii, Hoplolaimus californicus, Hoplolaimus columbus, Hoplolaimus galeatus, Hoplolaimus indicus, Hoplolaimus magnistylus, Hoplolaimus pararobustus, Longidorus africanus, Longidorus breviannulatus, Longidorus elongatus, Longidorus laevicapitatus, Longidorus vineacola, and ectoparasites Longidorus spp.), Meloidogyne acronea, Meloidogyne africana, Meloidogynearenaria, Meloidogyne arenaria thamesi, Meloidogyneartiella, Meloidogyne chitwoodi, Meloidogyne coffeicola, Meloidogyne ethiopica, Meloidogyne exigua, Meloidogyne fallax, Meloidogyne graminicola, Meloidogyne graminis, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne incognita acrita, Meloidogyne javanica, Meloidogyne kikuyensis, Meloidogyne minor, Meloidogyne naasi, Meloidogyne paranaensis, Meloidogyne thamesi and sedentary parasites, Meloinema spp., Nacobbus aberrans, Neotylenchus vigissi, Paraphelenchus pseudoparietinus, Paratrichodorus allius, Paratrichodorus lobatus, Paratrichodorus minor), Paratrichodorus nanus, Paratrichodorus porosus, Paratrichodorus teres, and Paratrichodorus spp.); Paratylenchus hamatus, Paratylenchus minutus, Paratylenchus projectus and generally Paratylenchus spp., Pratylenchus agilis, Pratylenchus alleni, Pratylenchus andinus, Pratylenchus brachyurus, Pratylenchus cerealis, Pratylenchus coffeae, Pratylenchus crenatus, Pratylenchus delattrei, Pratylenchus giibbicaudatus, Pratylenchus goodeyi), Pratylenchus hamatus, Pratylenchus hexincisus, Pratylenchus loosi, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus pratensis, Pratylenchus scribneri, Pratylenchus teres, Pratylenchus thornei, Pratylenchus vulnus, Pratylenchus zeae, and migratory endoparasites Pratylenchus spp.), Pseudohalenchus minutus, Psilenchusmagnidens, Psilenchus tumidus, Punctodera chalcoensis, Quinisulcius acutus, Radopholuscitrophilus, Radopholus similis, migratory endoparasites Radopholus spp., Rotylenchulus borealis, Rotylenchulus parvus, Rotylenchulus reniformis, and Rotylenchulus spp.; Rotylenchus laurentinus), Rotylenchus macrodorotus, Rotylenchus robustus, Rotylenchus uniformis and Rotylenchus spp., Scutellonema brachyurum, Scutellonema bradys, Scutellonema lathric audatum and migratory endoparasites Scutellonema spp., Subanguina radiciola, Tetylenchus nicotianae, Trichodorus cylindricalus, Trichodorus minor, Trichodorus primitivus, Trichodorus adjacent proximus), Trichodorus similis, Trichodorus sparsus, and ectoparasites Trichodorus spp.), Tylenchorhynchus agri, Tylenchorhynchus brassicae, Tylenchorhynchus clarus, Tylenchorhynchus claytoni, Tylenchorhynchus digitatus, Tylenchorhynchus ebriensis, Tylenchorhynchus maximus, Tylenchorhynchus nudus, Tylenchorhynchus vulgaris and Tylenchorhynchus spp.), Tylenchulus semipipenetrans and semiparasitic species of the genus Tylenchulus spp., Xiphinema americanum, Xiphinema brevicolle, Xiphinema dimorphica udatum, Xiphinema index and ectoparasites Xiphinema species.

[0456] Nematodes that can be controlled by the capsule suspension concentrate of the present invention include nematodes of the genus Meloidogyne, such as the southern root-knot nematode (Meloidogyne incognita), the Java root-knot nematode (Meloidogyne javanica), the northern root-knot nematode (Meloidogyne hapla) and the peanut root-knot nematode (Meloidogyne arenaria); nematodes of the genus Ditylenchus, such as the potato rot nematode (Ditylenchus destructor) and the stem and bulb nematode (Ditylenchus dipsaci); nematodes of the genus Pratylenchus, such as the corn root-lesion nematode (Pratylenchus penetrans), the chrysanthemum root-lesion nematode (Pratylenchus pra ... fallax), coffee root rot nematodes (Pratylenchus coffeae), tea root rot nematodes (Pratylenchus loosi) and walnut root rot nematodes (Pratylenchus vulnus); nematodes of the genus Heterodera, for example, yellow potato cyst nematodes (Globodera rostochiensis) and white potato cyst nematodes (Globodera pallida); nematodes of the genus Heterodera, for example, soybean Heterodera (Heterodera schachtii) and beet cyst nematodes (Heterodera schachtii); nematodes of the genus Aphelenchoides, for example, rice stem nematodes (aphelenchoides besseyi), chrysanthemum leaf bud nematode (aphelenchoieds ritzemabosi) and strawberry nematode (Aphelenchoides fragariae); nematodes of the genus Aphelenchus, for example, the fungus-feeding nematode (Aphelenchus avenae); nematodes of the genus Radopholus, for example, the piercing nematode (Radopholus similis); nematodes of the genus Tylenchulus, for example, the citrus root nematode (Tylenchulus semipenetrans);Nematodes of the genus Rotylenchulus, such as Rotylenchulus reniformis; nematodes that grow on trees, such as Bursaphelenchus xylophilus and red ring nematodes (Bursaphelenchus cocophilus), etc.;

[0457] Plants that can be protected using the capsule suspension concentrate of the present invention include the following plants: for example, cereals (e.g., rice, barley, wheat, rye, oats, corn, etc.), beans (soybeans, adzuki beans, lentils, broad beans, peas, peanuts, etc.), fruit trees / fruits (apples, citrus fruits, pears, grapes, peaches, Japanese apricots, cherries, walnuts, almonds, bananas, strawberries, etc.), vegetables (cabbage, tomatoes, spinach, broccoli, lettuce, onions, green onions, peppers, etc.), root crops (carrots, potatoes, sweet potatoes, radishes, lotus roots, turnips, etc.), industrial raw material plants (cotton, hemp, paper mulberry, etc.), mulberry), mitsumata, rapeseed, beet, hop, sugar cane, sugar beet, olive, rubber, palm, coffee, tobacco, tea, etc.), gourds (pumpkin, cucumber, watermelon, melon, etc.), forage plants (cocksfoot, milo, thimosy-grass, clover, alfalfa, etc.), lawn grasses (mascarene grass, evergreen grass, etc.), spice plants (lavender, rosemary, thyme, parsley, pepper, ginger, etc.), and flowers (chrysanthemum, rose, orchid, etc.).

[0458] The capsule suspension concentrate of the present invention is particularly suitable for controlling coffee nematodes, especially Pratylenchus brachyurus, Pratylenchus coffeae, Meloidogyne exigua, Meloidogyne incognita, Meloidogyne coffeicola, Helicotylenchus spp., and Meloidogyne paranaensis, Rotylenchus spp., Xiphinema spp., Tylenchorhynchus spp. and Scutellonema spp.

[0459] The capsule suspension concentrate of the present invention is particularly suitable for controlling potato nematodes, in particular Pratylenchus brachyurus, Pratylenchus pratensis, Pratylenchus scribneri, Pratylenchus penetrans, Pratylenchus coffeae, Ditylenchus dipsaci, as well as Pratylenchus alleni, Pratylenchus andinus, Pratylenchus cerealis, Pratylenchus crenatus, Pratylenchus hexincisus, Pratylenchus loosi, Pratylenchus neglectus), Pratylenchus teres, Pratylenchus thornei, Pratylenchus vulnus, Belonolaimus longicaudatus, Trichodorus cylindricus, Trichodorus primitivus, Trichodorus proximus, Trichodorus similis, Trichodorus sparsus, Paratrichodorus minor, Paratrichodorus allius, Paratrichodorus nanus, Paratrichodorus teres, Meloidogyne arenaria, Meloidogyne fallax), Meloidogyne hapla, Meloidogyne thamesi, Meloidogyne incognita, Meloidogyne chitwoodi, Meloidogyne javanicajavanica), Nacobbus aberrans, Globodera arostochiensis, Globodera pallida, Ditylenchus destructor, Radopholus similis, Rotylenchulus reniformis, Neotylenchus vigissi, Paraphelenchus pseudoparietinus, Aphelenchoides fragariae, and Meloinema spp.

[0460] The capsule suspension concentrate of the present invention is particularly suitable for controlling tomato nematodes, in particular, peanut root-knot nematode (Meloidogyne arenaria), northern root-knot nematode (Meloidogyne hapla), Java root-knot nematode (Meloidogyne javanica), southern root-knot nematode (Meloidogyne incognita), puncture short-bodied nematode (Pratylenchus penetrans), and short short-bodied nematode (Pratylenchus brachyurus), coffee short-bodied nematode (Pratylenchus coffeae), Steiner short-bodied nematode (Pratylenchus scribneri), wounded short-bodied nematode (Pratylenchus vulnus), micro short-bodied nematode (Paratrichodorus minor), short root-knot nematode (Meloidogyne exigua), abnormal branch nematode (Nacobbus aberrans), Solanacea ball nematode (Globoderasolanacearum), Dolichodorus heterocephalus and Rotylenchulus reniformis.

[0461] The capsule suspension concentrate of the present invention is particularly suitable for controlling nematodes of cucurbit plants, in particular, peanut root-knot nematode (Meloidogyne arenaria), northern root-knot nematode (Meloidogyne hapla), Java root-knot nematode (Meloidogyne javanica), southern root-knot nematode (Meloidogyne incognita), kidney-shaped wheel nematode (Rotylenchulus reniformis) and Thorn's short body nematode (Pratylenchus thornei).

[0462] The capsule suspension concentrate of the present invention is particularly suitable for controlling cotton nematodes, especially Belonolaimus longicaudatus, Meloidogyne incognita, Hoplolaimus columbus, Hoplolaimus galeatus and Rotylenchulus reniformis.

[0463] The capsule suspension concentrate of the present invention is particularly suitable for controlling corn nematodes, in particular, Belonolaimus longicaudatus, Paratrichodorus minor, and Pratylenchus brachyurus, Pratylenchus delattrei, Pratylenchus hexincisus, Pratylenchus penetrans, Pratylenchus zeae, Belonolaimus gracilis, Belonolaimus nortoni, Longidorus breviannulatus, Meloidogyne arenaria, Meloidogyne arenaria thamesi, Meloidogyne graminis, Meloidogyne incognita, and Meloidogyne zeae. incognita), Meloidogyne incognita acrita, Meloidogyne javanica, Meloidogyne naasi, Heterodera avenae, Heterodera oryzae, Heterodera zeae, Punctodera chalcoensis, Ditylenchus dipsaci, Hoplolaimus aegyptii, Hoplolaimus magnistylus, Hoplolaimus galeatus, Hoplolaimus indicus, Helicotylenchus digonicus, Helicotylenchus dihystera), Helicotylenchus pseudorobustus, Xiphinema americanum, Dolichodorus heterocephalus, Criconemellaornata), Criconemella onoensis, Radopholus similis, Rotylenchulus borealis, Rotylenchulus parvus, Tylenchorhynchus agri, Tylenchorhynchus clarus, Tylenchorhynchus claytoni, Tylenchorhynchus maximus, Tylenchorhynchus nudus, Tylenchorhynchus vulgaris, Quinisulcius acutus, Paratylenchus minutus, Hemicycliophora parvana, Aglenchus agricola), wheat grain gall nematode (Anguina tritici), peanut blade nematode (Aphelenchoides arachidis), small tail shield nematode (Scutellonema brachyurum) and root gall nematode (Subanguina radiciola).

[0464] The capsule suspension concentrate of the present invention is particularly suitable for controlling soybean nematodes, in particular, Pratylenchus brachyurus, Pratylenchus pratensis, Pratylenchus penetrans, Pratylenchus scribneri, Belonolaimus longicaudatus, Heterodera glycines, Hoplolaimus columbus, and Pratylenchus coffeae, Pratylenchus hexincisus, Pratylenchus neglectus, Pratylenchus crenatus, Pratylenchus alleni, Pratylenchus agilis, Pratylenchus serratus ... zeae, Pratylenchus vulnus, Belonolaimus gracilis, Meloidogyne arenaria, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne hapla, Hoplolaimus columbus, Hoplolaimus galeatus and Rotylenchulus reniformis.

[0465] The capsule suspension concentrate of the present invention is particularly suitable for controlling tobacco nematodes, especially southern root-knot nematodes (Meloidogyne incognita), Java root-knot nematodes (Meloidogyne javanica), and short-tailed short-bodied nematodes (Pratylenchus brachyurus), grassland short-bodied nematodes (Pratylenchus pratensis), six-line short-bodied nematodes (Pratylenchus hexincisus), piercing short-bodied nematodes (Pratylenchus penetrans), lost short-bodied nematodes (Pratylenchus neglectus), scratched short-bodied nematodes (Pratylenchus crenatus), Sow's short-bodied nematodes (Pratylenchus thornei), injured short-bodied nematodes (Pratylenchus vulnus), corn short-bodied nematodes (Pratylenchus zeae), extended long needle nematodes (Longidorus elongatu), lobed burr nematodes (Paratrichodorus lobatus, Trichodorus spp., Meloidogyne arenaria, Meloidogyne hapla, Globodera tabacum, Globodera solanacearum, Globodera virginiae, Ditylenchus dipsaci, Rotylenchus spp., Helicotylenchus spp., Xiphinema americanum, Criconemella spp., Rotylenchulus reniformis, Tylenchorhynchus claytoni, Paratylenchus spp., and Tetylenchus nicotianae.

[0466] The capsule suspension concentrate of the present invention is particularly suitable for controlling citrus nematodes, especially Pratylenchus coffeae, as well as Pratylenchus brachyurus, Pratylenchus vulnus, Belonolaimus longicaudatus, Paratrichodorus minor, Paratrichodorus porosus, Trichodorus, Meloidogyne incognita, Meloidogyne incognita acrita, Meloidogyne ja avanica, Rotylenchus macrodoratus, Xiphinema americanum, Xiphinema brevicolle, Xiphinema truncatula, and Xiphinema truncatula. index), Criconemella spp., Hemicriconemoides, Radopholus similis and Radopholus citrophilus, Hemicycliophora arenaria, Hemicycliophora nudata, and Tylenchulus semipenetrans.

[0467] The capsule suspension concentrate of the present invention is particularly suitable for controlling banana nematodes, especially Pratylenchus coffeae, Radopholus similis, and Pratylenchus giibbicaudatus, Pratylenchus loosi, Meloidogyne spp., Helicotylenchus multicinctus, Helicotylenchus dihystera and Rotylenchulus spp.

[0468] The capsule suspension concentrate of the present invention is particularly suitable for controlling pineapple nematodes, in particular, Pratylenchus zeae, Pratylenchus pratensis, Pratylenchus brachyurus, Pratylenchus goodeyi, Meloidogyne spp., Rotylenchulus reniformis, and Longidorus elongatus, Longidorus laevicapitatus, Trichodorus primitivus, Trichodorus minor, Heterodera spp., Ditylenchus myceliophagus, Hoplolaimus californicus, Hoplolaimus pararobustus), Hoplolaimus indicus, Helicotylenchus dihystera, Helicotylenchus nannus, Helicotylenchus multicinctus, Helicotylenchus erythrine, Xiphinema dimorphicaudatum, Radopholus similis, Tylenchorhynchus digitatus, Tylenchorhynchus ebriensis, Paratylenchus minutus, Scutellonema clathricaudatum, Scutellonema bradys, Psilenchus tumidus, Psilenchus magnidens), Pseudohalenchusminutus, Criconemoides ferniae, Criconemoides onoense and Criconemoides ornatum.

[0469] The capsule suspension concentrate of the present invention is particularly suitable for controlling grape nematodes, in particular Pratylenchus vulnus, Meloidogyne arenaria, Meloidogyne incognita, Meloidogyne javanica, Xiphinema americanum, Xiphinema index, as well as Pratylenchus pratensis, Pratylenchus scribneri, Pratylenchus neglectus, Pratylenchus brachyurus, Pratylenchus thornei and Tylenchulus semipenetrans.

[0470] The capsule suspension concentrate of the present invention is particularly suitable for controlling nematodes in woody crops-pome fruits, especially puncturing short-bodied nematodes (Pratylenchus penetrans), as well as wounding short-bodied nematodes (Pratylenchus vulnus), extending long needle nematodes (Longidorus elongatus), southern root-knot nematodes (Meloidogyne incognita) and northern root-knot nematodes (Meloidogyne hapla).

[0471] The capsule suspension concentrate of the present invention is particularly suitable for controlling nematodes in woody crops-drupes, in particular, Pratylenchus penetrans, Pratylenchus vulnus, Meloidogyne arenaria, Meloidogyne hapla, Meloidogyne javanica, Meloidogyne incognita, Criconemella xenoplax, and Pratylenchus brachyurus, Pratylenchus coffeae, Pratylenchus scribneri, Pratylenchus zeae, Belonolaimus longicaudatus, Helicotylenchus spp. dihystera, Xiphinema americanum, Criconemella curvata, Tylenchorhynchus claytoni, Paratylenchus hamatus, Paratylenchus projectus, Scutellonema brachyurum and Hoplolaimus galeatus.

[0472] The capsule suspension concentrate of the present invention is particularly suitable for controlling nematodes in woody crops, sugar cane and rice, in particular Trichodorus spp., Criconemella spp., as well as Pratylenchus spp., Paratrichodorus spp., Meloidogyne spp., Helicotylenchus spp., Tylenchorhynchus spp., Aphelenchoides spp., Heterodera spp., Xiphinema spp. and Cacopaurus pestis.

[0473] The capsule suspension concentrates according to the invention can also be used, optionally at certain concentrations or application rates, as herbicides, safeners, growth regulators or agents for improving plant properties, as microbicides or gametocides, for example as fungicides, antifungals, bactericides, viricides (including agents against viroids) or as agents against MLOs (mycoplasma-like organisms) and RLOs (rickettsia-like organisms). If appropriate, they can also be used as intermediates or precursors for the synthesis of other active ingredients.

[0474] The treatment of plants and plant parts with the capsule suspension concentrate according to the invention is carried out directly or by acting on their surroundings, habitat or storage space using conventional treatment methods, such as dipping, spraying, atomizing, irrigating, evaporating, dusting, misting, broadcasting, foaming, coating, spreading, injection, watering (drenching), drip irrigation, and in the case of propagation materials, in particular seeds, dry seed dressing treatment with powders, liquid seed dressing treatment with solutions, slurry treatment with water-soluble powders, by encrustation, by applying one or more coatings, etc. The capsule suspension concentrate according to the invention can also be applied by the ultra-low volume method, or the application form or the capsule suspension concentrate according to the invention itself can be injected into the soil.

[0475] The preferred direct treatment of plants is foliar application, ie application of the capsule suspension concentrate of the present invention to the leaves, wherein the frequency of treatment and the rate of application should be adjusted according to the degree of infestation of the pest of concern.

[0476] In the case of systemically active compounds, the capsule suspension concentrate according to the invention also enters the plant via the root system. The plant is then treated by allowing the capsule suspension concentrate according to the invention to act on the plant's habitat. This can be achieved, for example, by soaking; or mixing into the soil or nutrient solution, i.e. impregnating the plant's location (e.g. soil or hydroponic system) with the capsule suspension concentrate according to the invention in liquid form; or soil application, i.e. introducing the capsule suspension concentrate according to the invention in solid form (e.g. in the form of granules) to the plant's location; or drip irrigation application (also often referred to as "chemical irrigation"), i.e. applying the capsule suspension concentrate according to the invention liquidly from the surface or shallow surface drip line over a certain period of time at defined locations near the plant together with varying amounts of water. In the case of rice crops, this can also be achieved by metering the capsule suspension concentrate according to the invention in solid application form (e.g. as granules) into flooded rice fields.

[0477] Fungicide:

[0478] The capsule suspension concentrate of the present invention may be applied to any plant or plant part.

[0479] plantAll plants and plant populations are meant, for example desired and unwanted wild plants or crop plants (including naturally occurring crop plants). Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnology and genetic engineering methods or a combination of these methods, including transgenics (GMO or transgenic plants), and plant cultivars which may or may not be protectable by plant breeders' rights.

[0480] Plant cultivars It is understood to mean plants which have new properties ("traits") and which have been obtained by conventional breeding, mutagenesis or recombinant DNA techniques. They may be cultivars, varieties, biotypes or genotypes.

[0481] Plant parts It is understood to mean all parts and organs of plants above and below the ground, for example buds, leaves, needles, stems, trunks, flowers, fruiting bodies, fruits, seeds, roots, tubers and rhizomes. Plant parts also include harvested material and vegetative and sexual propagation material, for example cuttings, tubers, rhizomes, slips and seeds.

[0482] Plants that can be treated according to the invention include the following: cotton, flax, grapes, fruits, vegetables, for example Rosaceae sp. (e.g. pome fruits such as apples and pears, and stone fruits such as apricots, cherries, almonds and peaches, and soft fruits such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (e.g. banana trees and plantations), Rubiaceae sp. (e.g. coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. sp.) (e.g. lemons, oranges and grapefruits); Solanaceae sp. (e.g. tomatoes), Liliaceae sp., Asteraceae sp. (e.g. lettuce), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (e.g. cucumbers), Alliaceae sp. (e.g. leeks, onions), Papilionaceae sp. (e.g. peas); major crop plants, such as Gramineae sp. (e.g. corn, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale), Asteraceae sp. (e.g. sunflowers), Brassicaceae sp. (e.g. white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts) sprouts), pakchoi, kohlrabi, radish, and rapeseed, mustard, horseradish and watercress), Fabacae sp. (e.g. beans, peanuts), Fabaceae sp. (e.g. soybeans), Solanaceae sp. (e.g. potatoes), Chenopodiaceae sp. (e.g. beets, fodder beets, Swiss chard, beetroot); useful plants and ornamental plants in horticulture and forestry areas; and genetically modified varieties of each of these plants.

[0483] Plants and plant cultivars that may be treated according to the methods disclosed above include plants and plant cultivars that are resistant to one or more biotic stresses, i.e. the plants exhibit improved resistance to animal and microbial pests (e.g. nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and / or viroids).

[0484] Plants and plant cultivars that can be treated according to the methods disclosed above include those that are resistant to one or more abiotic stresses. Abiotic stress conditions can include, for example, drought, low temperature exposure, heat exposure, osmotic stress, waterlogging, increased soil salinity, enhanced mineral exposure, ozone exposure, high light exposure, limited nitrogen nutrient availability, limited phosphorus nutrient availability, shade avoidance.

[0485] Plants and plant cultivars that can be processed according to the method disclosed above include those plants characterized by the yield characteristics of improvement. The yield improved in the plant can be the result of the following factors: for example, improved plant physiology, growth and development, such as water use efficiency, water holding efficiency, improved nitrogen utilization, improved carbon assimilation, improved photosynthesis, increased germination rate and accelerated maturity. In addition, the yield is also affected by the improved plant structure (under stress and non-stress conditions), including but not limited to: early flowering, flowering control of hybrid seed production, rice seedling vigor, plant size, internode number and internode distance, root growth, seed size, fruit size, pod size, pod number or ear number, seed quantity of each pod or ear, seed quality, enhanced seed fullness, reduced seed dispersion, reduced pod cracking and lodging resistance. Other yield characteristics include seed composition, such as carbohydrate content and composition, such as cotton or starch, protein content, oil content and composition, nutritional value, reduction of anti-nutritional compounds, improved processability and better storage stability.

[0486] Plants and plant cultivars that may be treated according to the methods disclosed above include plants and plant cultivars that are hybrid plants that already express the characteristic of heterosis or hybrid vigour, which generally results in higher yield, vigour, health and resistance to biotic and abiotic stresses.

[0487] Pathogens

[0488] Non-limiting examples of pathogens of fungal diseases that can be treated according to the present invention include:

[0489] Diseases caused by powdery mildew pathogens, such as Blumeria species, for example Blumeria graminis; Podosphaera species, for example Podosphaeraleucotricha; Sphaerotheca species, for example Sphaerotheca fuliginea; Uncinula species, for example Uncinula necator;

[0490] Diseases caused by rust pathogens, such as species of the genus Gymnosporangium, for example Gymnosporangium sabinae; species of the genus Hemileia, for example Hemileia vastatrix; species of the genus Phakopsora, for example Phakopsora pachyrhizi and Phakopsora meibomiae; species of the genus Puccinia, for example Puccinia recondita, Puccinia graminis or Puccinia striiformis; species of the genus Uromyces, for example Uromyces appendiculatus;

[0491] Diseases caused by pathogens of the class Oomycetes, for example, species of the genus Albugo, such as Albugo candida; species of the genus Bremia, such as Bremia lactucae; species of the genus Peronospora, such as Peronospora pisi or P. brassicae; species of the genus Phytophthora, such as Phytophthora infestans; species of the genus Plasmopara, such as Plasmopara viticola; species of the genus Pseudoperonospora, such as Pseudoperonospora humuli or Pseudoperonospora cubensis; species of the genus Pythium, such as Pythium ultimum. ultimum);

[0492] Leaf blotch and leaf wilt diseases caused by, for example, Alternaria species, such as Alternaria solani; Cercospora species, such as Cercospora beticola; Cladiosporium species, such as Cladiosporium cucumerinum; Cochliobolus species, such as Cochliobolus sativus (conidial form: Drechslera, synonym: Helminthosporium), or Cochliobolus miyabeanus; Colletotrichum species, such as Colletotrichum lindemuthanium; Corynespora species, such as Corynespora cassiicola; Cycloconium species, such as Cycloconium oleaginum; Diaporthe species, such as Diaporthe citri; Elsinoe species, such as Elsinoe fawcettii; Gloeosporium species, such as Gloeosporium laeticolor; Glomerella species, such as Glomerella cingulata; Guignardia species, such as Guignardia bidwelli; Leptosphaeria species, such as Leptosphaeria stigmata. maculans; Magnaporthe species, for example Magnaporthe grisea; Microdochium species, for example Microdochium nivale; Mycosphaerella species, for example Mycosphaerella graminicola, Mycosphaerella arachidicola or Mycosphaerella fijiensis;Phaeosphaeria species, such as Phaeosphaeria nodorum; Pyrenophora species, such as Pyrenophorateres or Pyrenophora tritici repentis; Ramularia species, such as Ramularia collo-cygni or Ramularia areola; Rhynchosporium species, such as Rhynchosporium secalis; Septoria species, such as Septoria apii or Septoria lycopersici; Stagonospora species, such as Stagonospora spp. nodorum); species of the genus Typhula, such as Typhula incarnata; species of the genus Venturia, such as Venturia inaequalis;

[0493] Diseases of roots and stems caused by pathogens such as Corticium species, for example Corticium graminearum; Fusarium species, for example Fusarium oxysporum; Gaeumannomyces species, for example Gaeumannomyces graminis; Plasmodiophora species, for example Plasmodiophora brassicae; Rhizoctonia species, for example Rhizoctonia solani; Sarocladium species, for example Sarocladium oryzae; Sclerotium species, for example Sclerotium oryzae; oryzae); Tapesia species, such as Tapesia acuformis; Thielaviopsis species, such as Thielaviopsis basicola;

[0494] Diseases of spadix and panicle (including cobs) caused by, for example, Alternaria spp., such as Alternaria spp.; Aspergillus spp., such as Aspergillus flavus; Cladosporium spp., such as Cladosporium cladosporioides; Claviceps spp., such as Claviceps purpurea; Fusarium spp., such as Fusarium culmorum; Gibberella spp., such as Gibberella zeae; Monographella spp., such as Monographella nivalis; Stagnospora spp., such as Stagnospora nodorum;

[0495] Diseases caused by smut fungi: for example, species of the genus Sphacelotheca, such as Sphacelotheca reiliana; species of the genus Tilletia, such as Tilletiacaries or Tilletia controversa; species of the genus Urocystis, such as Urocystis occulta; species of the genus Ustilago, such as Ustilago nuda;

[0496] Fruit rot caused by pathogens such as Aspergillus species, such as Aspergillus flavus; Botrytis species, such as Botrytis cinerea; Monilinia species, such as Monilinia laxa; Penicillium species, such as Penicillium expansum or Penicillium purpurogenum; Rhizopus species, such as Rhizopus stolonifer; Sclerotinia species, such as Sclerotinia sclerotiorum; Verticilium species, such as Verticilium alboatrum;

[0497] Seed-borne and soil-borne rot and wilt diseases and seedling diseases caused by, for example, Alternaria species, such as Alternaria brassicicola; Aphanomyces species, such as Aphanomyces euteiches; Ascochyta species, such as Ascochytalentis; Aspergillus species, such as Aspergillus flavus; Cladosporium species, such as Cladosporium herbarum; Cochliobolus species, such as Cochliobolus graminis. sativus) (conidial form: Endotrichum, Bipolaris, synonym: Helminthosporium); Anthracnose species, such as Colletotrichum coccodes; Fusarium species, such as Fusarium culmorum; Gibberella species, such as Gibberella zeae; Macrophomina species, such as Macrophomina phaseolina; Microdochium species, such as Microdochium nivale; Monographella species, such as Monographella nivalis; Penicillium species, such as Penicillium expansum; Phoma species, such as Phoma nigromaculata; lingam; Phomopsis species, such as Phomopsis sojae; Phytophthora species, such as Phytophthora cactorum; Pyrenophora species, such as Pyrenophora graminea; Pyricularia species, such as Pyricularia oryzae; Pythium species, such as Pythium ultimum; Rhizoctonia species, such as Rhizoctonia solani; Rhizopus species, such as Rhizopus oryzae;Sclerotium species, such as Sclerotium rolfsii; Septoria species, such as Septoria nodorum; Typhula species, such as Typhula incarnata; Verticillium species, such as Verticillium dahliae;

[0498] Cancerous diseases, galls and witches' broom caused by, for example, species of the genus Nectria, such as Nectria galligena;

[0499] Wilt diseases caused by pathogens such as Verticillium species, such as Verticillium longisporum; Fusarium species, such as Fusarium oxysporum;

[0500] Deformities of leaves, flowers and fruits caused by pathogens such as Exobasidium species, for example Exobasidium vexans; Taphrina species, for example Taphrinadeformans;

[0501] Degenerative diseases of woody plants caused by pathogens such as species of the genus Esca, such as Phaeomoniella chlamydospora, Phaeoacremonium aleophilum or Fomitiporia mediterranea; species of the genus Ganoderma, such as Ganoderma boninense;

[0502] Plant tuber diseases caused by pathogens such as Rhizoctonia species, such as Rhizoctonia solani; Helminthosporium species, such as Helminthosporium solani;

[0503] Diseases caused by bacterial pathogens such as Xanthomonas species, such as Xanthomonas campestris pv. oryzae; Pseudomonas species, such as Pseudomonas syringae pv. lachrymans; Erwinia species, such as Erwinia amylovora; Liberibacter species, such as Liberibacter asiaticus; Xyella species, such as Xylella fastidiosa; Ralstonia species, such as Ralstonia solanacearum; Dickeya species, such as Dickeya spp. solani; Clavibacter species, such as Clavibacter michiganensis; Streptomyces species, such as Streptomyces scabies.

[0504] The following soybean diseases:

[0505] Fungal diseases of leaves, stems, pods and seeds caused by pathogens such as Alternaria leaf spot (Alternaria spec. atrans tenuissima), Anthracnose (Colletotrichum gloeosporoides dematium var.truncatum), brown spot (Septoria glycines), cercospora leaf spot and blight (Cercospora kikuchii), choanephora leaf blight (Choanephora infundibulifera trispora (synonym)), dactuliophora leaf spot (Dactuliophora glycines), downy mildew (Peronospora manshurica), drechslera blight (Drechslera lycini), frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot (Leptosphaerulina trifolii), phyllostica leaf spot (Phyllosticta sojaecola), stem blight (Phomopsis sojae), powdery mildew (Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines), rhizoctonia aerial, leaf blight and web blight (Rhizoctonia solani), rust (Phakopsora pachyrhizi, Phakopsora meibomiae), scab (Sphaceloma glycines), stemphylium leaf blight (Stemphylium botryosum), sudden death syndrome (Fusarium virguliforme); target spot (Corynespora cassiicola). .

[0506] Fungal diseases of the roots and base of the stem caused by pathogens such as black root rot (Calonectria crotalariae), charcoal rot (Macrophomina phaseolina), Fusarium wilt or wilt, root rot and pod and crown rot (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris), neocosmospora (Neocosmospora vasinfecta), pod and stem wilt (Diaporthe phaseolorum), stem canker (Diaporthe phaseolorum caulivora), phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregata), pythium diseases (Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylumn, Pythium ultimum), Rhizoctonia root, stem and damping-off (Rhizoctonia solani), sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotinia southern blight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).

[0507] The invention is illustrated by the following examples. Example

[0508] Substances and abbreviations used:

[0509] The terms used in the following examples have the following meanings:

[0510] Mepyrazoline-butyl (RS)-1-(2,4-dichlorophenyl)-5-methyl-2-pyrazoline-3,5-dicarboxylic acid diethyl ester (Bayer AG), melting point range 50-55°C

[0511] DCPMI 2-[(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, hereinafter abbreviated as DCPMI

[0512] Deltamethrin (1R, 3R)-[(S)-α-cyano-3-phenoxybenzyl-3-(2,2-dibromovinyl)]-2,2-dimethylcyclopropanecarboxylate, CAS No. 52918-63-5, Bayer AG

[0513] Citric acid polybasic organic acid

[0514] G Xanthan gum derivatives (Solvay)

[0515] SAG 1572 Silicone Defoamer (Momentive)

[0516] GXL Preservatives (Biocides, Proxel)

[0517] 200 ND Mineral oil, ExxonMobil, naphthalene free

[0518] 44V20L Polymeric MDI, Covestro AG, functionality 2.7.

[0519] HDA Hexamethylene-1,6-diamine, BASF

[0520] Kuraray 26-88 Polyvinyl alcohol, from Kuraray, about 88% hydrolyzed polyvinyl acetate

[0521] Reax 88B lignin sulfonate, MeadWestVaco

[0522] Compound N1 Ethane-1,2-diylbis(6-aminohexanoate) sulfate (prepared as described below), corresponding to 4.27 mmol NH2 / g sample (thus 1 g of hexamethylenediamine would be replaced by 4 g of compound X). This corresponds to compound IV according to the invention.

[0523] ε-Caprolactam (from Acros Organics)

[0524] Pyrrolidone (from Acros Organics)

[0525] Monoethylene glycol (from Sigma-Aldrich)

[0526] Polytetrahydrofuran (from Sigma-Aldrich)

[0527] Triethylene glycol (from Sigma-Aldrich)

[0528] Glycerol (from Sigma-Aldrich)

[0529] H2SO4(95%) (from VWR)

[0530] Example

[0531] Compound N1 (according to formula IV): Preparation of ethane-1,2-diylbis(6-aminohexanoate) sulfate

[0532] Preparation of ethane-1,2-diylbis(6-aminohexanoate) sulfate

[0533] Epsilon-caprolactam (89.9 g, 0.79 mol) and ethylene glycol (24.6 g, 0.4 mol) were loaded into a 250 mL flange glass reactor with an overhead stirrer, a thermometer and a cooler. The mixture was heated to 80 ° C. Then, sulfuric acid (95% aqueous solution, 55.94 g, 0.54 mol) was added and the mixture was heated to 140 ° C. After 8 hours, the mixture was cooled to room temperature and analyzed by NMR. The product in the form of a viscous liquid was obtained. The product contained ethane-1,2-diylbis(6-aminocaproate) salt, with a yield greater than 80%, and a small amount of hydroxyethyl-6-aminocaproic acid sulfate.

[0534] Alternative compounds:

[0535] Compound N2 - Preparation of diester diamine from triethylene glycol and caprolactam

[0536] Caprolactam (90.2 g, 797 mmol) and triethylene glycol (59.8 g, 399 mmol) were charged into a 500 mL flange glass reactor and heated to 60° C. (externally measured temperature) using mechanical stirring under a nitrogen stream. Sulfuric acid (60 g, 578 g) was added over 25 minutes, then the temperature was raised to 135° C., and the reaction was stopped after about 13 hours. The product was isolated and purified by 1 H NMR analysis determined a degree of substitution of about 50%.

[0537] Compound N3 - Preparation of diester diamine from polytetrahydrofuran and caprolactam

[0538] Caprolactam (16.9 g, 149 mmol) and Terathane 1400 (102.6 g, 75 mmol) were charged into a 1 L flange glass reactor and heated to 60° C. (temperature measured externally) using mechanical stirring under a nitrogen stream. Sulfuric acid (11 g, 108 mmol) was added over 25 minutes, then the temperature was raised to 135° C. and the mixture was further stirred for about 19 hours. The product was isolated and analyzed by 1H NMR. A degree of substitution of about 60% was determined.

[0539] Compound N4 - Preparation of Triester Triamine from Glycerol Caprolactam

[0540] Caprolactam (212 g, 1880 mmol) and glycerol (57.6 g, 625 mmol) were charged into a 500 mL flange glass reactor and heated to 60° C. (external measurement) using mechanical stirring under a nitrogen stream. Sulfuric acid (118 g, 1100 mmol) was added over 45 minutes, then the temperature was raised to 135° C. and the mixture was further stirred for about 14 hours. The product was isolated and purified by 1 HNMR analysis determined a degree of substitution of 60% for a mixture of mono / di / trisubstituted products.

[0541] Compound N5 - Preparation of diester diamine from ethylene glycol and 2-pyrrolidone

[0542] 2-Pyrrolidone (93.7 g, 1100 mmol) and ethylene glycol (34.5 g, 556 mmol) were charged into a 1 L flange glass reactor and heated to 60° C. (externally measured temperature) using mechanical stirring under a nitrogen stream. Sulfuric acid (82 g, 790 mmol) was added over 45 minutes, then the temperature was raised to 135° C. and the mixture was further stirred for about 25 hours. The product was isolated and purified by 1 H NMR analysis determined a degree of substitution of about 80%.

[0543] Example 1 (Comparative)

[0544] 14.23 g DCPMI and 7.14 g Mefenpyr-diethyl were dissolved in 21.4 g 200ND. Add 1.2g 44V20L. This mixture was added to 1.51 g Reax88B, 0.05 g SAG 1572, 0.18 g CG / ICP in a solution of 53.51 g of water. The mixture was dispersed for 10 minutes using a disperser at 15000 rpm. 0.39 g of hexamethylenediamine was dissolved in 0.39 g of water and added. The resulting reaction mixture was heated to a maximum of 70° C. within 1 hour and maintained at 70° C. for another 4 hours with gentle stirring. After subsequent cooling to room temperature, 0.2 g of a 30% aqueous ammonia solution was added. 0.2 g of G thickened the mixture and added 0.4g citric acid. In this way, a microcapsule preparation with a DCPMI content of 150g / L and 75g / L of mefenacet-butyl and a particle size of 12μm (d90) was obtained. In the chemical analysis, the amount of free, unencapsulated active ingredients was determined to be <0.05% (absolute value), so all active ingredients were encapsulated. The total amounts determined corresponded to 150g / L and 75g / L, respectively.

[0545] Example 2 (Invention)

[0546] 14.23 g DCPMI and 7.14 g pyraclostrobin were dissolved in 21.4 g 200 ND. Add 1.2g 44V20L. This mixture was added to 1.51 g Reax 88B, 0.05 g SAG1572, 0.18 g CG / ICP in a solution of 51.17 g of water. The mixture was dispersed with a disperser at 15000 rpm for 10 minutes. 1.56 g of compound N1 was dissolved in 1.56 g of water and added. The resulting reaction mixture was heated to a maximum of 70°C within 1 hour and maintained at 70°C for another 4 hours with gentle stirring. After subsequent cooling to room temperature, 0.2 g of 30% aqueous ammonia solution was added. 0.2 g of G thickened the mixture and added 0.4 g of citric acid. In this way, a microcapsule preparation with a DCPMI content of 150 g / l and 75 g / L of mefenacet-butyl and a particle size of 12 μm (d90) was obtained. In the chemical analysis, the amount of free, unencapsulated active ingredient was determined to be <0.05% (absolute value), so all active ingredients were encapsulated. The total amount was determined to correspond to 150 g / L and 75 g / L, respectively.

[0547] Example 3 (Invention)

[0548] 7.35 g of deltamethrin was dissolved in 35.9 g of 200ND. Add 0.85g 44V20L. This mixture was added to 0.43 g Borresperse NA, 0.02 g SAG 1572, 0.18 g CG / ICP in a solution of 44.63 g of water. The mixture was dispersed with a disperser at 4000 rpm. 1.43 g of compound N1 was dissolved in 1.43 g of water and added. The resulting reaction mixture was heated to a maximum of 70°C within 1 hour and maintained at 70°C for another 4 hours with gentle stirring. After subsequent cooling to room temperature, the mixture was heated with a mixture containing 0.2 g of The mixture was thickened with an aqueous solution of G. In this way, a microcapsule preparation having a deltamethrin content of 75 g / L and a particle size of 29 μm (d90) was obtained.

[0549] Table 1: Composition of capsule suspension concentrate

[0550]

[0551]

[0552] Determination of relative volatility of active ingredients

[0553] In a laboratory fume hood, at a constant air flow of 1.6 m / s, at 22° C. and 60% relative air humidity, the spray liquid (0.5 g active ingredient / l) is placed on three Teflon membranes in each case in a glass box with an open top. After drying for 0, 24 and 72 h, the residue on the Teflon membrane is determined by HPLC. The volatility is based on the value at 0 h.

[0554] Table 2 : Determination of volatility; the amount of active ingredient is the content of DCPMI in % by weight.

[0555]

[0556] The results show that both materials can reduce volatility very well and that the capsule material of the present invention has no disadvantages relative to the comparative state of the art capsules on the market. Thus, there are no disadvantages to using an ester-containing biodegradable shell material for the encapsulation process. The capsules of the present invention provide even better volatility control.

[0557] Apple cuticle permeation method for bioavailability determination

[0558] In each case, the spray liquor (0.5 g active ingredient / l) was applied to the cuticle of three apples. The amount of active ingredient in the cuticle was measured; after 0, 24 and 72 h of drying by HPLC.

[0559] Table 3: Permeation of DCPMI through apple cuticle, wt %

[0560]

[0561] The bioavailability of the inventive examples was at the same level as the comparison. Therefore, there is no disadvantage in using an ester-containing biodegradable shell material for the encapsulation process. The low bioavailability of this active substance for foliar absorption is known, as the mode of action is absorption of the ingredient by soil. This test was chosen as a relative, easy to use comparative test, as there is no rapid screening test available for soil absorption of the active ingredient.

[0562] Measurement of biodegradability:

[0563] To measure biodegradability, CS formulations were studied.

[0564] The test was conducted under OECD 301B conditions (CO2 release test) for 28 days under aerobic conditions. The test item concentration applied was 20 mg TOC / L, the inoculum concentration was 29.6 mg suspended solids / liter, and the total liquid volume was 2L in a 3L test container.

[0565] Biodegradation results

[0566] Components Day 28 / Degradation [%] 1 22 2 52

[0567] Compared to Reference 1, the polymer showed faster degradation after 28 days.

[0568] Hydrolysis test:

[0569] The capsule suspension concentrates were stored under accelerated storage conditions at 80° C. for 2 weeks. For the CS formulations, the increase in free, unencapsulated active ingredient was measured as a benchmark for hydrolysis and thus degradation of the shell material.

[0570] Table 4: Hydrolysis

[0571]

[0572]

[0573] In the case of sample 2, the unencapsulated amount increased 3-fold after 2 weeks at 80°C (pH 6), whereas sample 1 increased only 2-fold.

[0574] Table 5: Hydrolysis of samples adjusted to pH 9

[0575]

[0576] In the case of sample 2, the pH decreased after 2 weeks at 80°C, whereas it decreased only slightly in sample 1. The formation of free acid is evidence of formation of the free acid from the ester, thus showing increased hydrolysis and hence degradation of the polymer.

Claims

1. A microcapsule comprising a polymer shell, wherein the polymer shell comprises monomers a) and b) in polymerized form, in Monomer a) is at least one polyisocyanate containing at least 2 isocyanate groups; and Monomer b) is at least one compound of formula IV containing an ester group, where k is a value from 1 to 3, and wherein each R is independently hydrogen or C1-C4 alkyl or CH2CH2COOH or CH2COOH or (CH2)4HN2, and wherein A is a carbon chain having 2 to 36 carbon atoms, which may be aliphatic or aromatic, or CH2CH(OH)CH2, CH2C(CH2OH)2CH2, CH2C(CH2 H)(CH3)CH2, CH2C(CH2OH)(CH2CH3)CH2, polytetrahydrofuran, erythritol, or an ester of a dicarboxylic acid or tricarboxylic acid with ethylene glycol or propylene glycol, and wherein A may optionally be alkoxylated with one or more alkylene oxide units or reacted with one or more hydroxycarboxylic acids as defined above, and wherein each m is an integer from 1 to 8, and X is an anion obtainable by deprotonating a Bronsted-Lowry acid.

2. The microcapsule according to claim 1, which is used in agricultural chemical formulations.

3. The microcapsule according to claim 1, wherein the polymer shell comprises monomers a) and b) in polymerized form, wherein Monomer a) is at least one polyisocyanate containing at least 2 isocyanate groups; and Monomers b) are at least one compound of the formula IV containing ester groups and further isocyanate-reactive compounds b) different from IV.

4. The microcapsule according to claim 2, wherein the polymer shell comprises monomers a) and b) in polymerized form, wherein Monomer a) is at least one polyisocyanate containing at least 2 isocyanate groups; and Monomers b) are at least one compound of the formula IV containing ester groups and further isocyanate-reactive compounds b) different from IV.

5. The microcapsule according to any one of claims 1 to 4, characterized in that They comprise a polymer shell and a core, wherein the core comprises at least one active ingredient.

6. A microcapsule preparation comprising the microcapsules according to any one of claims 1 to 5, characterized in that The microcapsules contain the following substances as components: a): at least one isocyanate, b): at least one compound of formula IV, where k is a value from 1 to 3, and wherein each R is independently hydrogen or C1-C4 alkyl or CH2CH2COOH or CH2COOH or (CH2)4HN2, and wherein A is a carbon chain having 2 to 36 carbon atoms, which may be aliphatic or aromatic, or CH2CH(OH)CH2, CH2C(CH2OH)2CH2, CH2C(CH2 H)(CH3)CH2, CH2C(CH2OH)(CH2CH3)CH2, polytetrahydrofuran, erythritol, or an ester of a dicarboxylic acid or tricarboxylic acid with ethylene glycol or propylene glycol, and wherein A may optionally be alkoxylated with one or more alkylene oxide units or reacted with one or more hydroxycarboxylic acids as defined above, and wherein each m is an integer from 1 to 8, and X is an anion obtainable by protonating a Brønsted-Lowry acid, c): at least one active ingredient, d): optionally a water-immiscible solvent, e): optionally at least one emulsifier and / or dispersant, f): at least one protective colloid, g): optionally other additives, and i) water, Components a) and b) form the shell of the microcapsules.

7. The microcapsule preparation according to claim 6, characterized in that The median particle size d50 of the microcapsules is usually 1 to 50 μm.

8. The microcapsule preparation according to claim 6, characterized in that At least one component selected from d), e) and g) is essential.

9. The microcapsule preparation according to claim 7, characterized in that At least one component selected from d), e) and g) is essential.

10. The microcapsule preparation according to claim 6, characterized in that The active ingredient is selected from the group consisting of herbicides, safeners, fungicides, insecticides and biological agents.

11. The microcapsule preparation according to claim 6, characterized in that The active ingredient is selected from DCPMI, mefenpyr-butyl and deltamethrin.

12. The microcapsule preparation according to any one of claims 6 to 11, characterized in that The ratio of the isocyanate to the compound of formula IV is 0.1% to 8% by weight, The proportion of the active ingredient is 1% to 50% by weight, The proportion of the water-immiscible solvent is 0 wt % to 60 wt %, The proportion of the protective colloid is 0.1 wt % to 5 wt %, and The proportion of the other additives is 0.1% to 15% by weight.

13. Microcapsule preparation according to one of claims 6 to 11, characterized in that The ratio of the isocyanate to the compound of formula IV is 0.3% to 2.5% by weight, The proportion of active ingredients is 10% to 20% by weight, The proportion of the water-immiscible solvent is 0% to 40% by weight, The proportion of the protective colloid is 0.3% to 1.5% by weight, and The proportion of the other additives is 0.4% to 3% by weight.

14. Use of the microcapsule preparation according to any one of claims 6 to 13 for applying agrochemical active ingredients to plants, plant parts, seeds and their habitats.

15. A method for preparing microcapsules, characterized in that reacting at least one monomer which is an amine-functional ester of formula IV with at least one polyisocyanate containing at least 2 isocyanate groups, where k is a value from 1 to 3, and wherein each R is independently hydrogen or C1-C4 alkyl or CH2CH2COOH or CH2COOH or (CH2)4HN2, and wherein A is a carbon chain having 2 to 36 carbon atoms, which may be aliphatic or aromatic, or CH2CH(OH)CH2, CH2C(CH2OH)2CH2, CH2C(CH2 H)(CH3)CH2, CH2C(CH2OH)(CH2CH3)CH2, polytetrahydrofuran, erythritol, or an ester of a dicarboxylic acid or tricarboxylic acid with ethylene glycol or propylene glycol, and wherein A may optionally be alkoxylated with one or more alkylene oxide units or reacted with one or more hydroxycarboxylic acids as defined above, and wherein each m is an integer from 1 to 8, and X is an anion obtainable by deprotonating a Bronsted-Lowry acid.

16. A microcapsule prepared by the following method, characterized in that reacting at least one monomer which is an amine-functional ester of formula IV with at least one polyisocyanate containing at least 2 isocyanate groups, where k is a value from 1 to 3, and wherein each R is independently hydrogen or C1-C4 alkyl or CH2CH2COOH or CH2COOH or (CH2)4HN2, and wherein A is a carbon chain having 2 to 36 carbon atoms, which may be aliphatic or aromatic, or CH2CH(OH)CH2, CH2C(CH2OH)2CH2, CH2C(CH2 H)(CH3)CH2, CH2C(CH2OH)(CH2CH3)CH2, polytetrahydrofuran, erythritol, or an ester of a dicarboxylic acid or tricarboxylic acid with ethylene glycol or propylene glycol, and wherein A may optionally be alkoxylated with one or more alkylene oxide units or reacted with one or more hydroxycarboxylic acids as defined above, and wherein each m is an integer from 1 to 8, and X is an anion obtainable by deprotonating a Bronsted-Lowry acid.

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