Encapsulated pyrethroids with enhanced activity in soil and foliar applications

Abstract

The present invention relates to aqueous capsule suspensions based on various pyrethroids, their preparation and their use in the form of agrochemical preparations, in particular for soil application.

Description

[0001] Technical Problem / Purpose

[0002] The present invention relates to aqueous capsule suspensions based on various pyrethroids, a process for their preparation and their use in the form of agrochemical preparations, in particular for soil application. Prior art

[0003] Pyrethroids are an established class of active substances that are available in a variety of formulation types for a wide range of uses, such as foliar application, soil application, surface treatment, impregnation materials, etc.

[0004] For example (L-cyhalothrin in GR formulation), (Tefluthrin GR) or (Cypermethrin GR) is specifically targeted at soil applications, especially against corn rootworms and similar species. Compared to these known solid formulations, liquid formulations are less common in the field. However, one disadvantage of solid formulations is that they generally require relatively high application rates and low loadings of the formulation.

[0005] The successful microencapsulation of crop protection active substances has been widely described in the literature, for example in US77608085, EP0214936. Many documents also explicitly mention pyrethroids as potential active substances, for example US 5846554, WO1997 / 44125, WO 2016169683, EP183999.

[0006] Furthermore, for example, microencapsulated cyhalothrin (Karate Zeon) and deltamethrin preparations (DelCaps CS 050) are available on the market, in each case for foliar application.

[0007] Some patents also mention the potential use of capsule suspensions for soil application, such as WO2016169683, WO2016202659, where pyrethroids are also mentioned as potential active substances. There is also scientific literature on the general interaction of microcapsules in soil.

[0008] WO2011042495 explicitly mentions improving the soil mobility of poorly soluble crop protection active substances, in particular deltamethrin, for example by using polymer particles. However, no biological data are provided in WO2011042495, so there is no indication of a relationship between soil mobility, biological activity and / or bioavailability of the active substance. WO 2018 / 141594 describes the addition of a soil activator to a water-insoluble herbicide formulation. The substance is an alkyl C plant C 3 Phenyl ethoxylate type (C 2 -C a-EO) 1-100 Surfactants can be incorporated into the formulation (e.g. in SC) or added as a tank mix additive. In addition, WO 2018 / 141594 also mentions microencapsulated herbicide formulations as possible formulations that can be used, but there is also no data support.

[0009] WO 2017 / 149069 describes polyether-modified short-chain siloxanes as additional adjuvants for soil application to increase agronomic yields independently of the formulation type and the physical properties of the active substances.

[0010] WO 01 / 94001 describes microcapsules which additionally contain surface-modifying ingredients, including the example of pyrethroids. These substances are chemically bonded to the microcapsule shell to improve the properties of the capsule in the soil. This has been shown to improve soil fluidity.

[0011] Disadvantages of existing technology

[0012] Although the prior art describes the possibility of providing pyrethroids for soil application in the form of granular formulations, these formulations have only low active ingredient concentrations and therefore require high application rates, which also lead to high stress on the soil due to adjuvants and other formulation aids.

[0013] Furthermore, various options for providing pyrethroids as liquid formulations in encapsulated formulations are described in the prior art. However, it is not clear to what extent this is applicable to active ingredients with poor soil availability, such as deltamethrin, which cannot be used in solid formulations for soil application.

[0014] Furthermore, no formulations suitable for soil and foliar application are described in the prior art: in particular no formulations are known which are effective for soil application of deltamethrin.

[0015] In summary, it can be said that experts in the field currently consider deltamethrin to be particularly unsuitable for soil application.

[0016] Purpose

[0017] It was therefore an object of the present invention to provide a suitable formulation which has a highest possible active ingredient load and a low application rate for the pyrethroid active ingredients, in particular deltamethrin, and generally ensures sufficient bioavailability and also sufficient long-term soil application activity.

[0018] It is also an object of the present invention to provide a formulation which stresses the soil using only small amounts of formulation auxiliaries and inert materials.

[0019] It is also an object of the present invention to provide a formulation suitable for soil and foliar application.

[0020] Technical Solution

[0021] This object is solved by the capsule suspension concentrate (CS) according to the invention. It has surprisingly been found that the formulation according to the invention is generally suitable for soil application of pyrethroid compounds, regardless of their physicochemical properties. The CS according to the invention ensures a sufficiently high effectiveness and a sufficient duration of activity of the active ingredients. It has surprisingly been found that the formulation according to the invention exhibits good biological activity regardless of the soil conditions, such as the moisture content and the proportion of organic matter in the soil.

[0022] It could also be demonstrated that the capsule suspensions according to the invention are also suitable for foliar application. Summary of the invention

[0023] Accordingly, the present invention provides a capsule suspension concentrate comprising

[0024] A) a particle dispersed phase comprising

[0025] 1') the reaction product of at least one compound a1-1') having isocyanate-reactive groups and an isocyanate or an isocyanate mixture a1.2),

[0026] 2) Pyrethroids a2.1) in organic, water-immiscible solvents a2.2),

[0027] 3') one or more additives a3.1') and

[0028] B) a liquid aqueous phase comprising at least one protective colloid b1.1) and optionally further additives b1.2),

[0029] The average particle size of the dispersed phase A) is preferably 1-50 gm

[0030] and among them

[0031] a1-2) in a proportion of 0.1% to 2% by weight,

[0032] The proportion of the agrochemical active ingredient a2.1) is 1 to 50% by weight,

[0033] The proportion of organic solvent a2.2') is 1 to 90% by weight,

[0034] The proportion of the additive a3.1) is 0.5 to 5% by weight,

[0035] The proportion of protective colloid b1.1) is 0.1 to 5% by weight, and

[0036] The proportion of additive b1.2) is 0.1 to 15% by weight.

[0037] When a.1.1 is not an added amine or alcohol, a.1.1 is an amine released by hydrolysis of isocyanate.

[0038] Compounds according to a1.1 may also be referred to as crosslinkers. Therefore, unless defined otherwise, a crosslinker is a compound according to a1.1 for the purposes of the present invention.

[0039] The present invention also provides the use of the capsule suspension of the present invention in soil application of pyrethroids and in particular deltamethrin.

[0040] The particle size is determined according to the CIPAC (CIPAC = International Pesticide Analysis Cooperative Committee; www.cipac.org) method MT 187. In this method, the particle size distribution is determined by laser diffraction. For this purpose, a representative amount of the sample is dispersed in degassed water at ambient temperature (self-saturation of the sample), sonicated (typically 60 seconds) and then measured in an instrument of the Malvern Mastersizer series. The scattered light is measured at different angles with the aid of a multi-element detector and the relevant values ​​are recorded. The proportions of specific particle size classes are calculated from the scattering data with the aid of the Fraunhofer model and the volume-weighted particle size distribution is calculated from this. The reported values ​​are typically the d50 and d90 values ​​= particle size of the active ingredient (50% and 90% of the total volume of the particles). The median particle size is referred to as the d50 value.

[0041] The particle size d50 of the particles of the dispersed phase A) is preferably 1-50 pm (micrometers), particularly preferably 1-20 pm, very particularly preferably 2-15 gm.

[0042] The present invention also provides a method for preparing the capsule suspension concentrate of the present invention, characterized in that it comprises the following process steps:

[0043] I. Preparation of organic phase A')

[0044] II. Preparation of aqueous phase B)

[0045] III. Preparation of an emulsion of A') in B')

[0046] IV. Optional addition of component a1.1) (when a1.1. is not water)

[0047] V. Heating Step

[0048] VI.Completion.

[0049] In step (I), the active ingredient a2.1) and the further additives a3.1) are dissolved in the organic solvent a2.2) with stirring. Step (I) of the process according to the invention is generally carried out at a temperature of 0° C. to 80° C., preferably 0° C. to 50° C., more preferably 2° C. to 40° C. The isocyanate a1.2) is then added to the resulting mixture. The addition can be carried out, for example, by direct addition to the mixture or by continuous metering with the aid of apparatus customary for such purposes (e.g. static mixers), the addition being carried out shortly before the combination with the aqueous phase B).

[0050] In step (II), at least one protective colloid b1.1) and optionally further additives b1.2) are dissolved in water while stirring. This step is generally carried out at a temperature of 0°C to 80°C, preferably 15°C to 80°C.

[0051] In step (III), the organic phase A) is added to the aqueous phase B) and an emulsion is prepared. All devices that generate strong shear forces commonly used for such purposes can be used for the preparation. Examples include rotor / stator mixers and jet dispersers. Step (III) is usually carried out at a temperature of 0° C. to 80° C., preferably 10° C. to 75° C. The preparation of the emulsion can be carried out batchwise or continuously.

[0052] In step (IV) of the process according to the invention, the emulsion obtained from step (III) is mixed in step (IV) with diamines, polyamines, diols, polyols and / or amino alcohols a1.1) under stirring. The amine or alcohol component a1.1) is conveniently added here in the form of an aqueous solution. However, in the process according to the invention, preference is given to using exclusively water as component a1.1), which, as mentioned above, is to be understood in the context of the present invention as component a1.1 formed by the hydrolysis of isocyanates with water. "Water" here therefore refers to the hydrolysis product (amine).

[0053] In step (V), the mixture is heated under stirring for a certain time to ensure that the reaction has been completed. The time period is generally 0 to 24 hours, preferably 0.5 to 8 hours, more preferably 1 to 5 hours, and the reaction is preferably carried out at a temperature of 0°C to 80°C, preferably 20°C to 75°C.

[0054] In step (VI), the capsule suspension is brought to room temperature at the end of the reaction leading to capsule formation and then further mixed with additive b1.2′) optionally with stirring. Additive b1.2′) can in principle be added in step (II) or step (VI) as desired.

[0055] The process of the present invention is preferably carried out under atmospheric pressure.

[0056] In the implementation of the method according to the present invention, the ratio of the NCO groups from component a1.2) to the NCO-reactive groups from component a1.1) can vary within a specific range. Preferably, 0 to 1.5 equivalents of the added amine or alcohol component are used per 1 mol of isocyanate. Preferably, no crosslinking agent is used, i.e., a1-1) is formed by the hydrolysis of isocyanate with water (or "water" as defined above).

[0057] In another embodiment, 0.1 to 1.5 equivalents of the added amine or alcohol component are used per 1 mol of isocyanate.

[0058] Depending on the amounts of the shell-forming components a1.1) and a.1.2) used and the resulting particle size, the theoretical wall thickness of the capsule can be calculated based on the average particle size (d50) of the capsule and the particle size of the shell-forming material used. The density of the polymer is set to 1 (1 g / cm 3 ). The wall thickness calculated for the capsules in the capsule suspension concentrate of the present invention is preferably 0.001 to 4 μm, more preferably 0.01 to 2 μm, and particularly preferably 0.01 to 1 μm.

[0059] In the reaction of a1.1) and a1.2), 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, particularly preferably 2.0 ≤ x ≤ 3.5, and very particularly preferably 2.2 < x < 2.8.

[0060] The "number-average functionality x" as a feature in the method according to the present invention is as follows. The key here is the compound with a higher functionality; the value obtained by subtracting 2 from the compound with a lower functionality is added to the compound with a higher functionality. For example, if the (average) functionality of a1-1) is 2.1 and that of a1.2) is 2.6, then: 2.1 - 2 = 0.1. This difference is added to 2.6: 2.6 + 0.1 = 2.7. Thus, the number-average functionality is 2.7. Or, if a1) is 2.7 and a2) is 2.3, then the resulting number-average functionality is 2.7 + 2.3 - 2 = 3.0.

[0061] Useful compounds a1.1') having isocyanate-reactive groups include aliphatic, aromatic, cyclic and alicyclic primary and secondary diamines, and polyamines. Examples include ethylenediamine (EDA), diethylenetriamine (DETA), monoisopropylamine, 4-aminopyridine (4-AP), n-propylamine, vinyl or acrylimidopolyethylenimine, triethylenetetramine (TETA), tetraethylenepentamine, 2,4,4'-triaminodiphenyl ether, bis(hexamethylene)triamine, trimethylenedipiperidine (TMDP), guanidine carbonate (GUCA), phenylenediamine, toluenediamine, pentamethylenehexamine, 2,4-.-amino-6-methyl-1,3,5-triazine, 1,2-diaminocyclohexane, 4,4'-diaminodiphenylformamide, 2,4-diaminodiphenylamine ... alkane, 1,5-diaminonaphthalene isophorone diamine, diaminopropane, diaminobutane, piperazine, aminovinylpiperazine (AEP), poly(propylene glycol) bis(2-aminopropyl ether) or O,O'-bis(2-aminopropyl)polypropylene glycol block polyethylene glycol block polypropylene glycol, hexamethylenediamine, bis(3-aminopropyl)amine, bis(2-methylaminoethyl)methylamine, 1,4-diaminocyclohexane, 3-amino-1-methylaminopropane, N-methylbis(3-aminopropyl)amine, 1,4-diamino-n-butane and 1,6-diamino-n-hexane. Hexamethylenediamine and diethylenetriamine are preferred.

[0062] Useful compounds a1) having isocyanate-reactive groups 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.

[0063] Compounds a1.1′) having isocyanate-reactive groups also include amino alcohols. Examples include triethanolamine, monoethanolamine, triisopropanolamine, diisopropylamine, N-methylethanolamine, N-methyldiethanolamine.

[0064] In a very particularly preferred embodiment, only water is used as isocyanate-reactive component a1.1). It reacts in situ with the (poly / di)isocyanate to form the (poly / di)amine, which then itself has isocyanate-reactivity.

[0065] It is likewise possible to use mixtures of a1.1').

[0066] Isocyanates or isocyanate mixtures a1.2) are mixtures of mono-, di- and / or polyisocyanates, or the reaction products of isocyanate mixtures. Suitable compounds a1.2′) 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, 1,4-diisocyanatocyclohexyl, 1,8-diisocyanato-4-methyloctylisocyanate (nonane triisocyanate), 1,4-diisocyanato- Phenyl esters, 2,4- and / or 2,6-toluene 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-isocyanatopropyl-2-yl)benzene (TMXDI), 1,3-ylidene (isocyanatomethyl)benzene (xDI), 2,6-.=-isocyanatohexanoic 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, urethane, isocyanurate, biuret, imino-oxadiazinedione or oxadiazinedione structures and based on the diisocyanates are also suitable structural units for component a1.2), as are polycyclic compounds, for example polymeric MDI (pMDI, for example PAPI-27 from Dow or Desmodur 44V20 from Covestro AG) and combinations of the above.

[0067] Preference is given to using modifiers having an isocyanate (NCO) functionality of 2 to 6, preferably 2.0 to 4.5, particularly preferably 2.3 to 4.2 and very particularly preferably 2.3 to 3.8. Particular preference is given to modifiers having an NCO functionality of 2.4 to 3.

[0068] Preferably, diisocyanates selected from HDI, IPDI, H12-MDI, TDI and MDI are used for modification. HDI, TDI and MDI and their derivatives are particularly preferred. MDI is particularly preferably used in the form of polymeric MDI, such as PAPI-270

[0069] The preferred NCO content of the isocyanate or polyisocyanate or blend is 3% to 50% by weight, particularly preferably 10% to 40% by weight, particularly preferably 15% to 35% by weight, very particularly preferably 20% to 35% by weight. The isocyanate groups can also be present in partially or completely blocked form before their reaction with the isocyanate-reactive groups, in such a way that they cannot react immediately with the isocyanate-reactive groups. This ensures that no reaction occurs before a certain temperature (blocking temperature) is reached. Typical blocking agents can be found in the prior art and are selected in such a way that at temperatures of 60 to 220° C., depending on the substance, they are eliminated again from the isocyanate groups and only then react with the isocyanate-reactive groups. There are blocking agents that are incorporated into the polyurethane, as well as blocking agents that remain in the polyurethane as solvents or plasticizers, or that are released from the polyurethane as gases. Sometimes the expression "blocked NCO value" is used. When the expression "NCO value" is used in the present invention, this usually refers to the unblocked NCO value. The usual degree of blocking is up to <0.5%. Examples of typical blocking agents are caprolactam, methyl ethyl ketone oxime, pyrazoles, such as 3,5-dimethyl 1,2-n-t: azole or pyrazole, triazoles, such as 1,2,4-triazole, diisopropylamine, diethyl malonate, diethylamine, phenol and its derivatives, and imidazole.

[0070] Component a1.2') can also be used in the form of mixtures of the abovementioned compounds or in the form of prepolymers. In this case, for example, compounds containing isocyanate groups and having an NCO content of 3 to 50% by weight are reacted with compounds containing isocyanate-reactive groups and having an OH value of 10 to 150 mg KOH / g.

[0071] Particular preference is given to using only one isocyanate and not mixtures.

[0072] Useful organic solvents a2.2') include all customary organic solvents which are immiscible with water (phase separation) but readily dissolve the agrochemical active ingredients used. Preferred examples include optionally halogenated aliphatic and aromatic hydrocarbons, such as toluene, xylene, Solvesso 100, 100ND, 150, 150ND or 200, 200ND (mineral oil), tetrachloromethane, chloroform, dichloromethane and dichloroethane, esters, such as ethyl acetate, and alkanecarboxamides, such as N,N-dimethyloctanamide and N,N-di-methyldecanamide. Also vegetable oils and modified oils (e.g. by methylation, ethylation and hydrogenation and hydration) based on, for example, rapeseed oil, corn kernel oil, coconut oil, etc. are particularly preferably used. Particular preference is given to using mineral oils, very particular preference to using solvents based on dialkylnaphthalenes (e.g. diisopropylnaphthalene), as well as 1-methylnaphthalene and 2-methylnaphthalene and mixtures of naphthalenes (e.g. the product Solvesso 200ND, CAS No.: 64742-94-5).

[0073] In principle, it is also possible to use mixtures of organic solvents a2.2′). Preference is given to using only one solvent.

[0074] Useful further additives a3.1') include all oil-soluble surface-active additives. Particular preference is given to alkyl ethoxylates, alkyl propoxy ethoxylates, fatty acid esters of sorbitan and glycerol and organomodified trisiloxanes. Very particular preference is given to alkyl ethoxylates and alkyl propoxy ethoxylates. Particular preference is given to alkyl ethoxylates and alkyl propoxy ethoxylates having terminal hydroxyl functions. Examples include Vibrant, Synergen W06, Genapol EP2584 and Genapol X 060.

[0075] The aqueous phase B') of the capsule suspension concentrates according to the invention comprises, in addition to water, at least one protective colloid b1.1) and may comprise further additives b1.2), for example emulsifiers, preservatives, defoamers, cold stabilizers, thickeners, pH stabilizers and neutralizers.

[0076] Useful protective colloids b1-1') (emulsifiers for the dispersed phase A) include all substances usually used for such purposes. Preferred examples include natural and synthetic water-soluble polymers, such as gelatin, starch and cellulose derivatives, in particular cellulose esters and cellulose ethers, such as methylcellulose, and also polyvinyl alcohol, partially hydrolyzed polyvinyl acetate (degree of saponification <98%), lignin sulfonates (e.g. NA, 88 or Kraftsperse 25S), modified naphthalenesulfonates (e.g. D-425), polyvinylpyrrolidone and polyacrylamide. Particular preference is given to using polyvinyl alcohol, partially hydrolyzed polyvinyl acetate and lignin sulfonates. Very particular preference is given to polyvinyl alcohol, partially hydrolyzed polyvinyl acetate and lignin sulfonates.

[0077] Useful thickeners b1.2) include organic thickeners and inorganic thickeners. Useful organic thickeners include organic natural or biotechnologically modified or organically synthesized thickeners. Typical synthetic thickeners are (croda) and Thixin or Thixatrol 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 a combination thereof. Other typical representatives are based on cellulose or lignin. Preferably, natural modified thickeners based on xanthan gum are used. Typical representatives are, for example, (Solvay) and (Kelco Corp.), and (Cargill). Inorganic thickeners are usually based on silica or clay minerals.

[0078] Useful preservatives b1.2) include all substances which are usually present for this purpose in crop protection compositions, for example dichlorophenol, benzyl alcohol hemiformal, 5-chloro-2-methyl-4-isothiazolin-3-one [CAS No. 26172-55-4], 2-methyl-4-isothiazolin-3-one [CAS No. 2682-20-4] or 1,2-benzisothiazol-3(2H)-one [CAS No. 2634-33-5]. Examples include Acticide SPX (Thor), Proxel GXL (Lonza), Preventol D7 or Kathon CG / ICP.

[0079] Useful antifoams b1.2) include all substances which can usually be used for such purposes in crop protection compositions. Preference is given to silane derivatives, such as polydimethylsiloxane and magnesium stearate. 484, 426R, SRE (Solvay, Silioxane Emulsion) and 1571 (Momentive) was used as a typical product.

[0080] Substances which serve as cold stabilizers b1.2) may be all substances which can usually be used for this purpose in crop protection compositions. Examples include urea, glycerol and propylene glycol.

[0081] Useful neutralizing agents b1.2') include customary acids and bases. Examples include phosphoric acid, citric acid, sodium hydroxide solution and aqueous ammonia solution.

[0082] The composition of the capsule suspension concentrate according to the invention can vary within a specific range. The proportion of the dispersed phase A) based on the entire preparation is generally 10 to 90% by weight, preferably 30 to 70% by weight, more preferably 40 to 60% by weight.

[0083] The proportion of a1.2′) based on the entire preparation is generally 0.1 to 8% by weight, preferably 0.2 to 4.5% by weight, more preferably 0.5 to 4% by weight.

[0084] In an alternative preferred embodiment, the proportion of a1.2) is generally 0.1 to 2% by weight, preferably 0.2 to 2% by weight, more preferably 0.5 to 2% by weight, based on the entire preparation.

[0085] The proportion of the agrochemical active ingredient a2.1′) based on the entire preparation is generally from 1 to 50% by weight, preferably from 5 to 40% by weight, more preferably from 5 to 15% by weight.

[0086] The proportion of the organic solvent a2.2′) based on the entire preparation is generally 1 to 90% by weight, preferably 10 to 60% by weight, more preferably 25 to 40% by weight.

[0087] The proportion of the additive a3.1) based on the entire preparation is generally 0.1 to 10% by weight, preferably 0.5 to 5% by weight, more preferably 1 to 5% by weight, very particularly preferably 2 to 5% by weight.

[0088] The proportion of protective colloids b1.1) based on the entire preparation is generally 0.1 to 5% by weight, preferably 0.2 to 3% by weight, more preferably 0.2 to 1% by weight, and the proportion of additives b1.2) is generally 0.1 to 15% by weight, preferably 0.2 to 10% by weight, more preferably 0.3 to 3% by weight.

[0089] The ratio of a1.2) to the total organic phase A) is preferably 40:1 to 60:1, more preferably 45:1 to 60:1, particularly preferably 45:1 to 55:1. If a1-1) in the organic phase A) is water, the water required for the reaction with the isocyanate is not included in the organic phase.

[0090] Regarding the above-mentioned proportions of the individual components, it will be clear to a person skilled in the art that the preferred ranges of the individual components can be freely combined with each other, and therefore compositions having different preferred ranges of the individual components are also considered to be disclosed.

[0091] However, unless stated otherwise, the same level of preference ranges, ie for example all preferred or more preferred ranges, are particularly preferred and the specific disclosure is not intended to replace these general combinations but to be added thereto.

[0092] The same applies to other statements of preferred ranges elsewhere in the specification.

[0093] In a preferred embodiment, the proportion of a1.2) is from 0.1 to 8% by weight,

[0094] The proportion of the agrochemical active ingredient a2.1) is 1 to 50% by weight,

[0095] The proportion of organic solvent a.2.2) is 1 to 90% by weight,

[0096] The proportion of the additive a3.1') is 0.1 to 10% by weight,

[0097] The proportion of protective colloid b1.1') is 0.1 to 5% by weight,

[0098] and the additive b1.2) in a proportion of 0.1 to 15% by weight.

[0099] In an alternative embodiment, the proportion of a1.2) is from 0.2 to 4.5% by weight,

[0100] The proportion of the agrochemical active ingredient a2.1) is 5 to 40% by weight,

[0101] The proportion of organic solvent a.2.2) is 10 to 60% by weight,

[0102] The proportion of the additive a3.1') is 0.5 to 5% by weight,

[0103] The proportion of protective colloid b1.1') is 0.2 to 3% by weight,

[0104] and the proportion of additive b1.2) is 0.2 to 10% by weight.

[0105] In an alternative embodiment, the proportion of a1.2) is from 0.5 to 4.0% by weight,

[0106] The proportion of the agrochemical active ingredient a2.1) is 5 to 15% by weight,

[0107] The proportion of organic solvent a.2.2) is 25 to 40% by weight,

[0108] The proportion of additive a3.1) is 2 to 5% by weight,

[0109] The proportion of protective colloid b1.1) is 0.2 to 1% by weight,

[0110] and the additive b1.2) in a proportion of 0.3 to 3% by weight.

[0111] In a preferred embodiment, the proportion of a1.2) is 0.1 to 2% by weight,

[0112] The proportion of the agrochemical active ingredient a2.1) is 1 to 50% by weight,

[0113] The proportion of organic solvent a.2.2) is 1 to 90% by weight,

[0114] The proportion of the additive a3.1') is 0.5 to 5% by weight,

[0115] The proportion of protective colloid b1.1') is 0.1 to 5% by weight,

[0116] and the additive b1.2) in a proportion of 0.1 to 15% by weight.

[0117] In an alternative embodiment, the proportion of a1.2) is from 0.2 to 2% by weight,

[0118] The proportion of the agrochemical active ingredient a2.1) is 5 to 40% by weight,

[0119] The proportion of organic solvent a.2.2) is 10 to 60% by weight,

[0120] The proportion of additive a3.1) is 1 to 5% by weight,

[0121] The proportion of protective colloid b1.1') is 0.2 to 3% by weight,

[0122] and the additive b1.2) in a proportion of 0.2 to 10% by weight.

[0123] In an alternative embodiment, the proportion of a1.2) is from 0.5 to 2% by weight,

[0124] The proportion of the agrochemical active ingredient a2.1) is 5 to 15% by weight,

[0125] The proportion of organic solvent a.2.2') is 25 to 40% by weight,

[0126] The proportion of the additive a3.1') is 2 to 5% by weight,

[0127] The proportion of protective colloid b1.1') is 0.2 to 1% by weight,

[0128] and the additive b1.2) in a proportion of 0.3 to 3% by weight.

[0129] Preferably, the ratio of the agrochemical active ingredient a2.1) to the isocyanate or isocyanate mixture a1.2) is 1:1 to 30:1, preferably 1:1 to 15:1, more preferably 2:1 to 10:1.

[0130] When an amino-functional compound is used as component a1.1), the ratio of aminoisocyanate-reactive groups a1.1) to isocyanate mixture a1.2) is from 0 to 1.5, preferably from 0 to 1, more preferably from 0 to 0.5 and particularly preferably from 0 to 0.3. Very particularly preferably, it is 0, i.e. no amino-functional compound a1.1) is used and water is used instead as isocyanate-reactive groups.

[0131] Furthermore, the organic solvent a2.2) in the above embodiment is preferably a mineral oil, more preferably a solvent based on dialkylnaphthalene (e.g. diisopropylnaphthalene), 1-methylnaphthalene and 2-methylnaphthalene and a mixture of naphthalene (e.g. Solvesso 200ND product, CAS No.: 64742-94-5), and very particularly preferably 1-methylnaphthalene and 2-methylnaphthalene and a mixture of naphthalene as solvent.

[0132] In principle the formulations according to the invention can be mixed with other formulations to combine two or more active ingredients. For example, the invention can be combined with water-based formulations such as SC, SL or other CS.

[0133] Pyrethroids are synthetic insecticides based on the main active substances present in natural insecticides.

[0134] Preferably, the suitable pyrethroid is selected from acrinathrin, allethrin, d-cis-trans allethrin, d-transallethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, isomer), bioresmethrin, cycloprothrin, cyfiuthrin, beta-cyfiuthrin, cyhalothrin, 1ambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [(1R)-trans isomer] isomer】), deltamethrin, empenthrin [(EZ)-(1R) isomer], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, nucythrinate, numethrin, tau-fiuvalinate, halfenprox, imiprothrin, kadethrin, momfluorothrin, permethrin, phenothrin [(1R)-trans]isomer】), prallethrin, pyrethrins (pyrethrum), resmethrin, silafiuofen, tefiuthrin, tetramethrin, tetramethrin [(1R) isomer], tralomethrin, transfiuthrin', and methoxychlor'o

[0135] More preferred are deltamethrin, β-cyhalothrin, cypermethrin and cyhalothrin, and particularly preferred is deltamethrin.

[0136] Furthermore, in alternative embodiments, the capsule suspension concentrate may contain other insecticides, acaricides and / or nematicides, for example also as a result of mixing the above drugs with another formulation.

[0137] Insecticides, acaricides and / or nematicides that can be used in the context of the present invention, usually referred to herein by their common names, are known and described, for example, in "The Pesticide Manual", 16th ed., British Crop Protection Council 2012, or can be retrieved on websites such as www.alanwood.net / pesticides. The classification is based on the IRAC mode of action classification scheme applicable at the time of filing this patent application.

[0138] (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, formetanamide, ate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC and xylylcarb; or an organophosphate selected from acephate, azamethi phos), azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotoph os), dimethoate, dimethylvinphos, disulphoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl o-(methoxyaminothiophosphoryl) salicylateo-(methoxyaminothiophosphoryl) salicylate), isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamide amidon), phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclolos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, triclorfon, and vamidothion.

[0139] (2) GABA-gated chloride channel blockers, preferably cyclopentadiene-organochlorines selected from chlordane and endosulfan; or phenylpyrazoles (fiproles) selected from ethiprole and fipronil.

[0140] (4) Competitive modulators of nicotinic acetylcholine receptors (nAChR), preferably neonicotinoids, selected from acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam, or nicotine, or sulfoximine, selected from sulfoxaflor, or butenolide, selected from nupyradifurone, or mesoionic, selected from triflumezopyrim'.

[0141] (5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators, preferably spinosyns, selected from spinetoram and spinosad.

[0142] (6) Glutamate-gated chloride channel (GluCl) allosteric modulators, preferably avermectins / milbemycins, selected from abamectin, emamectin benzoate, lepimectin and milbemycin'.

[0143] (7′) Juvenile hormone analogs, preferably juvenile hormone analogs selected from hydroprene, kinoprene and methoprene, or fenoxycarb or pyriproxifen.

[0144] (8) Various types of non-specific (multi-site) inhibitors, preferably halogenated hydrocarbons, selected from methyl bromide and other halogenated hydrocarbons: or chloropicrine or sulphuryl fluoride or borax or tartar emetic or methyl isocyanate generators selected from diazomet and metam.

[0145] (9) A chord organ TRPV channel modulator selected from pymetrozine and nonicamid.

[0146] (10) Mite growth inhibitors selected from ciofentezine, hexythiazox, diflovidazin' and etoxazole'.

[0147] (11) A microbial disruptor of insect gut membranes, selected from Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies ai z The invention relates to a Bacillus thuringiensis plant protein selected from the group consisting of: Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb and Cry34Abl / 35Abl.

[0148] (12) Mitochondrial ATP synthase inhibitors, preferably ATP disruptors, selected from diafenthiuron, or organotin compounds selected from azocyclotin, cyhexatin and fenbutatinoxide, or propargite or tetradifon.

[0149] (13) An uncoupler of oxidative phosphorylation that disrupts the proton gradient, selected from chlorfenapyr, dinitrocresol (DNOC) and sulfiuramid.

[0150] (14) A nicotinic acetylcholine receptor channel blocker selected from the group consisting of bensultap, cartap hydrochloride, thiocylam and thiosultap-sodium.

[0151] (15) A type-0 chitin biosynthesis inhibitor selected from the group consisting of bistrifiuron, chlofiuazuron, difiubenzuron, nucycloxuron, nufenoxuron, hexaflumuron, 1ufenuron, novaluron, novifiumuron, tefiubenzuron and trifiumuron.

[0152] (16) A type 1 chitin biosynthesis inhibitor selected from buprofezin.

[0153] (17) Molting disruptors (especially Diptera), selected from cyromazine.

[0154] (18) An ecdysone receptor agonist selected from the group consisting of chromafenozide, halofenozide, methoxyfenozide and tebufenozide.

[0155] (19) An octopamine receptor agonist selected from amitraz.

[0156] (20) A mitochondrial complex III electron transfer inhibitor selected from the group consisting of hydramethylnone, acequinocyl and nuacrypyrim.

[0157] (21) A mitochondrial complex I electron transfer inhibitor, preferably a METI acaricide selected from fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad, or rotenone (Derris).

[0158] (22) A voltage-dependent sodium channel blocker selected from indoxacarb and metaflumizone.

[0159] (23) Acetyl-CoA carboxylase inhibitors, preferably tetronic acid and tetramic acid derivatives selected from spirodiclofen, spiromesifen and spirotetramate.

[0160] (24) Mitochondrial complex IV electron transfer inhibitors, preferably phosphine compounds selected from aluminum phosphide, calcium phosphide, phosphine and zinc phosphide, or cyanides, such as calcium cyanide, potassium cyanide and sodium cyanide.

[0161] (25) Mitochondrial complex II electron transfer inhibitors, preferably beta-ketonitrile derivatives selected from cyenopyrafen and cyfiumetofen, or carboxanilides selected from pyfiubumide.

[0162] (28) A ryanodine receptor modulator, preferably a diamide selected from chlorantraniliprole, cyantraniliprole and nubendiamide.

[0163] (29) A string tuner (with an undefined target structure) selected from flonicamid.

[0164] (30) Other active compounds selected from the group consisting of acynonapyr, afidopyropen, afoxolaner, azadirachtin, benclothiaz, benzoximate, benzpyrimoxan, bifenazate, brofianilide, bromopropylate, chinomethionat, chlorroprallethrin, cryolite, cyclobromide, cycloxaprid, cyhalodiamide, dicloromezotiaz, dicofol, dimpropyridaz, epsilon Metofiuthrin), ￡-Momfluthrin, Flometoquin, Luazaindolizine, Luensulfone, Lufenerim, Flufenoxystrobin, Flufiprole, Fluhexafon, Fluopyram, Flupyrimin, Fluralaner, Fluxametamide, Fufenozide, Guadipyr, Heptafiuthrin, Imidaclothiz, Iprodione, Isocycloseram, K-Bifenthrin, K-TefluthrinTefiuthrin, Lotilaner, Meperfiuthrin, Oxazosul, Paichongding, Pyridalyl, Pyrifiuquinazon, Pyriminostrobin, Spirobudiclofen, Spiropidion, Tetramethylfiuthrin, Tetrazolamide raniliprole'), tetrachlorantraniliprole', Tigolaner, Tioxazafen, thiofiuoximate, and iodomethane; other Bacillus firmus-based agents (I-1582, BioNeem, Votivo), and the following compounds: 1-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethane)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine (derived from WO 2006 / 043635) (CAS 885026-50-6), {1'-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]-5-fluorospirocycloindol-3,4'-piperidinyl]-1(2H)-yl}(2-chloropyridin-4-yl)methanone (known from WO 2003 / 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 WO 2006 / 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 WO 2010 / 052161) (CAS 1225292-17-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-ylethyl carbonate (known from EP 2647626) (CAS 1440516-42-6), 4-(but-2-yn-1-oxy)-6-(3,5-dimethylpiperidin-1-yl)-5-fluoropyrimidine (known from WO 2004 / 099160) (CAS 792914-58-0'), PF1364 (by JP2010 / 018586) (CAS Registry No. 1204776-60-2), (3E)-3-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene-1,1,1-trifluoro-propane-2-one (known from WO 2013 / 144213) (CAS 1461743-15-6), N-[3-(benzyloxycarbamoyl)-4-chlorophenyl]-1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide (known from WO 2010 / 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 (obtained from CN103232431) (CAS 1449220-44-3), 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxido-3-thietanyl)-benzamide, 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(trans-1-oxido-3-thietanyl)-benzamide and 4-[(5S)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxido-3-thietanyl')-benzamide (known from WO 2013 / 050317A1) (CAS 1332628-83-7'), N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl-1-propionamide, (+)-N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl-1-propionamide and (-)-N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl-1-propionamide (known from WO 2013 / 162715A2, WO2013 / 162716A2, US2014 / 0213448A1) (CAS 1477923-37-7), 5-II(2E)-3-chloro-2-propen-1-yl]amino]-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile (obtained from CN 101337937 A) (CAS1105672-77-2), 3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)thiomethyl]phenyl]-1-(3-chloro-2-pyridyl)-1H-oxadiazole-5-carboxamide (thiobenzamide (Liudaibeniiaxuanan', known from CN 103109816 A') (CAS 1232543-85-9); N-[4-chloro-2-II (1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-,'1t:pyridyl)-3-(fluoromethoxy)-1H-oxadiazole-5-carboxamide (known from WO 2012 / 034403A1) (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 201I / 085575A1) (CAS 1233882-22-8), 4-[3-[2,6-dichloro-4-[(3,3-dichloro-2-propenyl-1-yl)oxy]phenoxy]propoxy]-2-methoxy-6-(trifluoromethyl)-pyrimidine (known from CN 101337940 A) (CAS 1108184-52-6): (2E)- and 2(z)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylene-N-[4-(difluoromethoxy)phenyl-1-hydrazinecarboxamide (known from CN 101715774 A) (CAS 1232543-85-9): 3-(2,2-dichlorovinyl)-2,2-dimethyl-4-(1H-benzimidazol-2-yl)phenyl-cyclopropanecarboxylate (known from CN 103524422 A) (CAS 1542271-46-4): (4aS)-7-chloro-2,5-dihydro-2-[[(methoxycarbonyl)[4-[(trifluoromethyl)thio]phenyl]amino]carbonyl-1-indeno[1,2-eIll,3,4]oxadiazine-4a(3H)-carboxylic acid methyl ester (known from CN102391261 A) (CAS1370358-69-2); 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-1-uL-,It: mannosyl (known from US 2014 / 0275503A1) (CAS1181213-14-8'): 8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-azabicyclo[3.2.1]octane (CAS 1253850-56-4), (8-trans)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-azabicyclo[3.2.1]octane (CAS 933798-27-7), (8-cis)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-azabicyclo[3.2.11 octane (from WO 2007 / 040280A1, WO 2007 / 040282A1') (CAS 934001-66-8), N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl-N-ethyl-3-[(3,3,3-trifluoropropyl')thio]-1-propionamide (known from WO 2015 / 058021A1 and WO 2015 / 058028A1') (CAS 1477919-27-9) and N-[4-(aminothiomethyl)-2-methyl-6-[(methylamino)carbonyl]phenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazol-5-carboxamide (known from CN 103265527 A) (CAS 1452877-50-7), 5-(1,3-dioxane-2-yl)-4-1,14-(trifluoromethyl)phenyl]methoxy-1-pyrimidine (known from WO 2013 / 115391A1) (CAS 1449021-97-9), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-1,8-diazaspiro-14.5]decane-2,4-dione (known from WO 2014 / 187846A1) (CAS 1638765-58-8), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-2-oxo-1,8-diazaspiro-14.5]dec-3-en-4-yl-ethyl carbonate (known from WO2010 / 066780A1 and WO2011151146A1) (CAS 1229023-00-0), 4-[(5S)-5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[(4R)-2-ethyl-3-oxo-4-isoxazolinyl]-2-methylbenzamide (known from WO2011 / 067272 and WO2013 / 050302) (CAS 1309959-62-3).

[0165] Crop protection – treatment types

[0166] Plants and plant parts are treated with the capsule suspension according to the invention using customary treatment methods directly or by acting on their surroundings, growth environment or storage space, for example by dipping, spraying, atomizing, sprinkling, evaporating, dusting, misting, overseeding, foaming, painting, spreading, injecting, watering (drenching), drip irrigation and in the case of propagation material, in particular in the case of seeds, additionally by dry seed treatment, liquid seed treatment, slurry treatment, by encrustation, by coating with one or more coatings, etc. It is also possible to apply the capsule suspension according to the invention by the ultra-low dosage method or to inject the application form according to the invention or the capsule suspension itself into the soil.

[0167] A preferred direct treatment of plants is foliar application, i.e. applying the capsule suspension of the present invention to the leaves, in which case the frequency of treatment and the application rate should be adjusted according to the infestation level of the pest concerned.

[0168] In the case of a systemic action of the active ingredient, the capsule suspension according to the invention also enters the plant through the root system. The plant is then treated by the action of the capsule suspension according to the invention on the plant's growth environment. This can be achieved, for example, by drenching or by mixing into the soil or nutrient solution, i.e., impregnating the plant locus (e.g., soil or hydroponic system) with the liquid form of the capsule suspension according to the invention, or by soil application, i.e., the capsule suspension according to the invention is introduced into the plant locus in solid form (e.g., in the form of granules), or by drip irrigation application (also commonly referred to as "chemical irrigation"), i.e., the capsule suspension according to the invention is introduced into a specific location near the plant together with different amounts of water over a specific period of time through an underground or underground drip irrigation pipe. In the case of rice crops, this can also be achieved by metering the compound of formula (I) in a solid application form (e.g., as granules) into a rice field filled with water.

[0169] Soil application according to the invention is the preferred form of application of the capsule suspension according to the invention.

[0170] In an alternative embodiment, the capsule suspension of the present invention is applied as a foliar application.

[0171] The capsule suspension concentrates according to the invention are very suitable for applying the present agrochemical active ingredients to plants and / or their growth environment. They ensure the release of the active ingredients in the corresponding desired amount over a relatively long period of time. The capsule suspension concentrates according to the invention can be used conventionally as such or after prior dilution with water.

[0172] Application is carried out by customary methods, ie, for example, by pouring, spraying or atomizing.

[0173] The application rate of the capsule suspension concentrate according to the invention can be varied within a relatively wide range. This is guided by the relevant agrochemical active ingredient and its content in the microcapsule preparation.

[0174] The capsule suspension concentrate of the present invention can be produced by known methods, for example as a mixed preparation of individual components optionally with other active ingredients, additives and / or conventional formulation auxiliaries, which are then diluted with water and applied in a conventional manner, or by diluting the individual components prepared individually or partially individually with water to form a tank mix. It is also possible to apply the individual components prepared individually or partially individually at different times (separate application). It is also possible to apply the individual components or the capsule suspension concentrate of the present invention in more than one form (sequential application).

[0175] The invention is illustrated by the following examples.

[0176] Passing

[0177] Preparation of 1-CS preparation

[0178] Preparation of the organic phase: Dissolve the active ingredient in an organic solvent with stirring, optionally mix with other additives, then add the polyisocyanate in the specified proportions.

[0179] Preparation of the aqueous phase: Dissolve the protective colloid in water and then add the defoamer.

[0180] The organic phase is added to the aqueous phase and emulsified with the aid of a rotor / stator mixing tool (ultraTurrax) until the desired particle size is reached. Optionally, an amine component is additionally added to the emulsion. The mixture is heated to about 70° C. for 4 hours to ensure complete reaction of the wall-forming polyurea.

[0181] The mixture is then cooled to room temperature and biocide and thickener are added to adjust the desired viscosity. Optionally, ammonia is added to ensure that all isocyanate has reacted.

[0182] The particle size of the final capsules was determined by laser diffraction (Malvern Mastersizer').

[0183]

[0184]

[0185] 2. Tests of different formulation types in greenhouse

[0186] Method Description:

[0187] The activity test was carried out in a long plastic container filled with 5.9 kg of sandy loam (containing 1.8% humus) with a pH value of 7.1. A 5 cm deep trench was formed and four corn seeds (Ronaldino variety) were placed in it at 7 cm intervals. The test preparation was diluted in 4 ml of tap water and mixed evenly with 700 g of sandy loam. The treated soil was used to fill the trench and cover the seeds, which resulted in a total soil weight of 6.6 kg per container. One day after sowing, each container was infested with 450 Diabrotica balteata' using a pipette. The soil moisture content was adjusted to 50% of the specific field capacity and increased to 80% after the first hatched Diabrotica balteata larvae appeared. The growth conditions were a constant temperature of 25 ° C, a relative humidity of 60-70%, and sodium vapor lamp irradiation for 14 hours. The test setup included three replicates per treatment. 21 days after infestation, the test was evaluated by counting the number of damaged plants and measuring the weight of fresh buds in each container.

[0188] Since the absolute numbers can vary greatly from one test series to the next, the tables in all cases show only the results that were also performed in parallel. Where appropriate, two or more tables with respective reference results are shown.

[0189] Comparison of different formulation types:

[0190]

[0191] # Healthy plants / % / 83-3 Nl 25.0 N2 44.4 N3 0.05 N4 0.0 UTC not infected 100 UTC has been infected 0.0

[0192] Formulation #1 of the present invention exhibited significantly better activity than all comparative examples.

[0193] 3. Comparison of different CS preparations

[0194] (Unless otherwise stated, the following test conditions apply: DLT application conditions are always 60 g / ha and the observation period is 21 days after infestation)

[0195] a.AI concentration

[0196] # Healthy plants / % Bud weight / g 2 100 89.7 J 100 9l Summon 100 84.7 UTC not infected 100 79.7 UTC has been infected 0 29-3

[0197] The concentration of the AI ​​in the formulation can be varied at the same active ingredient application rate while having equally good activity.

[0198] b. Different active ingredients

[0199] Comparison of the formulation of the present invention with commercial products (capsule suspension or granules) of long-cyhalothrin, beta-cyhalothrin, and cypermethrin

[0200]

[0201]

[0202] All formulations according to the invention showed at least comparable, and mostly significantly better, effectiveness at the same AI application rate compared to commercial products with the same active ingredient.

[0203] c. Composition of capsule shell

[0204] Preparations according to the invention with different capsule thicknesses, isocyanate types, crosslinking and protective colloids were tested below.

[0205] # Healthy plants / % Bud weight / g S 33-3 38.8 UTC not infected 100 36.4 UTC has been infected 0 13.6

[0206] # Healthy plants / % Bud weight / g J 66.7 41.2 9 16.7 42.2 / O 1.0 28.0 ll 1.0 14.86 12 0.0 31.6 13 25.0 39.2 UTC not infected 100 34 UTC has been infected 0 21.6

[0207] # Healthy plants / % Bud weight / g 9 83-3 72.8 J 83-3 71.8 14 66.7 67.0 UTC not infected 100 72.2 UTC has been infected 8 26.2

[0208] # Healthy plants / % Bud weight / g J 100 26.4 15 100 37 / 6 100 39-3 UTC not infected 100 27.4 UTC has been infected 8 15.7

[0209] All formulations according to the invention showed activity. The activity after 21 days depended largely on the properties of the capsule shell. By properly selecting the shell components or by mixing different formulations, the desired release profile can be adjusted accordingly.

[0210] d. Type and dosage of adjuvant

[0211]

[0212] It was unexpectedly found that the adjuvant needed to be present in the capsule for optimal activity, whereas tank mix additives did not show sufficient activity. Furthermore, adjuvants with terminal hydroxyl functional groups showed better activity than adjuvants with methoxy functional groups.

[0213] After the formulation was dried, the capsule suspension was optically evaluated under a microscope:

[0214] Protective colloid <![CDATA[0%Br e akThru Vibrant]]> 0.5% BTV 1% BTV 2% BT V 3% BT V <![CDATA[ K uraray P ova l 26 - 88 ]]> <![CDATA[# 27 :.]]> <![CDATA[# 2S :.]]> <![CDATA[# 29 :0]]> <![CDATA[# 30 : + ]]> <![CDATA[ B to resist NA ]]> <![CDATA[# J / :.]]> <![CDATA[# / S .]]> <![CDATA[# 20 :0]]> <![CDATA[# J : + ]]>

[0215] Evaluation scheme: 1 = poor, 0 = marginal, + = good

[0216] e. Influence of soil conditions

[0217] 1. Standard soil, 2. Standard soil + 20% peat;

[0218]

[0219] Surprisingly, the activity was found to be independent of soil composition.

[0220] Soil moisture content

[0221] Application scenario:

[0222] A') Introduction of the formulation according to the invention into the topmost soil layer (approximately 40-50% of water retention capacity) = Standard

[0223] B') The formulation according to the invention was introduced into the uppermost soil layer (approximately 40-50% of the water holding capacity) and stored under moist conditions for 7 days.

[0224] C') The formulation according to the invention was introduced into the uppermost soil layer (about 40-50% water holding capacity) and the treated soil was dried for 7 days (<20% water absorption capacity).

[0225] D) The soil was allowed to dry out for 7 days (<20% water absorption capacity), the formulation of the invention was applied to the dry soil and then re-watered after sowing.

[0226]

[0227] Surprisingly, it was found that the activity was independent of soil moisture conditions.

[0228] f. Comparison with commercial products

[0229] # Healthy plants / % Bud weight / g 9 83.3 72.8 DelCaps CS050 4.2 32.5 UTC not infected 100 72.2 UTC has been infected 8 26.2

[0230] For soil application, this commercial product exhibits significantly poorer activity than the formulations according to the invention.

[0231] g. Effect of particle size of different batches of the same preparation

[0232] # Healthy plants / % Bud weight / g J mouth 100 61.2 J Convex 100 67.1 <![CDATA[S 口 ]]> 100 63.7 S-convex 100 67.6 UTC not infected 100 69.7 UTC has been infected 0 34.1

[0233] Relatively small changes in particle size had no effect on activity.

[0234] 4. Outdoor test

[0235] The formulation according to the invention was tested in an outdoor trial against nematodes in corn in comparison with Belem GR (active ingredient: cypermethrin) as a standard. The capsule formulation was sprayed (furrow application) at an application rate of 60 g ai / ha (compared to Belem MG 0.8 applied at 96 g ai / ha) into the seed furrow.

[0236] The reported activity is the average of 4 individual results.

[0237] # active / % Unprocessed 46.9 S 73.8 J 75.7 9 70.7 / O 62.0 ll 45.9 8+11 65.0 <![CDATA[Bele m MG 0.8]]> 6l-3

[0238] Compared to the standard, the formulation of the present invention showed better activity. In addition, the release rate can be adjusted by mixing two formulations (#8+#11) with different releases. This will give an average activity.

[0239] 5. Foliar application

[0240] The formulations according to the invention were tested in a greenhouse for pre-infestation of:

[0241] Peach aphid (Myzus persicae) (MYZUPE) on cabbage (Melissa) and bell pepper (Feher);

[0242] Aphis gossypii (APHIGO) on cotton (Viky);

[0243] and mixed populations.

[0244] The application concentration was 400 l / ha using a track sprayer. Three replicates were performed in each case. The tests for MYZUPE were carried out at 20° C. and for APHIGO at 23° C. The evaluation was carried out 1, 4 and 7 days after application (1, 4, 7 days).

[0245] Application rate: 400 1 / ha, track sprayer, contact type, three replicates in each case.

[0246]

[0247] The formulation according to the invention showed better activity than SC025(N1).

[0248] Jiaoqie Fish Wall

[0249] Deltamethrin is the active substance from Bayer AG, Leverkusen.

[0250] p-Cyfluthrin is the active substance from Bayer AG, Leverkusen.

[0251] Cypermethrin was obtained from Agros Organics BVBA, Geel, Belgium.

[0252] Vibrant is a nonionic organic surfactant from Evonik Industries AG, Essen.

[0253] S240 is a polyether-modified trisiloxane from Evonik Industries AG, Essen.

[0254] Synergen w 06 is a fatty alcohol alkoxylate from Clariant Produkte (Deutschland) GmbH, Frankfurt.

[0255] Genapol EP 2584 is a fatty alcohol alkoxylate from Clariant Produkte (Deutschland) GmbH, Frankfurt.

[0256] Genapol X-060 is a fatty alcohol polyglycol ether from Clariant Produkte (Deutschland) GmbH, Frankfurt.

[0257] Genapol XM 060 is a fatty alcohol polyglycol ether having terminal methyl groups based on Genapol X-060 from Clariant Produkte (Deutschland) GmbH, Frankfurt.

[0258] 44V 20L is a polymeric isocyanate mixture based on diphenylmethane 4,4' diisocyanate from Covestro AG, Leverkusen.

[0259] T80 is a TDI (toluene diisocyanate) mixture from Covestro AG, Leverkusen.

[0260] 426R is a defoamer from Elkem Silicones Germany GmbH, Liibeck.

[0261] SRE is a defoamer from Wacker Chemie AG, Munich.

[0262] Kuraray 26-88 is a partially saponified polyvinyl alcohol from Kuraray Europe GmbH, Hattersheim.

[0263] NA is lignin sulfonate from Borregaard, Sarpsborg, Norway.

[0264] Standard chemicals:

[0265] Xanthan gum is a thickener for water-based systems (various suppliers).

[0266] Biocides that can be used are all commercially available and licensed biocides, examples of which include GXL and KathonTM CG / ICP from Dupont.

[0267] Solvesso 200ND is an aromatic hydrocarbon (multiple suppliers).

[0268] Diethylenetriamine and ammonia are standard chemicals available from a number of suppliers.

[0269] Select the fish L

[0270] DelCaps 050CS is a product from INNVIGO, Warsaw, Poland containing encapsulated deltamethrin.

[0271] 0.8MG is a commercial product containing cypermethrin as the active ingredient.

Claims

1. A capsule suspension concentrate comprising: A) a particle dispersed phase comprising: 1) the reaction product of at least one compound having isocyanate-reactive groups and an isocyanate or an isocyanate mixture, wherein the compound having isocyanate-reactive groups is selected from aliphatic, aromatic, cyclophatic and cycloaliphatic primary or secondary diamines or polyamines, primary and secondary, aliphatic and aromatic diols or polyols, amino alcohols, or water, and the isocyanate or isocyanate mixture is selected from mono-, di- and / or polyisocyanate mixtures, or reaction products of isocyanates, 2) a pyrethroid in an organic, water-immiscible solvent, wherein the pyrethroid is selected from the group consisting of deltamethrin, beta-cyfluthrin, cypermethrin and lambda-cyhalothrin, and 3) one or more first additives, wherein the first additive comprises at least one compound selected from alkyl ethoxylates and alkyl propoxy ethoxylates having terminal hydroxyl functional groups, and organically modified trisiloxanes, as well as, B) a liquid aqueous phase comprising: 1) at least one protective colloid selected from polyvinyl alcohol, partially hydrolyzed polyvinyl acetate and lignin sulfonate, and 2) optionally a second additive; in, The average particle size of the particles of the particle dispersed phase is 1 to 50 μm, and among them The proportion of isocyanate or isocyanate mixture is 0.1 to 2% by weight, The proportion of pyrethroids is 1% to 50% by weight, an organic, water-insoluble solvent in a proportion of 1 to 90% by weight, and The proportion of the first additive is 2 to 5% by weight, The proportion of protective colloid is 0.1 to 5% by weight, and The proportion of the second additive is 0.1 to 15% by weight.

2. The capsule suspension concentrate according to claim 1, characterized in that The compound having an isocyanate reactive group is selected from the following group: Aliphatic, aromatic, cyclic and alicyclic primary and secondary amines selected from ethylenediamine, diethylenetriamine, monoisopropylamine, 4-aminopyridine, n-propylamine, vinyl or acrylimido polyaziridine, triethylenetetramine, 2,4,4′-triaminodiphenyl ether, bis(hexamethylene)triamine, trimethylenebispiperidine, guanidine carbonate, phenylenediamine, toluenediamine, pentamethylenehexamine, 2,4-diamino-6-methyl-1,3,5-triazine, 1,2-diaminocyclohexane, 4,4′-diaminodiphenylmethane, 1, 5-Diaminonaphthylisophoramine, diaminopropane, diaminobutane, piperazine, aminovinylpiperazine, polypropylene glycol bis(2-aminopropyl ether) or o,o′-bis(2-aminopropyl)polypropylene glycol block polyethylene glycol block polypropylene glycol, hexamethylenediamine, bis(3-aminopropyl)amine, bis(2-methylaminoethyl)methylamine, 1,4-diaminocyclohexane, 3-amino-1-methylaminopropane, N-methylbis(3-aminopropyl)amine, 1,4-diaminobutane and 1,6-diaminohexane; Primary and secondary hydroxyl, aliphatic and aromatic diols and polyols selected from ethylene glycol, propylene glycol (1,2), propylene glycol (1,3), butylene glycol (1,4), pentanediol (1,5), hexanediol (1,6), glycerol and diethylene glycol; an amino alcohol selected from the group consisting of triethanolamine, monoethanolamine, triisopropanolamine, diisopropanolamine, N-methylethanolamine and N-methyldiethanolamine; and water.

3. The capsule suspension concentrate according to claim 1, characterized in that The compound having an isocyanate reactive group is selected from the group consisting of hexamethylenediamine, diethylenetriamine, glycerol, propane-1,2-diol and water.

4. The capsule suspension concentrate according to claim 1, characterized in that The compound having an isocyanate reactive group is selected from diethylenetriamine and water.

5. The capsule suspension concentrate according to claim 1, characterized in that The compound having an isocyanate-reactive group is water.

6. The capsule suspension concentrate according to claim 1, characterized in that The particles of the particle dispersed phase have an average particle size of 2 to 15 μm.

7. The capsule suspension concentrate according to claim 1, characterized in that The isocyanate is selected from diisocyanates or polymeric isocyanates.

8. The capsule suspension concentrate according to claim 1, characterized in that The isocyanate is a diisocyanate selected from hexamethylene 1,6-diisocyanate, isophorone diisocyanate, isomeric bis(4,4'-isocyanatocyclohexyl)methane and mixtures thereof with any isomer content, 2,4- and / or 2,6-toluenediphenylmethane 2,2'- and / or 2,4'- and / or 4,4'-diisocyanate or diphenylmethane polymerizing 4,4'-diisocyanate.

9. The capsule suspension concentrate according to claim 1, characterized in that The proportion of isocyanate or isocyanate mixture is 0.5 to 2.0% by weight, The proportion of pyrethroids is 5% to 15% by weight, The proportion of organic, water-insoluble solvent is 25 to 40% by weight, The proportion of the first additive is 2 to 5% by weight, The proportion of protective colloid is 0.2 to 1% by weight, and The proportion of the second additive is 0.3 to 3% by weight.

10. The capsule suspension concentrate according to claim 1, characterized in that The ratio of pyrethroid to isocyanate or isocyanate mixture is from 2:1 to 10:1 by weight.

11. The capsule suspension concentrate according to claim 1, characterized in that The ratio of isocyanate or isocyanate mixture to total organic phase is from 40:1 to 60:1 by weight.

12. The capsule suspension concentrate according to claim 1, characterized in that The ratio of isocyanate or isocyanate mixture to total organic phase is from 45:1 to 60:1 by weight.

13. The capsule suspension concentrate according to claim 1, characterized in that The ratio of isocyanate or isocyanate mixture to total organic phase is from 45:1 to 55:1 by weight.

14. The capsule suspension concentrate according to claim 1, characterized in that The organic, water-insoluble solvent is selected from the group consisting of dialkylnaphthalenes, and mixtures of 1-methylnaphthalene, 2-methylnaphthalene and naphthalene.

15. The capsule suspension concentrate according to claim 1, characterized in that The second additive is selected from the group consisting of emulsifiers, preservatives, defoamers, cold stabilizers, thickeners, pH stabilizers, neutralizers and mixtures thereof.

16. The capsule suspension concentrate according to claim 1, characterized in that The proportion of the particulate dispersed phase based on the entire preparation is 30 to 70% by weight.

17. The capsule suspension concentrate according to claim 1, characterized in that The proportion of pyrethroids based on the entire preparation is 5 to 15% by weight.

18. A method for preparing a capsule suspension concentrate according to any one of claims 1 to 17, characterized in that The process steps include:

1. Preparation of organic phase A), 2. Preparation of aqueous phase B), 3. Preparation of an emulsion of A) in B), 4. When the compound having an isocyanate reactive group is not water, optionally adding one or more compounds having an isocyanate reactive group selected from diamines, polyamines, diols, polyols and amino alcohols, 5. A heating step, and 6. Done.

19. Use of a capsule suspension concentrate according to any one of claims 1 to 17 for foliar application.

20. Use of a capsule suspension concentrate according to any one of claims 1 to 17 for soil application.

21. The use according to claim 20, characterized in that The release takes place over a relatively long period of time.

22. The capsule suspension concentrate according to any one of claims 1 to 17 for use in soil application of pyrethroids.

23. The capsule suspension concentrate according to any one of claims 1 to 17 for soil application of deltamethrin.

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