Aqueous formulation of dicamba

Abstract

The present invention relates to an agrochemical composition comprising a salt of dicamba and an N-C2-C 15 -alkylpyrrolidone. It also relates to a method for controlling unwanted vegetation and / or regulating plant growth, in which the agrochemical composition acts on the respective pests, their environment or the crop to be protected against the respective pests, acts on the soil and / or acts on the crop and / or acts on their environment; relates to a method for producing an agrochemical composition; relates to an adjuvant composition for increasing the solubility of a salt of dicamba in an aqueous composition, which comprises N-C2-C 15 -alkylpyrrolidone.

Description

[0001] The present invention relates to an aqueous formulation, in particular an aqueous SL formulation, which contains a salt of dicamba, hereinafter referred to as dicamba salt, in particular a dicamba salt of dicamba and a water-miscible organic amine, hereinafter referred to as dicamba-N, or a potassium salt of dicamba, hereinafter referred to as dicamba-K, and water.

[0002] Dicamba is the common name for the pesticide 3,6-dichloro-2-methoxybenzoic acid. Dicamba is a well-known synthetic auxin herbicide compound and is suitable for controlling unwanted vegetation, especially dicotyledonous plants. Dicamba salts are the preferred form of dicamba because they can be formulated in various agrochemical formulations to enable easy and safe handling by the applicator. A particular class of dicamba formulations is aqueous formulations, in particular aqueous SL formulations of dicamba salts.

[0003] Aqueous SL formulations, also known as "soluble liquid formulations" or "soluble (liquid) concentrates", are homogeneous solutions of the respective pesticides in an aqueous solvent which may contain, in addition to water, a water-miscible solvent. Generally, aqueous SL formulations can be easily diluted with water to the desired application concentration of the respective pesticide, and they are particularly suitable for tank mixing with other pesticides.

[0004] Aqueous SL formulations of dicamba salts are advantageous because dicamba can be formulated at high concentrations, usually at least 300 g / L, and they contain only a small amount of organic solvent relative to dicamba. The total amount of the formulation can be minimized, which is particularly beneficial for treating large land areas.

[0005] Unfortunately, aqueous SL formulations of dicamba may not be completely stable with respect to the formation of insoluble precipitates, especially if the SL formulation is stored at low temperatures. Without being bound by theory, it is believed that the formation of the precipitate may be caused by some by-products formed during the production process of the dicamba herbicide. Unfortunately, these precipitates cannot be easily redissolved by warming the formulation, and they may cause blockage of the spray nozzle equipment, making the metering of dicamba more difficult.

[0006] Reducing the off - target movement of pesticides from the treated area minimizes potential negative environmental impacts and maximizes pesticide efficacy where pesticides are most needed. By their nature, herbicides affect sensitive plants, and reducing their off - target movement reduces their impact on neighboring crops and other vegetation while maximizing weed control in the treated field. Off - target movement can occur through various mechanisms and is generally classified into the following categories: primary losses (direct losses from the application equipment before reaching the intended target) and secondary losses (indirect losses from the treated plants and / or soil). Primary losses from spray equipment typically occur in the form of fine dust or spray droplets, which take longer to settle and are more easily blown away from the target. The off - target movement of spray particles or droplets is commonly referred to as "spray drift". Primary losses can also include the use of contaminated equipment resulting in inadvertent application to sensitive crops. Contamination can occur when a product (i.e., pesticide) is not adequately cleared from the spray equipment and the contaminated equipment is subsequently used to apply a different product to sensitive crops, causing crop damage. Secondary losses describe the off - target movement of pesticides after they have contacted the target soil and / or foliage and are lost from the treated surface by means such as airborne dust (e.g., crystalline pesticide particles or pesticides bound to soil or plant particles), volatilization (i.e., the change in state from the applied solid or liquid form to a gas), or runoff in rain or irrigation water. Off - target movement is typically mitigated through appropriate application techniques (e.g., spray nozzle selection, nozzle height, and wind restrictions) and improved pesticide formulations. This is also the case for dicamba, where appropriate application techniques mitigate potential primary losses and equipment contamination. The secondary losses of dicamba have been further reduced by the development of formulations using improved dicamba salts such as dicamba BAPMA.

[0007] WO 2011 / 019652 describes an aqueous formulation of a dicamba salt containing a polymeric amine to reduce the off - target movement and volatility of the formulation. This formulation may suffer from cold storage stability problems.

[0008] Accordingly, there is a desire to provide an aqueous formulation of a dicamba salt that alleviates at least some of the above problems. In particular, the aqueous formulation should be less sensitive to the formation of precipitates during cold storage. The formulation should have good biological activity, exhibit favorable spraying properties, and be safe to handle during application. There is a further desire to provide an aqueous formulation of a dicamba salt, especially an SL formulation, that has a high loading of dicamba and does not have the above stability problems.

[0009] It is also desired to provide formulations that can be admixed with glyphosate and / or glufosinate and / or their salts (especially the ammonium salts, diammonium salts, isopropylammonium salts and potassium salts of glyphosate and / or glufosinate), or formulations that can be tank-mixed with formulations of glyphosate and / or glufosinate and / or their salts. Such pesticidal coformulations containing dicamba and glyphosate and / or glufosinate should be less sensitive to the formation of precipitates, exhibit favorable spraying properties, have good biological activity, and be safe to handle during application.

[0010] Surprisingly, it has been found that these and further objects are solved by aqueous formulations of dicamba salts, which formulations contain at least one organic solvent selected from N-C2-C 15 -alkylpyrrolidones, where the alkyl may be hydroxy-substituted, especially at least one organic solvent selected from N-C3-C 12 -alkylpyrrolidones, more especially at least one organic solvent selected from N-C3-C6-alkylpyrrolidones.

[0011] Accordingly, a first aspect of the present invention relates to an aqueous formulation of dicamba, especially an aqueous SL formulation, which contains

[0012] a) dicamba in the form of a dicamba salt, and

[0013] b) at least one organic solvent selected from N-C2-C 15 -alkylpyrrolidones, where the alkyl may be hydroxy-substituted, which is referred to herein as solvent b).

[0014] Another (second) aspect of the present invention also relates to a method for producing an aqueous formulation of a dicamba salt as defined herein, which comprises the step of mixing a dicamba salt with water and at least one solvent b) and optional additional ingredients of the formulation.

[0015] Yet another (third) aspect of the present invention also relates to a method for controlling unwanted vegetation and / or regulating plant growth, in which an aqueous formulation of a dicamba salt as defined herein is made to act on the respective pests, their environment, or the crop to be protected from the respective pests, on the soil and / or on the crop and / or on their environment.

[0016] Another (fourth) aspect of the present invention relates to the use of solvent b) as defined herein for reducing the formation of precipitates in aqueous formulations containing dicamba salts, especially aqueous SL formulations.

[0017] It has also been found that the combination of solvent b) as defined herein with at least one additive d) imparts stability to aqueous formulations of dicamba salts, especially aqueous formulations of dicamba-K. The additive d) is selected from

[0018] d1) Polyalkylene oxide block copolymer of formula (I)

[0019] R 1 O(EO) n (PO) m (EO) p R 2 (I),

[0020] wherein

[0021] EO is CH2CH2O;

[0022] PO is CH2CH(CH3)O;

[0023] R 1 、R 2 are H or C1-C3-alkyl;

[0024] n and p are independently natural numbers from 10 to 250; and

[0025] m is a natural number from 10 to 100; and

[0026] d2) Hyperbranched polycarbonate, which is attached to a linear polymer containing polyethylene oxide.

[0027] Additive d) can be combined with one or more solvents e) selected from C1-C6-alkyl lactates, C3-C6-lactones, and mixtures thereof.

[0028] Accordingly, another (fifth) aspect of the present invention relates to an adjuvant composition comprising a solvent b) as defined herein and at least one additive d) selected from the group consisting of the polyalkylene oxide block copolymer of formula (I) of d1), the hyperbranched polycarbonate of d2), and combinations of d1) and d2), and optionally a mixture of one or more solvents e). The sixth aspect of the present invention relates to the use of these adjuvant compositions for improving the stability of aqueous formulations of dicamba salts to prevent the formation of precipitates.

[0029] Solvent b) as defined herein, and combinations of solvent b) with one or both of additives d1) and / or d2) and / or with solvent e) are capable of reducing droplet formation when preparing an aqueous dilution of a formulation of a dicamba salt (i.e., an aqueous spray solution obtained by diluting a formulation of a dicamba salt with water). Accordingly, another (seventh) aspect of the present invention relates to the use of solvent b) as defined herein, or a combination of solvent b) and at least one additional component selected from additives d1) and d2) and solvent e) as defined herein, for reducing droplet formation when preparing an aqueous dilution of a formulation of a dicamba salt (in particular, an aqueous SL formulation of a dicamba salt). Another (eighth) aspect of the present invention relates to a method for reducing droplet formation when applying an aqueous spray solution obtained by diluting a formulation of a dicamba salt (in particular, an aqueous SL formulation of a dicamba salt). Such a method comprises the step of incorporating solvent b) as defined herein, or a combination of solvent b) and at least one component selected from additives d1) and d2) and solvent e) as defined herein, into the spray solution or into the formulation of the dicamba salt.

[0030] The following explanations apply to the various aspects of the present invention. Combinations of embodiments with other embodiments, regardless of their respective preferred levels, are within the scope of the present invention.

[0031] Prefix C n -C m relates to the number of carbon atoms that a molecule or group may have. For example, C n -C m -alkyl refers to a straight-chain or branched alkyl having from n to m carbon atoms. In particular, C1-C3-alkyl refers to an alkyl having from 1 to 3 carbon atoms, and C2-C 15 -alkyl refers to an alkyl having from 2 to 15 carbon atoms, and so on.

[0032] In the present invention, an aqueous SL formulation, also referred to as a "soluble concentrate" or "soluble (liquid) concentrate", is an almost homogeneous solution of the ingredients in an aqueous solvent which, in addition to water, contains at least one solvent b). Almost homogeneous means that the formulation is optically clear, i.e., it is not turbid or does not contain solids.

[0033] The aqueous formulation contains an N-C2-C 15 -alkylpyrrolidone, in particular selected from N-C3-C 12-alkylpyrrolidone, more particularly at least one organic solvent b) selected from N-C3-C8-alkylpyrrolidone. The alkyl group may be unsubstituted or may be substituted with a hydroxyl group. In particular, the alkyl group may be unsubstituted. The alkyl group may be branched or straight-chain. In particular, the alkyl group is straight-chain. Examples of solvent b) include, but are not limited to, N-ethylpyrrolidone, N-(2-hydroxyethyl)pyrrolidone, N-(n-propyl)pyrrolidone, N-(2-propyl)pyrrolidone, N-(n-butyl)pyrrolidone, N-(2-butyl)pyrrolidone, N-(isobutyl)pyrrolidone, N-(tert-butyl)pyrrolidone, N-(n-pentyl)pyrrolidone, N-(n-hexyl)pyrrolidone, N-(2-hexyl)pyrrolidone, N-(n-heptyl)pyrrolidone, N-(2-heptyl)pyrrolidone, N-(n-octyl)pyrrolidone, N-(2-octyl)pyrrolidone, N-(2-ethyl-1-hexyl)pyrrolidone, N-(n-nonyl)pyrrolidone, N-(n-decyl)pyrrolidone, N-(n-undecyl)pyrrolidone, N-(n-dodecyl)pyrrolidone, N-(n-tridecyl)pyrrolidone, N-(n-tetradecyl)pyrrolidone or N-(n-pentadecyl)pyrrolidone. Preferred is N-C3-C 12 -alkylpyrrolidone, more particularly N-C3-C8-alkylpyrrolidone.

[0034] In particular, solvent b) comprises at least one N-C3-C6-alkylpyrrolidone in which the alkyl group is straight-chain, more particularly at least one N-C3-C6-alkylpyrrolidone in which the alkyl group is straight-chain, especially N-(n-butyl)pyrrolidone. In a particular set (1) of embodiments, solvent b) is selected from N-C3-C6-alkylpyrrolidone in which the alkyl group is straight-chain, more particularly from N-C4-C5-alkylpyrrolidone in which the alkyl group is straight-chain, and solvent b) is especially N-(n-butyl)pyrrolidone. In a second set (2) of embodiments, solvent b) is at least one N-C3-C6-alkylpyrrolidone (in which the alkyl group is straight-chain), more particularly at least one N-C3-C6-alkylpyrrolidone (in which the alkyl group is straight-chain), especially N-(n-butyl)pyrrolidone, together with at least one other N-C2-C 15 -alkylpyrrolidone, especially together with at least one N-C7-C 15 -alkylpyrrolidone. An example of such a combination is the combination of N-(n-butyl)pyrrolidone with N-(n-octyl)pyrrolidone and / or N-(n-dodecyl)pyrrolidone.

[0035] In the aqueous formulation of the present invention, N-C2-C 15The amount of N-alkylpyrrolidone is generally in the range of 10 to 200 g / l, especially in the range of 15 to 100 g / l, preferably in the range of 20 to 80 g / l, especially in the range of 25 to 60 g / l. These amounts generally correspond to a concentration of N-C2-C 15 -alkylpyrrolidone in the range of 0.8 to 16% by weight, especially in the range of 1.2 to 8.0% by weight, preferably in the range of 1.5 to 6.5% by weight, especially in the range of 2.0 to 5.0% by weight, based on the total weight of the formulation.

[0036] The aqueous formulations of the present invention generally contain a dicamba salt in an amount such that the concentration of dicamba, calculated as the free acid, is at least 350 g / l, especially at least 380 g / l, especially at least 400 g / l, based on the total volume of the formulation. Generally, based on the total volume of the formulation, the concentration of the salt is not higher than 850 g / l, especially not higher than 830 g / l or 810 g / l, and is generally in the range of 350 to 850 g / l, especially in the range of 380 to 830 g / l, especially in the range of 400 to 810 g / l.

[0037] The aqueous formulations of the present invention generally contain a dicamba salt at a concentration of at least 450 g / l, especially at least 500 g / l, especially at least 520 g / l, based on the total volume of the formulation. Generally, based on the total volume of the formulation, the concentration of the salt is not higher than 1000 g / l, especially not higher than 975 g / l or 950 g / l, and is generally in the range of 450 to 1000 g / l, especially in the range of 500 to 975 g / l, especially in the range of 520 to 810 g / l.

[0038] The aqueous formulations of the present invention generally contain a dicamba salt at a concentration of at least 30% by weight, especially at least 35% by weight, preferably at least 40% by weight, especially at least 42% by weight, based on the total weight of the aqueous formulation. Based on the total weight of the aqueous formulation, the concentration of the dicamba salt generally does not exceed 80% by weight, especially 75% by weight. In particular, based on the total weight of the agrochemical composition, the concentration of the dicamba salt in the aqueous formulation is in the range of 35 to 80% by weight, preferably in the range of 40 to 75% by weight, especially in the range of 42 to 70% by weight.

[0039] In the aqueous formulations of the present invention, the dicamba salt is generally completely soluble at 20 °C.

[0040] The agrochemical composition typically contains one or more minor components, which are by-products of the dicamba manufacturing process. Such by-products include 3,5-dichloro-2-methoxybenzoic acid (CAS 22775-37-7), 3,6-dichloro-2-hydroxybenzoic acid (CAS 3401-80-7), 3,5-dichloro-2-hydroxybenzoic acid (CAS 320-72-9), 3-chloro-2,6-dimethoxybenzoic acid (CAS 36335-47-4), 3,4-dichloro-2-methoxybenzoic acid (CAS 155382-86-8), 3,4-dichloro-2-hydroxybenzoic acid (CAS 14010-45-8) and / or 3,5-dichloro-4-methoxybenzoic acid (CAS 37908-97-7) or their salts. At least some of these compounds typically tend to form insoluble precipitates in common liquid aqueous formulations. These precipitates may form sediment over time or cause cloudiness of the liquid aqueous formulation. In other words, at least some of the minor components cause instability of the aqueous formulation of the dicamba salt. In extreme cases, this instability may lead to clogging of the spray nozzle device and make metering of the concentrated formulation of the dicamba salt more difficult. The dicamba salt formulation of the present invention alleviates the problems associated with these minor components.

[0041] Calculated as the free acid of dicamba and the free acids of the minor components, the relative amount of all minor components relative to the total mass of dicamba in the aqueous formulation is typically in the range of 1 wt% to 20 wt%. The relative amount can be at least 1.5 wt%, particularly at least 2 wt%, especially at least 5 wt%. The relative amount of the minor components relative to dicamba can be at most 18 wt%, particularly at most 15 wt%, especially at most 10 wt%. In particular, calculated as the free acid of dicamba and the free acids of the minor components, the relative amount of all minor components relative to the total mass of dicamba in the aqueous formulation is in the range of 1.5 wt% to 15 wt%, especially in the range of 2 wt% to 10 wt%.

[0042] Without being bound by theory, it is believed that this instability is particularly caused by at least one of the above dichloro-2-hydroxybenzoic acid compounds, i.e., by one of 3,6-dichloro-2-hydroxybenzoic acid, 3,5-dichloro-2-hydroxybenzoic acid and 3,4-dichloro-2-hydroxybenzoic acid and their combinations.

[0043] Surprisingly, it has been found that due to the presence of solvent b) or its combination with at least one additional component selected from additive d1), additive d2) and solvent e), these minor components with low water solubility remain dissolved in the formulations of the present invention. Thus, aqueous formulations of dicamba salts containing at least one solvent b) or its combination with at least one additional component selected from additive d1), additive d2) and solvent e) remain clear, homogeneous and transparent, even when stored at low temperatures below 10 °C and even below 0 °C.

[0044] In one embodiment, the formulation of the present invention contains 3,5-dichloro-2-methoxybenzoic acid as a minor component. In another embodiment, the formulation of the present invention contains the by-product 3,6-dichloro-2-hydroxybenzoic acid. In another embodiment, the formulation of the present invention contains the by-product 3,6-dichloro-2-hydroxybenzoic acid. In another embodiment, the formulation of the present invention contains the by-product 3,5-dichloro-2-hydroxybenzoic acid. In yet another embodiment, the formulation of the present invention contains the by-product 3-chloro-2,6-dimethoxybenzoic acid. In yet another embodiment, the formulation of the present invention contains the by-product 3,4-dichloro-2-methoxybenzoic acid. In yet another embodiment, the formulation of the present invention contains the by-product 3,4-dichloro-2-hydroxybenzoic acid. In a further embodiment, the formulation of the present invention contains the by-product 3,5-dichloro-4-methoxybenzoic acid. In particular, the formulation of the present invention contains 3,5-dichloro-2-methoxybenzoic acid, 3,6-dichloro-2-hydroxybenzoic acid and 3,5-dichloro-2-hydroxybenzoic acid as minor components.

[0045] Generally, the relative amount of 3,5-dichloro-2-methoxybenzoic acid relative to the total mass of dicamba in the formulation can be in the range of 0.5 wt% to 10 wt%, particularly in the range of 1 wt% to 8 wt%. The relative amount of 3,6-dichloro-2-hydroxybenzoic acid relative to the total mass of dicamba in the formulation can be in the range of 0.1 wt% to 10 wt%, particularly in the range of 0.2 wt% to 5 wt% or in the range of 0.5 wt% to 5 wt%. The relative amount of 3,5-dichloro-2-hydroxybenzoic acid relative to the total mass of dicamba in the formulation can be in the range of 0.1 wt% to 10 wt%, preferably in the range of 0.2 wt% to 5 wt%. In particular, the relative amount of 3,5-dichloro-2-hydroxybenzoic acid relative to the total mass of dicamba in the formulation can be in the range of 0.5 wt% to 5 wt%, in the range of 0.8 wt% to 3 wt%.

[0046] Calculated as the free acid of dicamba and the free acid of the dichloro-2-hydroxybenzoic acid compound, the total amount of the minor components of the dichloro-2-hydroxybenzoic acids is generally in the range of 0.5% to 18% by weight, particularly in the range of 0.7% to 15% by weight, especially in the range of 1.0% to 10% by weight, relative to the total mass of dicamba in the aqueous formulation. The minor components can be present as free carboxylic acids or in the form of salts. It is preferably present in the form of salts, especially salts having the same counterions as the dicamba salts contained in the formulation.

[0047] The aqueous formulations of the present invention generally have a pH in the range of pH 6.0 to pH 11.0, particularly in the range of pH 6.5 to pH 10.5, especially in the range of pH 7.0 to pH 10.2. The pH value of the aqueous formulations given herein refers to the pH value measured at 22 °C and 1 bar in the undiluted aqueous formulation by means of a glass electrode.

[0048] The aqueous formulations of the present invention can contain an inorganic buffer as additional component d). The type of buffer is preferably selected to maintain the pH of the aqueous dilution of the aqueous formulation in the range of pH 4.5 to pH 6.5, particularly in the range of pH 5.0 to pH 6.0.

[0049] Preferably, the inorganic buffer is selected from alkali metal carbonates such as sodium carbonate and potassium carbonate. In particular, the buffer is potassium carbonate.

[0050] If present, the amount of the buffer is preferably in the range of 50 to 300 g / L, particularly in the range of 80 to 200 g / L, especially in the range of 110 to 180 g / L, based on the volume of the formulation, or in the range of 4 to 24% by weight, particularly in the range of 6.2 to 16% by weight, especially 8.5 to 13.6% by weight, based on the total weight of the formulation.

[0051] If component a) is a salt of dicamba with an amine, the aqueous formulation preferably contains an inorganic buffer, particularly potassium carbonate.

[0052] In the case of an aqueous formulation containing an alkali metal salt of dicamba as component a) (such as dicamba-K or dicamba-Na), no buffer is required. Thus, an aqueous formulation containing an alkali metal salt of dicamba as component a) generally does not contain an inorganic buffer.

[0053] The aqueous formulation of the present invention contains water. The amount of water is preferably selected such that the components of the formulation form an almost homogeneous solution. Such a formulation is also referred to as an aqueous SL formulation, or simply as aqueous SL (soluble liquid). The water content is usually at least 10% by weight, especially at least 15% by weight, preferably at least 20% by weight, particularly preferably at least 22% by weight, such as at least 25% by weight, based on the total weight of the aqueous formulation. Based on the total weight of the agrochemical composition, the water content usually does not exceed 60% by weight, especially at most 50% by weight, particularly at most 45% by weight. Based on the total weight of the agrochemical composition, the water content is usually in the range of 10 to 60% by weight, especially in the range of 15 to 50% by weight, particularly in the range of 20 to 45% by weight.

[0054] One group (3) of embodiments relates to aqueous formulations in which the dicamba salt is a salt of dicamba with a water-miscible amine. These salts are abbreviated hereinafter as dicamba-N.

[0055] As used herein, the term "water-miscible" refers to an amine that is completely miscible with deionized water at a temperature of 298 K and 1 bar or is soluble in water in an amount of at least 100 g / L at a temperature of 298 K and 1 bar.

[0056] Suitable organic amines miscible with water are those having at least one amino group, where 1, 2, or 3 of the amino hydrogen atoms are replaced by alkyl, hydroxyalkyl, alkoxyalkyl, hydroxyalkoxyalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, N-(aminoalkyl)aminoalkyl, N-(N’,N’-dialkylaminoalkyl)aminoalkyl, etc. As used herein, alkyl and alkoxy preferably have 1 to 4 carbon atoms, especially 1 or 2 carbon atoms, while the substituted alkyl moiety of alkoxyalkyl, hydroxyalkoxyalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, N-(aminoalkyl)aminoalkyl, and N-(N’,N’-dialkylaminoalkyl)aminoalkyl preferably has 2 to 4 carbon atoms.

[0057] Preferred are amines having a primary or secondary amino group and at least one additional functional group selected from primary amino, secondary amino, tertiary amino, hydroxyl, and ether groups.

[0058] Examples of suitable amines miscible with water include, but are not limited to, dimethylamine, diethylamine, n-propylamine, isopropylamine, 2-hydroxyethylamine (ethanolamine or MEA), 2-(2-hydroxyethoxy)ethan-1-amine (diethylene glycol amine or DGA), bis(2-hydroxyethan-1-yl)amine (diol amine), tris(2-hydroxyethyl)amine (triethanolamine), tris(3-propanol)amine, tris-(hydroxypropyl)amine (tripromine), N-(3-aminopropyl)-N-methylamine, N,N-bis-(3-aminopropyl)-N-methylamine (biproamine, BAPMA), N,N-dimethyldipropylenetriamine (DMAPAPA). Further examples are oligomeric amines having a number average molecular weight in the range of 200 to 500 g / mol, such as polyetheramines, such as Jeffamine types having a number average molecular weight in the range of 200 to 500 g / mol and oligomeric polyamines, such as polyalkyleneimines and N-substituted polyalkyleneimines, such as poly-N,N-bis-(3-aminopropyl)methylamine (MPPI).

[0059] In the formulations of the group (1) embodiments, preferred are those in which component a) is a formulation of dicamba with an amine selected from: monoalkanolamines, N,N-dialkanolamines, N-(dialkylene glycol)amines and N-(aminoalkyl)alkylamines, N,N-bis(aminoalkyl)alkylamines and N-(N,N-dialkylaminoalkylamino)alkylamines, especially selected from mono-C2-C4-alkanolamines, N,N-bis(C2-C4-alkanol)amines, N-(di-C2-C4-alkylene glycol)amines and N-(amino-C2-C4-alkyl)-C1-C2-alkylamines, N,N-bis(amino-C2-C4-alkyl)-C1-C2-alkylamines, N-(N’,N’-di-C1-C2-alkylamino-C2-C4-alkyl)-C1-C2-alkylamines, especially selected from N-(di-C2-C4-alkylene glycol)amines and N,N-bis(amino-C2-C4-alkyl)-C1-C2-alkylamines.

[0060] In the formulations of the group (1) embodiments, particularly preferred are those in which component a) is a formulation of dicamba with an amine selected from: 2-hydroxyethylamine (ethanolamine or MEA), 2-(2-hydroxyethoxy)ethan-1-amine (diethylene glycol amine or DGA), bis(2-hydroxyethan-1-yl)amine (diol amine), tris(2-hydroxyethyl)amine (triethanolamine), N-(3-aminopropyl)-N-methylamine, N,N-bis-(3-aminopropyl)-N-methylamine (BAPMA) and N,N-dimethyldipropylenetriamine (DMAPAPA), and in which the amine is especially DGA or BAPMA.

[0061] A particular group (3a) of embodiments relates to formulations in which component a) is a formulation of dicamba with the salt of DGA.

[0062] A specific group (3b) of embodiments relates to formulations in which component a) is a salt of dicamba with BAPMA.

[0063] Salts of dicamba with amines (dicamba-N) are known and most are commercially available. Dicamba-N can be prepared by reacting the free acid form of dicamba with one of the above amines. Dicamba-N can refer to a 1:1 salt of dicamba with an amine, but can also refer to a non-1:1 molar ratio, provided that the molar amount of the amine is sufficient for neutralization. If the amine bears more than one amino group, the molar ratio of the amine to dicamba is generally at least (1 / n):1, especially in the range of (1 / n):1 to (1.5 / n):1, particularly in the range of (1 / n):1 to (1.3 / n):1, where n is the number of amino groups in the amine. For example, in the case of DGA, the molar ratio of dicamba to DGA is in the range of 1:1 to 1.5:1, especially in the range of 1:1 to 1.3:1. In the case of BAPMA, the ratio is generally at least 0.34:1, especially in the range of 0.34:1 to 0.5:1, particularly in the range of 0.35:1 to 0.43:1.

[0064] The above disclosure regarding the type, amount thereof, concentration of the dicamba salt, type and amount of minor components, presence and amount of buffer, pH, and amount of water applies to the embodiments of groups (3), (3a), and (3b).

[0065] In particular, the embodiments of groups (3), (3a), and (3b) relate to aqueous formulations of dicamba, especially aqueous SL formulations, which contain

[0066] a) a salt of dicamba with a water-miscible amine in an amount of 450 to 1000 g / l, especially in the range of 500 to 975 g / l, particularly in the range of 520 to 810 g / l, based on the total volume of the formulation;

[0067] b) at least one organic solvent b) in an amount of 10 to 200 g / l, especially 15 to 100 g / l, preferably in the range of 20 to 80 g / l, particularly 25 to 60 g / l, selected from N-C2-C 15 -alkylpyrrolidones, where the alkyl may bear a hydroxyl group, and where the solvent b) is preferably selected from N-C3-C 12 -alkylpyrrolidones, more particularly selected from N-C3-C8-alkylpyrrolidones, and where the solvent b) especially comprises or is N-(n-butyl)pyrrolidone;

[0068] c) optionally, an inorganic buffer in an amount of 50 to 300 g / l, especially 80 to 200 g / l, particularly 110 to 170 g / l, preferably selected from alkali metal carbonates, especially potassium carbonate, and

[0069] f) Water up to the total volume of the formulation, and the amount of water is especially as given above.

[0070] More particularly, embodiments of groups (3), (3a) and (3b) relate to aqueous formulations of dicamba, especially aqueous SL formulations, which contain

[0071] a) A salt of dicamba with a water-miscible amine, in an amount of 450 to 1000 g / l, especially in the range of 500 to 975 g / l, particularly in the range of 520 to 810 g / l, based on the total volume of the formulation, wherein the dicamba contains one or more of the above-mentioned minor products, and the relative amount thereof with respect to dicamba is in the range of 1% to 20% by weight, especially in the range of 1.5% to 15% by weight, particularly in the range of 2% to 10% by weight;

[0072] b) At least one organic solvent b) in an amount of 10 to 200 g / l, especially 20 to 100 g / l, particularly 25 to 60 g / l, selected from N-C2-C 15 -alkylpyrrolidones, wherein the alkyl group may be substituted with a hydroxyl group, and the solvent b) is preferably selected from N-C3-C 12 -alkylpyrrolidones, more particularly selected from N-C3-C8-alkylpyrrolidones, and the solvent b) especially comprises or is N-(n-butyl)pyrrolidone;

[0073] c) Optionally, an inorganic buffer in an amount of 50 to 300 g / l, especially 80 to 200 g / l, particularly 110 to 170 g / l, preferably selected from alkali metal carbonates, especially potassium carbonate, and

[0074] f) Water up to the total volume of the formulation, and the amount of water is especially as given above.

[0075] In particular, embodiments of groups (3), (3a) and (3b) relate to aqueous formulations of dicamba, especially aqueous SL formulations, which contain

[0076] a) A salt of dicamba with a water-miscible amine, in an amount of 450 to 1000 g / l, especially in the range of 500 to 975 g / l, particularly in the range of 520 to 810 g / l, based on the total volume of the formulation, wherein the dicamba contains one or more of the above-mentioned minor products, and the relative amount thereof with respect to dicamba is in the range of 1% to 20% by weight, especially in the range of 1.5% to 15% by weight, particularly in the range of 2% to 10% by weight;

[0077] b) from 10 to 200 g / l, in particular from 20 to 100 g / l, especially from 25 to 60 g / l of at least one organic solvent b), which is selected from the solvents of embodiment of group (1), wherein the solvent b) is selected from N-C3-C6-alkylpyrrolidones, wherein the alkyl is straight-chain, more particularly selected from N-C4-C5-alkylpyrrolidones, wherein the alkyl is straight-chain, and the solvent b) is especially N-(n-butyl)pyrrolidone;

[0078] c) from 50 to 300 g / l, in particular from 80 to 200 g / l, especially from 110 to 170 g / l of an inorganic buffer, which is preferably selected from alkali metal carbonates, especially potassium carbonate,

[0079] f) water up to the total volume of the formulation, and the amount of water is especially as given above.

[0080] Generally, the formulations of embodiment of group (3) have a pH in the range from pH 6.0 to pH 11.0, especially in the range from pH 6.5 to pH 10.5 or in the range from pH 7.0 to pH 10.2, as measured with a glass electrode in the undiluted aqueous formulation at 22 °C and 1 bar.

[0081] Embodiment of group 4 relates to an aqueous formulation, wherein the dicamba salt is the salt of dicamba and potassium. These salts are abbreviated hereinafter as dicamba-K. Dicamba-K is commercially available. It can be prepared by the reaction of the free acid form of dicamba with KOH. Dicamba-K generally refers to the 1:1 salt of the dicamba anion and potassium.

[0082] If not otherwise stated, the above disclosure regarding the type, amount thereof, concentration of the dicamba salt, type and amount of the minor components and amount of water applies to the embodiments of group 4.

[0083] Generally, the formulations of embodiment of group 4 have a pH in the range from pH 6.0 to pH 11.0, especially in the range from pH 6.5 to pH 10.5 or in the range from pH 7.0 to pH 10.2, as measured with a glass electrode in the undiluted aqueous formulation at 22 °C and 1 bar.

[0084] As an additional component, the aqueous formulations of the present invention may contain an additional component selected from additives d1) and d2) or a combination thereof with a solvent e) selected from C1-C6-alkyl lactates and C3-C6-lactones. In particular, the formulations of embodiment of group (4) may contain an additional component selected from additives d1) and d2) or a combination thereof with a solvent e) selected from C1-C6-alkyl lactates and C3-C6-lactones.

[0085] The additive d1) is commercially available. Typical products are those of the product series Pluriol E, Pluronic PE, Genapol PF, and Synperonic PE. The additive d1) can be prepared by the reaction of ethylene oxide and propylene oxide in a non-aqueous solvent by a ring-opening reaction. Generally, the additive d1) is prepared in two steps. In the first step, propylene glycol or dipropylene glycol is dissolved in a non-aqueous organic solvent, such as petroleum ether, and propylene oxide is added in gaseous or liquid form. Optionally, a catalyst is added to the reaction mixture to increase the reaction yield and the dispersibility of the reaction product. In the second step, ethylene oxide is added to the reaction mixture to produce the final additive of formula d1).

[0086] In one embodiment, R in formula (I) 1 and R 2 are H. In another embodiment, R in formula (I) 1 and R 2 are C1-C3-alkyl. In another embodiment, R in formula (I) 1 and R 2 are CH3.

[0087] The ratio (n + p) / m in formula (I) is generally at least 1:1, preferably at least 3:2. The ratio (n + p) / m in formula (I) is generally at most 10:1, preferably at most 8:1, more preferably at most 6:1. The ratio (n + p) / m in formula (I) is generally from 1:1 to 10:1, preferably from 1:1 to 9:1, more preferably from 3:2 to 7:1.

[0088] In the first embodiment PA-1 of the additive d1), the exponents n and p in formula (I) are each independently 20 to 100, preferably 30 to 80, more preferably 40 to 70, most preferably 40 to 60, and particularly preferably 45 to 55. In the same embodiment PA-1, the exponent m in formula (I) is 20 to 100, preferably 30 to 80, more preferably 40 to 70, and most preferably 50 to 60.

[0089] In the second embodiment PA-2 of the additive d1), the exponents n and p in formula (I) are each independently 50 to 100, preferably 60 to 80, and more preferably 65 to 75. In the same embodiment PA-2, the exponent m in formula (I) is 10 to 60, preferably 15 to 40, more preferably 20 to 40, and most preferably 25 to 35.

[0090] Generally, the weight-average molecular weight of additive d1) is from 1000 g / ml to 10000 g / ml, preferably from 2000 g / mol to 9000 g / mol. In the case of embodiment PA-1, the weight-average molecular weight of additive d1) is generally from 4000 g / mol to 8000 g / mol, preferably from 5000 g / mol to 7000 g / mol, more preferably from 5500 g / mol to 6500 g / mol. In the case of embodiment PA-2, the weight-average molecular weight of additive d1) is generally from 5000 g / mol to 10000 g / mol, preferably from 6000 g / mol to 9000 g / mol, more preferably from 7000 g / mol to 9000 g / mol, particularly preferably from 7500 g / mol to 8500 g / mol.

[0091] The formulations of the present invention, in particular the formulations of embodiment group 4, may contain additive d1) at a concentration of at least 1% by weight, preferably at least 3% by weight, more preferably at least 4% by weight, particularly preferably at least 5% by weight, based on the total weight of the aqueous formulation. The aqueous formulations of the present invention, in particular the formulations of embodiment group 4, may contain additive d1) at a concentration of at most 50% by weight, preferably at most 40% by weight, more preferably at most 30% by weight, most preferably at most 20% by weight, particularly preferably at most 10% by weight, most preferably at most 5% by weight, based on the total weight of the aqueous formulation. The aqueous formulations of the present invention, in particular the formulations of embodiment group 4, may comprise additive d1) at a concentration of from 1 to 25% by weight, preferably from 2 to 15% by weight, more preferably from 5 to 10% by weight, particularly preferably from 4 to 6% by weight. Generally, additive d1) is completely soluble in the formulations of the present invention at 20°C.

[0092] Additive d2) is a hyperbranched polycarbonate. The term "hyperbranched polycarbonate" refers to non-crosslinked polycarbonate macromolecules having hydroxyl and carbonate or carbamoyl chloride groups, which may be structurally and molecularly inhomogeneous. On the one hand, they can be synthesized starting from a central molecule in the same way as dendrimers, but unlike dendrimers, their branches have uneven chain lengths. Hyperbranched polymers thus differ from dendrimers (US 6,399,048). For the purposes of the present invention, hyperbranched polymers do not include dendrimers. On the other hand, hyperbranched polymers may also have a linear structure, with branched side functional groups, or as a combination of these two extremes, may include linear and branched molecular structural parts. For the definitions of dendrimers and hyperbranched polymers, also see P.J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, 2499.

[0093] "Hyperbranched" in the present invention refers to the degree of branching (DB), in other words, the ratio of the sum of the average number of dendritic linkages per molecule plus the average number of end groups to the sum of the average number of dendritic and linear linkages per molecule plus the average number of end groups, multiplied by 100, is 10% to 99.9%, preferably 20% to 99%, more preferably 20% to 95%. "Dendritic" in the present invention refers to a degree of branching of 99.9% - 100%. For the definition of the degree of branching, see H. Frey et al., Acta Polym. 1997, 48, 30.

[0094] One advantage of the present invention is that the additive d2) is a non-crosslinked polymer. For the purposes of this specification, "non-crosslinked" means that the degree of crosslinking present is less than 15% by weight, preferably less than 10% by weight, as determined by the insoluble portion of the polymer. The insoluble portion of the polymer can be determined by extracting for 4 hours in a Soxhlet apparatus with the same solvent used for gel permeation chromatography for determining the molecular weight distribution of the polymer, i.e., tetrahydrofuran, dimethylacetamide or hexafluoroisopropanol (depending on which solvent has better dissolving ability for the polymer), and weighing the remaining residue after drying to constant weight.

[0095] Hyperbranched polycarbonates can generally be obtained as follows

[0096] a) By reacting an organic carbonate (E) or a phosgene derivative with an alcohol (F1) having at least three hydroxyl groups to prepare a condensation product (K), and

[0097] b) Intermolecularly converting K into a hyperbranched polycarbonate,

[0098] The stoichiometric ratio of the OH groups to the carbonate or phosgene groups is selected such that K has on average i) one carbonate or carbamoyl chloride group and more than one OH group, or ii) one OH group and more than one carbonate or carbamoyl group. Polycarbonates are preferably obtained in this way.

[0099] The condensation product (K) can be prepared using an organic carbonate (E) or a phosgene derivative. Examples of suitable phosgene derivatives are phosgene, diphosgene or triphosgene, preferably phosgene. Organic carbonates are preferably used.

[0100] The general formula R 3 O[(CO)O] o R 3 The groups R in the organic carbonate (E) 3 are each independently a straight-chain or branched aliphatic, aromatic / aliphatic (araliphatic) or aromatic hydrocarbon group having 1 to 20 C atoms. Two groups R 3 can also be linked to each other to form a ring. Two groups R 3may be the same or different; they are preferably the same. The groups involved are preferably aliphatic hydrocarbon groups, more preferably straight-chain or branched alkyl groups having 1 to 5 C atoms, or substituted or unsubstituted phenyl groups. R 3 in this case is a straight-chain or branched, preferably straight-chain (cyclo)aliphatic, aromatic / aliphatic or aromatic, preferably (cyclo)aliphatic or aromatic, more preferably aliphatic hydrocarbon group having 1 to 20 C atoms, preferably 1 to 12, more preferably 1 to 6, very preferably 1 to 4 carbon atoms. Examples of such groups are methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, phenyl, o- or p-tolyl or naphthyl. Methyl, ethyl, n-butyl and phenyl are preferred. These groups R 3 may be the same or different; they are preferably the same. The group R 3 may also be linked to each other to form a ring. Examples of such divalent groups R 3 are 1,2-ethylene, 1,2-propylene and 1,3-propylene. Generally, the index o is an integer from 1 to 5, preferably 1 to 3, more preferably 1 to 2. The carbonate may preferably be a simple carbonate of the general formula R 3 O(CO)OR 3 i.e. the index o is 1 in this case.

[0101] Examples of suitable carbonates include aliphatic, aromatic / aliphatic or aromatic carbonates such as ethylene carbonate, 1,2- or 1,3-propylene carbonate, diphenyl carbonate, dimethylxylene carbonate, bisdimethylxylene carbonate, dinaphthyl carbonate, ethylphenyl carbonate, dibenzyl carbonate, dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, dipentyl carbonate, dihexyl carbonate, dicyclohexyl carbonate, diheptyl carbonate, dioctyl carbonate, didecyl carbonate or didodecyl carbonate. Examples of carbonates where n is greater than 1 include dialkyl dicarbonates such as di-tert-butyl dicarbonate, or trialkyl tricarbonates such as di-tert-butyl tricarbonate. A preferred aromatic carbonate is diphenyl carbonate. Preferred are aliphatic carbonates, more particularly those in which the groups contain 1 to 5 C atoms, such as dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, di-n-butyl carbonate or diisobutyl carbonate. Diethyl carbonate is particularly preferred.

[0102] Alcohols (F1) having at least three hydroxyl groups are generally aliphatic or aromatic alcohols, or mixtures of two or more different alcohols of this type. The alcohol (F1) can be branched or unbranched, substituted or unsubstituted, and has 3 to 26 carbon atoms. It is preferably an aliphatic alcohol. Examples of compounds having at least three OH groups include glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, trimethylolbutane, 1,2,4-butanetriol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, tris(hydroxymethyl)amine, tris(hydroxyethyl)amine, tris(hydroxypropyl)amine, pentaerythritol, diglycerol, triglycerol, polyglycerol, bis(trimethylolpropane), tris(hydroxymethyl)isocyanurate, tris(hydroxyethyl)isocyanurate, phloroglucinol, trihydroxytoluene, trihydroxydimethylbenzene, phloroglucides, hexahydroxybenzene, 1,3,5-benzenetriol, 1,1,1-tris(4'-hydroxyphenyl)methane, 1,1,1-tris(4'-hydroxyphenyl)ethane, saccharides such as glucose, sugar derivatives such as sorbitol, mannitol, diglycerol, threitol, erythritol, adonitol (ribitol), alitol (lyxitol), xylitol, dulcitol (galactitol), maltitol, isomaltitol or polyester alcohols. In addition, F1 can be a trifunctional or higher functional polyether alcohol based on an alcohol having at least three OH groups and C2-C 24 An alkylene oxide. The polyether alcohol contains generally 1 to 30, preferably 1 to 20, more preferably 1 to 10, most preferably 1 to 8 ethylene oxide and / or propylene oxide and / or isobutylene oxide molecules per hydroxyl group. Preferably, the polyether alcohol is based on an alcohol having at least 3 OH groups and 1 to 30 molecules of alkylene oxide, more preferably based on an alcohol having at least 3 OH groups and 5 to 20 molecules of propylene oxide.

[0103] The hyperbranched polycarbonate preferably contains such an alcohol (F1) which is a trifunctional or higher functional polyether alcohol based on an alcohol having at least three OH groups and C3-C 24 An alkylene oxide. Suitable alcohols having at least three OH groups are as described above, preferably glycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, pentaerythritol, more preferably glycerol or trimethylolpropane. Preferred C3-C 24 Alkylene oxides include propylene oxide, butylene oxide, pentylene oxide and mixtures thereof, more preferably propylene oxide. The trifunctional or higher functional polyether alcohol generally contains at least 1 to 30, preferably 2 to 30, more preferably 3 to 20 polymerized forms of C3-C 24 Alkylene oxide molecules. Particularly preferred alcohols (F1) are trifunctional polyether alcohols based on glycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol and / or pentaerythritol, and propylene oxide, wherein the polyether alcohol contains at least 3, preferably 3 to 30, more preferably 3 to 20 polymerized forms of propylene oxide molecules.

[0104] In addition to the alcohol (F1), the polycarbonate may also have a difunctional alcohol (F2) as a forming component, provided that the average OH functionality of all alcohols F used together is greater than 2. The alcohols (F1) and (F2) are hereinafter referred to together as (F). Suitable difunctional alcohols F2 include diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1,2-, 1,3- and 1,4-butanediol, 1,2-, 1,3- and 1,5-pentanediol, 1,6-hexanediol, 1,2- or 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,1-, 1,2-, 1,3- or 1,4-cyclohexanedimethanol, bis(4-hydroxycyclohexyl)methane, bis(4-hydroxycyclohexyl)ethane, 2,2-bis(4-hydroxycyclohexyl)propane, 1,1'-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, resorcinol, hydroquinone, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(hydroxymethyl)benzene, bis(hydroxymethyl)toluene, bis(p-hydroxyphenyl)methane, bis(p-hydroxyphenyl)ethane, 2,2-bis(p-hydroxyphenyl)propane, 1,1-bis(p-hydroxyphenyl)cyclohexane, dihydroxybenzophenone, difunctional polyether polyols based on ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, polytetrahydrofuran having a molar mass of 162 to 2000, polycaprolactone or polyester polyols based on diols and dicarboxylic acids. Preferred difunctional alcohols (F2) are difunctional polyether polyols based on ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, and polyester polyols based on diols and dicarboxylic acids.

[0105] The diol is used for fine-tuning the properties of the polycarbonate. If a difunctional alcohol is used, the ratio of the difunctional alcohol (F2) to the at least trifunctional alcohol (F1) is determined by those skilled in the art according to the desired properties of the polycarbonate. Generally, based on the total weight of all alcohols (F1) and (F2), the amount of alcohol (F2) is 0 to 50 mol%. This amount is preferably 0 to 35 mol%, more preferably 0 to 25 mol%, and most preferably 0 to 10 mol%.

[0106] The reaction of phosgene, diphosgene or triphosgene with an alcohol or alcohol mixture is usually carried out while eliminating hydrogen chloride; the reaction of a carbonate with an alcohol or alcohol mixture is carried out while eliminating a monofunctional alcohol or phenol from the carbonate molecule to obtain the highly functional and highly branched polycarbonate of the present invention.

[0107] After this reaction, i.e. without any further modification, the hyperbranched polycarbonates have highly functional end groups containing hydroxyl and carbonate or carbamoyl chloride groups. Highly functional polycarbonates are understood in the context of the present invention to mean products which, in addition to the carbonate groups forming the polymer backbone, have at least three, preferably at least four, more preferably at least six functional groups at the terminal or lateral positions. The functional groups are carbonate or carbamoyl chloride groups and / or OH groups. In principle, there is no upper limit to the number of terminal or laterally attached functional groups, but products with an extremely high number of functional groups may have unwanted properties, such as high viscosity or poor solubility. The highly functional polycarbonates according to the invention generally have no more than 500 terminal or laterally attached functional groups, preferably no more than 100 terminal or laterally attached functional groups.

[0108] In the preparation of the highly functional polycarbonates, the ratio of the compound containing OH groups to phosgene or carbonate (A) must be adjusted so that the simplest condensation product obtained (hereinafter referred to as condensation product (K)) contains on average i) one carbonate or carbamoyl chloride group and more than one OH group, or ii) one OH group and more than one carbonate or carbamoyl chloride group, preferably on average i) one carbonate or carbamoyl chloride group and at least two OH groups, or ii) one OH group and at least two carbonate or carbamoyl chloride groups.

[0109] In order to fine-tune the properties of polycarbonate, it is also desirable to use at least one difunctional carbonyl reactive compound (E1). This is understood to refer to those compounds with two carbonates and / or carboxyl groups. The carboxyl group can be a carboxylic acid, phosgene, carboxylic anhydride or carboxylate, preferably carboxylic anhydride or carboxylate, more preferably carboxylate. If such a difunctional compound (E1) is used, the ratio of (E1) to carbonate or phosgene (E) is determined by those skilled in the art according to the desired properties of polycarbonate. Generally speaking, the amount of the difunctional compound (E1) is 0 to 40 mol% based on the total weight of all carbonates / phosgene (E) and compound (E1). The amount is preferably 0 to 35 mol%, more preferably 0 to 25 mol%, and very preferably 0 to 10 mol%. Examples of compounds (E1) are dicarbonates or dicarbamoyl chlorides of diols, examples of diols being ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,1-dimethylethane-1,2-diol, 2-butyl-2-ethyl-1,3-propylene glycol, 2-ethyl-1,3-propylene glycol, 2-methyl-1,3-propylene glycol, neopentyl glycol, neopentyl glycol hydroxypivalate, 1,2-, 1,3- or 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, bis(4-hydroxycyclohexane)-1,2-diol, 1,3-diol, 1,4-diol, 1,6-hexanediol, 1,10-decanediol, 1,2-diol, 1,3-diol, 1,1-diol, 1,2-diol, 1,3 ...3-diol, 1,4-diol, 1,6-hexanediol, 1,10-decanediol, 1,2-diol, 1,3-diol, 1,3-diol, 1,1-diol, 1,2-diol, 1,3-diol, 1,3-diol, 1,3- 1,2-, 1,3- or 1,4-cyclohexanediol, cyclooctanediol, norbornanediol, pinanediol, decalindiol, 2-ethyl-1,3-hexanediol, 2,4-diethyloctane-1,3-diol, hydroquinone, bisphenol A, bisphenol F, bisphenol B, bisphenol S, 2,2-bis(4-hydroxycyclohexyl)propane, 1,1-, 1,2-, 1,3- and 1,4-cyclohexanedimethanol, and 1,2-, 1,3- or 1,4-cyclohexanediol. These compounds can be prepared, for example, by reacting the diols with an excess of, for example, the above-mentioned carbonate R 3 O(CO)OR 3 or chlorocarbonate reaction, so that the dicarbonate thus obtained is substituted on both sides with groups R 3 O(CO)-substitution. Another possibility is to react the diols first with phosgene to give the corresponding chlorocarbonates of the diols and then to react these esters with alcohols.

[0110] Further compounds (E1) are dicarboxylic acids, esters of dicarboxylic acids, preferably methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl or tert-butyl esters, more preferably methyl, ethyl or n-butyl esters. Examples of such dicarboxylic acids are oxalic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid or tetrahydrophthalic acid, suberic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, dimerized fatty acids, their isomers and their hydrogenation products.

[0111] The simplest structure of the condensation product (K) illustrated by the reaction of a carbonate (E) with a diol or polyol (F) gives the arrangement XY q or Y q X, where X is a carbonate or carbamate group, Y is a hydroxyl group, and the exponent q is generally an integer greater than 1 to 6, preferably greater than 1 to 4, more preferably greater than 1 to 3. The reactive group generated as a single group is hereinafter generally referred to as the "focal group".

[0112] If, for example, the molar reaction ratio is 1:1 in the preparation of the simplest condensation product (K) from a carbonate and a diol, the average result is an XY-type molecule of the general formula (II).

[0113]

[0114] In the case of preparing the condensation product (K) from a carbonate and a triol with a molar reaction ratio of 1:1, the average result is an XY2-type molecule of the general formula (III). The focal group here is the carbonate group.

[0115]

[0116] When preparing the condensation product (K) from a carbonate and a tetrol still with a molar reaction ratio of 1:1, the average result is an XY3-type molecule of the general formula (IV). The focal group here is the carbonate group.

[0117]

[0118] In formulas (II) to (IV), R 3 is as defined for the organic carbonate (E), and R 4 is an aliphatic or aromatic group.

[0119] The condensation product (K) can also be prepared, for example, from a carbonate and a triol, as shown in the general formula (V), where the reaction ratio on a molar basis is 2:1. The average result here is an X2Y-type molecule, and the focal group here is the OH group. In formula (V), R 3 and R 4 are defined as above in formulas (II) to (IV).

[0120]

[0121] If a bifunctional compound, such as a dicarbonate or a diol, is additionally added to the components, this results in chain extension, as shown, for example, in the general formula (VI). The average result is again an XY2-type molecule, and the focal group is the carbonate group.

[0122]

[0123] In formula (VI), R 5 is an aliphatic or aromatic group, and R 3 and R 4 are defined as described above.

[0124] In formula (VI), R 5 is an aliphatic or aromatic group, and R 3 and R 4 are defined as described above.

[0125] It is also possible to use two or more condensation products (K) for the synthesis. In this case, on the one hand, two or more alcohols and / or two or more carbonates can be used. In addition, by selecting the ratio of the alcohol and carbonate or phosgene used, it is possible to obtain a mixture of different condensation products with different structures. This can be illustrated by the reaction of a carbonate with a triol. If the starting products are used in a 1:1 ratio, as shown in (III), the molecule XY2 is obtained. If the starting products are used in a 2:1 ratio, as shown in (V), the molecule X2Y is obtained as a result. A mixture of the molecules XY2 and X2Y is obtained at ratios between 1:1 and 2:1.

[0126] The stoichiometric ratio of components (E) and (F) is usually selected so that the resulting condensation product (K) contains one carbonate or carbamoyl chloride group and more than one OH group, or one OH group and more than one carbonate or carbamoyl chloride group. This is achieved in the first case by a stoichiometric ratio of 1 mole of carbonate group: > 2 moles of OH groups, for example a stoichiometric ratio of 1:2.1 to 8, preferably 1:2.2 to 6, more preferably 1:2.5 to 4, very preferably 1:2.8 to 3.5. In the second case, it is achieved by a stoichiometric ratio of > 1 mole of carbonate group: < 1 mole of OH groups, for example a stoichiometric ratio of 1:0.1 to 0.48, preferably 1:0.15 to 0.45, more preferably 1:0.25 to 0.4, very preferably 1:0.28 to 0.35.

[0127] The preparation of additive d2) is described in WO2010 / 130599, particularly preferably on pages 13, line 5 to page 16, line 25 and the synthesis examples.

[0128] Hyperbranched polycarbonates generally have a glass transition temperature of less than 50 °C, preferably less than 30 °C, more preferably less than 10 °C. The OH value is generally at least 30 mg KOH / g, preferably between 50 and 250 mg / g. The weight-average molar weight M w is generally between 1000 and 150 000, preferably between 1500 and 100 000 g / mol, and the number-average molar weight M nBetween 500 and 50,000, preferably between 1,000 and 40,000 g / mol.

[0129] The hyperbranched polycarbonate is attached to a linear polymer containing polyethylene glycol. Examples of polyethylene glycol are polyethylene glycol or polyethylene glycol monoalkyl ether, which has a number-average molar mass M of 200 to 10,000 g / mol, preferably 300 - 2,000 g / mol. n . The polyethylene glycol is preferably polyethylene glycol mono-C1-C 18 -alkyl ether, especially polyethylene glycol monomethyl ether. The molar ratio of the hyperbranched polycarbonate to the linear polymer is generally in the range of 1:1 to 1:100, preferably 1:1 to 1:50, more preferably 1:1 to 1:25.

[0130] Generally, the linear polymer is attached to the polycarbonate via a linker. Suitable functionalizing reagents for covalent attachment via the linker are hydroxycarboxylic acids, aminocarboxylic acids, hydroxy sulfonic acids, hydroxy sulfates, amino sulfonic acids or amino sulfates, hydroxylamines (such as diethanolamine), polyamines (e.g., diethylenetetraamine) or polyols (e.g., glycerol, trimethylolpropane, pentaerythritol). Preferred linkers for this purpose are the following polyisocyanates, preferably diisocyanates, more preferably aliphatic diisocyanates (such as hexamethylene diisocyanate and isophorone diisocyanate).

[0131] The preferred diisocyanates are aliphatic diisocyanates (such as hexamethylene diisocyanate and isophorone diisocyanate). Generally, the linker is first covalently bonded to the terminal OH-groups of the linear polymer, and then the polymer containing the linker is coupled to the hyperbranched polycarbonate. The reaction of the linear polymer with the diisocyanate is described in WO2010 / 130599, p.23, l.33 to p.24, l.42.

[0132] Alternatively, the linear polymer can be generated by direct alkoxylation of the polycarbonate as described in WO2011069895. The direct alkoxylation can be carried out by reaction with ethylene oxide or a mixture of ethylene oxide and C3-C5 epoxides. If the alcohol (F1) is a higher functionality polyether alcohol based on an alcohol having at least three OH groups and C3-C 24 epoxides, the weight ratio of the oligomeric or polymeric C3-C 24 epoxides plus C3-C5 epoxides to ethylene oxide is 3:1 to 1:3.

[0133] The molar ratio of the hyperbranched polycarbonate to the linear polymer is 1:1 to 1:25, preferably 1:2 to 1:15. The reaction continues until the isocyanate value drops to zero.

[0134] Additives d1) and d2) contain certain monomers in polymeric form. Although traces of unreacted monomers may still be present in the polymer, they are substantially monomer-free. Throughout this specification, the terms "containing monomer [x] in polymeric form" and "containing monomer [x]" have the same meaning.

[0135] The aqueous formulations of the present invention may contain additive d2) at a concentration of at least 0.5% by weight, preferably at least 1% by weight, more preferably at least 2% by weight, based on the total weight of the agrochemical composition. The aqueous formulations of the present invention may contain additive d2) at a concentration of at most 30% by weight, preferably at most 25% by weight, more preferably at most 20% by weight, most preferably at most 18% by weight, particularly preferably at most 17.5% by weight, based on the total weight of the agrochemical composition. The aqueous formulations of the present invention, in particular the formulations of embodiment group 4, may contain additive d2) at a concentration of 0.5 to 25% by weight, preferably 1 to 25% by weight, more preferably 1 to 20% by weight, most preferably 2 to 20% by weight, based on the total weight of the aqueous formulation.

[0136] The aqueous formulations of the present invention, in particular the formulations of embodiment group 4, may contain additive d2) at a concentration of at least 5 g / l, preferably at least 10 g / l, more preferably at least 25 g / l. The aqueous formulations of the present invention may contain additive d2) at a concentration of at most 350 g / l, preferably at most 300 g / l, more preferably at most 250 g / l. The aqueous formulations of the present invention may contain additive d2) at a concentration of 1 to 350 g / l, preferably 5 to 250 g / l, more preferably 25 to 250 g / l.

[0137] Generally, additive d2) is completely soluble in the aqueous formulations of the present invention at 20 °C.

[0138] The aqueous formulations of the present invention, in particular the formulations of embodiment group 4, may further contain a solvent selected from C1-C6-alkyl lactates and C3-C6-lactones and combinations thereof as component e). The terms component e) and solvent e) are used synonymously.

[0139] In one embodiment, the aqueous formulations of the present invention, in particular the formulations of embodiment group 4, contain a solvent selected from C1-C6-alkyl lactates, preferably C1-C3-alkyl lactates, more preferably ethyl lactate or n-propyl lactate. In one embodiment, the solvent is selected from methyl lactate, ethyl lactate, propyl lactate, butyl lactate, pentyl lactate and hexyl lactate. In another embodiment, the solvent is ethyl lactate. In another embodiment, the solvent is n-propyl lactate. In another embodiment, the solvent is methyl lactate. In another embodiment, the solvent is pentyl lactate. In another embodiment, the solvent is hexyl lactate.

[0140] In a further set of preferred embodiments, the aqueous formulations of the invention, in particular those of embodiment group 4, contain a solvent e) selected from C3-C6-lactones, preferably C4-C6-lactones. In one embodiment, the solvent e) is γ-butyrolactone. In another embodiment, the solvent e) is ε-caprolactone. In another embodiment, the solvent e) is β-propiolactone.

[0141] The aqueous formulations of the invention, in particular those of embodiment group 4, may contain the solvent e) in a concentration in the range from 1 to 25% by weight, in particular in the range from 1 to 20% by weight, preferably in the range from 1 to 18% by weight and in the range from 2 to 17% by weight, based on the total weight of the formulation.

[0142] If no other additives d1) or d2) are present in the aqueous formulations of the invention, the total concentration of solvents b) and e) is generally at least 2% by weight, preferably at least 2.5% by weight, more preferably at least 3% by weight, most preferably at least 4% by weight, based on the total weight of the aqueous formulation of the invention. If no other additives d1) or d2) are present in the aqueous formulations of the invention, the total concentration of solvents b) and e) is generally from 2 to 25% by weight, more preferably from 3 to 20% by weight, most preferably from 4 to 18% by weight, based on the total weight of the aqueous formulation of the invention.

[0143] Correspondingly, if no other additives d1) or d2) are present in the aqueous formulations of the invention, the total concentration of solvents b) and e) is generally at least 15 g / l, preferably at least 20 g / l, more preferably at least 25 g / l. If no other additives d1) or d2) are present in the aqueous formulations of the invention, the total concentration of solvents b) and e) is generally from 10 to 250 g / l, in particular from 15 to 200 g / l, especially from 20 to 180 g / l, based on the total volume of the formulation.

[0144] In a specific set of embodiments, in particular in a subgroup of embodiment group 4, the solvent e) is a C3-C6-lactone, preferably γ-butyrolactone. In this set of embodiments, the concentration of the solvent c) is generally at least 10 g / l, preferably at least 20 g / l, more preferably at least 25 g / l, most preferably at least 50 g / l, most preferably at least 80 g / l; and the concentration of adjuvant e) is at most 300 g / l, preferably at most 250 g / l, more preferably at most 200 g / l, based on the total volume of the aqueous formulation.

[0145] In another set of embodiments, the aqueous formulations of the invention, in particular those of embodiments 3, 3a and 3b, do not contain the solvent e) or contain the solvent e) in an amount of not more than 80 g / l, in particular not more than 50 g / l, preferably not more than 10 g / l, especially not more than 1 g / l, based on the total volume of the aqueous formulation.

[0146] In another set of embodiments, the aqueous formulations of the present invention, particularly those of embodiments of groups 3, 3a, and 3b, do not contain d) or contain no more than 10 g / l, particularly no more than 5 g / l, preferably no more than 2 g / l, especially no more than 1 g / l of additive d) based on the total volume of the aqueous formulation.

[0147] In another set of embodiments, the aqueous formulations of the present invention do not contain γ-butyrolactone or contain no more than 80 g / l, particularly no more than 50 g / l, preferably no more than 10 g / l, especially no more than 1 g / l of γ-butyrolactone based on the total volume of the aqueous formulation.

[0148] In one embodiment, the aqueous formulation of the present invention comprises dicamba-K, N-C1-C 15 -alkylpyrrolidone and additive d1). In another embodiment, the aqueous formulation of the present invention comprises dicamba-K, N-octylpyrrolidone and additive d1), preferably wherein additive d1) is defined as in embodiment PA-1 or PA-2, more preferably wherein additive d1) is defined as in embodiment PA-2. In another embodiment, the aqueous formulation of the present invention comprises dicamba-K, N-butylpyrrolidone and additive d1), preferably wherein additive d1) is defined as in embodiment PA-1 or PA-2, more preferably wherein additive d1) is defined as in embodiment PA-2. In another embodiment, the aqueous formulation of the present invention comprises dicamba-K, N-dodecylpyrrolidone and additive d1), preferably wherein additive d1) is defined as in embodiment PA-1 or PA-2, more preferably wherein additive d1) is defined as in embodiment PA-2.

[0149] In one embodiment, the aqueous formulation of the present invention comprises dicamba-K, solvent b), C3-C6-lactone and additive d1). In another embodiment, the aqueous formulation of the present invention comprises dicamba-K, solvent b), γ-butyrolactone and additive d1), preferably wherein additive d1) is defined as in embodiment PA-1 or PA-2, more preferably wherein additive d1) is defined as in embodiment PA-2. In another embodiment, the aqueous formulation of the present invention comprises dicamba-K, solvent b), ε-caprolactone and additive d1), preferably wherein additive d1) is defined as in embodiment PA-1 or PA-2, more preferably wherein additive d1) is defined as in embodiment PA-2.

[0150] In one embodiment, the aqueous formulation of the present invention comprises dicamba-K, N-C1-C 15-alkylpyrrolidone and additive d2). In another embodiment, the aqueous formulation of the present invention comprises dicamba-K, N-octylpyrrolidone and additive d2), wherein additive d2) is preferably a hyperbranched polycarbonate linked to a polyethylene glycol mono-C1-C 18 -alkyl ether, more preferably wherein the hyperbranched polycarbonate is linked to polyethylene glycol monomethyl ether, and most preferably wherein additive d2) is a hyperbranched polycarbonate linked to polyethylene glycol monomethyl ether via a linker.

[0151] In another embodiment, the aqueous formulation of the present invention comprises dicamba-K, N-butylpyrrolidone and additive d2), wherein additive d2) is preferably a hyperbranched polycarbonate linked to a polyethylene glycol mono-C1-C 18 -alkyl ether, more preferably wherein the hyperbranched polycarbonate is linked to polyethylene glycol monomethyl ether, and most preferably wherein additive d2) is a hyperbranched polycarbonate linked to polyethylene glycol monomethyl ether via a linker.

[0152] In another embodiment, the aqueous formulation of the present invention comprises dicamba-K, N-dodecylpyrrolidone and additive d2), wherein additive d2) is preferably a hyperbranched polycarbonate linked to a polyethylene glycol mono-C1-C 18 -alkyl ether, more preferably wherein the hyperbranched polycarbonate is linked to polyethylene glycol monomethyl ether, and most preferably wherein additive d2) is a hyperbranched polycarbonate linked to polyethylene glycol monomethyl ether via a linker.

[0153] In another embodiment, the aqueous formulation of the present invention comprises dicamba-K, solvent b), a C3-C6-lactone and additive d2), wherein additive d2) is preferably a hyperbranched polycarbonate linked to a polyethylene glycol mono-C1-C 18 -alkyl ether, more preferably wherein the hyperbranched polycarbonate is linked to polyethylene glycol monomethyl ether, and most preferably wherein additive d2) is a hyperbranched polycarbonate linked to polyethylene glycol monomethyl ether via a linker.

[0154] In another embodiment, the aqueous formulation of the present invention comprises dicamba-K, solvent b), γ-butyrolactone and additive d2), wherein additive d2) is preferably a hyperbranched polycarbonate linked to a polyethylene glycol mono-C1-C 18 -alkyl ether, more preferably wherein the hyperbranched polycarbonate is linked to polyethylene glycol monomethyl ether, and most preferably wherein additive d2) is a hyperbranched polycarbonate linked to polyethylene glycol monomethyl ether via a linker.

[0155] If the formulation of the present invention contains solvent e), especially a C3-C6-lactone, solvent e) and solvent b) N-C2-C 15The weight ratio of -alkylpyrrolidone is usually in the range of 5:1 to 1:5, especially in the range of 1:1 to 1:3.

[0156] If the aqueous formulation of the present invention, especially the aqueous formulation of Embodiment Group 4, contains at least one additional component selected from Additive d2, Additive d2), and Solvent e), the total concentration of Solvent b), Additive d2, Additive d2), and Solvent e) is usually at least 60 g / l, especially at least 80 g / l, particularly at least 100 g / l. The total concentration of Solvent b), Additive d2, Additive d2), and Solvent e) can be at most 400 g / l, especially not more than 250 g / l, particularly not more than 230 g / l.

[0157] If the formulation contains Additive d1), the weight ratio of Additive d2) to the total amount of Solvent b) and e) is usually in the range of 20:1 to 1:20, especially in the range of 10:1 to 1:10, particularly in the range of 5:1 to 1:5 or in the range of 2:1 to 1:3.

[0158] If the formulation contains Additive d2), the weight ratio of Additive d2) to the sum of Solvent b) and e) is usually in the range of 20:1 to 1:20, especially in the range of 10:1 to 1:10, particularly in the range of 8:1 to 1:8.

[0159] The aqueous formulation of the present invention may contain one or more additional cosolvents different from Solvent b) and e). Suitable cosolvents are those miscible with water up to at least 1:1, preferably at least 2:1, more preferably at least 4:1 cosolvent / water ratio. Suitable cosolvents are alcohols such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; diols; DMSO; ketones such as heptanone, cyclohexanone; esters such as carbonates, fatty acid esters, fatty acids; phosphonates; amines; amides such as fatty acid dimethylamide; and mixtures thereof. The concentration of the cosolvent in the formulation usually does not exceed 5% by weight, especially 2% by weight or 1% by weight. In particular, the formulation of the present invention does not contain additional cosolvents or contains less than 1% by weight of cosolvent.

[0160] The formulations of the present invention can be prepared in a manner analogous to known methods as described, for example, in Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. Generally, the formulations of the present invention are made by mixing the dicamba salt with water and at least one solvent b) and any additional components optionally included in the formulation. The components can be mixed in any order. The mixing is generally achieved by stirring, shaking, homogenizing, etc. Generally, the dicamba salt is used as an aqueous concentrate obtained from the production site and is mixed with the other components in any order.

[0161] The aqueous formulations of the present invention can be co-formulated with additional pesticides. Accordingly, the present invention also relates to co-formulations, in which the additional pesticides are included in the formulations of the present invention.

[0162] The term "pesticide" refers to at least one active substance selected from fungicides, insecticides, nematicides, herbicides, safeners, biopesticides, and / or plant growth regulators. In one embodiment, the pesticide is an insecticide. In another embodiment, the pesticide is a fungicide. In yet another embodiment, the pesticide is a herbicide. Those skilled in the art are familiar with such pesticides, which can be found, for example, in Pesticide Manual, 16th Ed. (2013), The British Crop Protection Council, London. Suitable insecticides are insecticides selected from the following classes: carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosyns, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds, nereistoxin analogs, benzoylureas, diacylhydrazines, METI acaricides, and insecticides such as chloropicrin, pymetrozine, flonicamid, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorofenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or derivatives thereof. Suitable fungicides are fungicides selected from the following classes: dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic diamides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethyl phosphonates, ethylaminothiazole carboxamides, guanidines, hydroxy-(2-amino)pyrimidines, hydroxyanilines, imidazoles, imidazolinones, inorganic substances, isobenzofuranones, methoxyacrylates, methoxycarbamates, morpholines, N-phenylcarbamates, oxazolidinediones, oxime acetates, oxime acetamides, peptide pyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, thiophosphates, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridylmethyl benzamides, pyrimidinamines, pyrimidines, pyrimidinone hydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfonamides, amidosulfonyltriazoles, thiazole carboxamides, thiocarbamates, thiophanates, thiophene carboxamides, toluamides, triphenyltin compounds, triazines, triazoles.Suitable herbicides are herbicides selected from the following classes: acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofurans, benzoic acids, benzothiadiazinones, bipyridyls, carbamates, chloroacetamides, chloro-carboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenols, diphenyl ethers, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, picolinic acids, picolinamides, pyrimidinediones, pyrimidinyl(thio)benzoates, quinolinic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazoloformamides, triazolo-pyrimidines, triones, uracils, ureas. Examples of herbicides are glyphosate, glufosinate, paraquat, diquat, imazamox, 2,4-dichlorophenoxyacetic acid, clopyralid, picloram, fluroxypyr, imazapyr, imazapic, triclopyr, and pyroxasulfone.

[0163] In one embodiment, the additional herbicide is glyphosate. In a further embodiment, the herbicide is 2,4-dichlorophenoxyacetic acid. In a further embodiment, the herbicide is pyroxasulfone. In a further embodiment, the herbicide is imazamox. In a further embodiment, the herbicide is selected from glyphosate, glufosinate, paraquat, diquat, imazamox, 2,4-dichlorophenoxyacetic acid. In a further embodiment, the herbicide is selected from glyphosate, glufosinate, imazamox, 2,4-dichlorophenoxyacetic acid.

[0164] In a particular set of embodiments, the additional herbicide is selected from glyphosate, glufosinate, and mixtures thereof.

[0165] Preferably, the additional pesticide has a water solubility at 20 °C of at least 10 g / l, in particular at least 50 g / l.

[0166] The aqueous co-formulation may comprise an additional pesticide at a concentration of at least 10% by weight, preferably at least 20% by weight, more preferably at least 30% by weight, more preferably at least 40% by weight, most preferably at least 50% by weight, based on the total weight of the agrochemical composition. The agrochemical composition may comprise an additional pesticide in an amount of 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight, based on the total weight of the agrochemical composition.

[0167] The ratio of dicamba salt to the additional pesticide can be from 10:1 to 1:10, preferably from 5:1 to 1:5, more preferably from 2:1 to 1:2. The ratio of dicamba-K to the additional pesticide can be at least 1:1, preferably at least 3:1, more preferably 4:1.

[0168] The co-formulation may further contain one or more conventional auxiliaries, depending on the type of co-formulation. Conventional auxiliaries are liquid carriers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, wetting agents, repellents, attractants, feeding stimulants, solubilizers, fungicides, antifreeze agents, defoamers, colorants, tackifiers and binders.

[0169] Suitable surfactants include anionic surfactants and nonionic surfactants. Suitable anionic surfactants are the alkali metal, alkaline earth metal or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, α-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes 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 alkyl carboxylates and carboxylated alcohol or alkylphenol ethoxylates.

[0170] Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, glycosyl surfactants, polymeric surfactants and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters that have been alkoxylated with 1 to 50 equivalents of alkylene oxide. For alkoxylation, ethylene oxide and / or propylene oxide can be used, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or glycerol monoesters. Examples of glycosyl surfactants are sorbitan, ethoxylated sorbitan, sucrose esters and glucose esters or alkyl polyglucosides. Examples of polymeric surfactants are homopolymers or copolymers of vinylpyrrolidone, vinyl alcohol or vinyl acetate.

[0171] Suitable adjuvants are compounds which have negligible pesticidal activity per se or even no pesticidal activity and improve the biological performance of the dicamba salts at the target site. Examples are surfactants, mineral or vegetable oils and other auxiliaries. Further examples are listed in Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, Chapter 5.

[0172] Suitable thickeners are polysaccharides (such as xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates and silicates.

[0173] Suitable fungicides are bronopol and isothiazolone derivatives, such as alkyl isothiazolones and benzisothiazolones.

[0174] Suitable antifreezes are ethylene glycol, propylene glycol, urea and glycerol.

[0175] Suitable defoamers are silicones, salts of long-chain alcohols and fatty acids.

[0176] Suitable colorants (such as red, blue or green) are poorly water-soluble pigments and water-soluble dyes. Examples are inorganic colorants (such as iron oxide, titanium oxide, Prussian blue) and organic colorants (such as alizarin, azo and phthalocyanine colorants).

[0177] Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylates, biological or synthetic waxes, and cellulose ethers.

[0178] In addition, formulations of other pesticides (such as herbicides, insecticides, fungicides, growth regulators, safeners) and / or adjuvants and / or additional additives such as fertilizers or micronutrients can be added to the formulations of the present invention immediately before use, i.e., as a tank mix. These reagents can be mixed with the composition according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

[0179] The user generally applies the formulations of the present invention from a pre-dosage device, a knapsack sprayer, a spray tank, a spray plane or an irrigation system. For this purpose, the formulations of the present invention are formulated with water, optionally a buffer and / or other auxiliaries to the desired application concentration and thereby obtain a ready-to-use spray liquid or agrochemical composition according to the present invention. Generally, 20 to 2000 liters, preferably 50 to 400 liters of the ready-to-use spray liquid are applied per hectare of agricultural useful area.

[0180] According to one embodiment, the user can mix the individual components of the composition according to the present invention himself in a spray tank, such as parts of a kit or parts of a binary or ternary mixture, and can optionally add further auxiliaries.

[0181] In a further embodiment, the individual components or partially premixed components of the formulation according to the invention can be mixed by the user in a spray can, for example components comprising dicamba-K and / or a solvent and / or a polymer, and further adjuvants and additives can be added as appropriate. In a further embodiment, the individual components or partially premixed components of the agrochemical composition, for example components comprising dicamba-K and / or a solvent and / or a polymer, can be applied together (for example after tank mixing) or successively.

[0182] The invention further relates to a method for controlling unwanted vegetation and / or regulating plant growth, in which the agrochemical composition acts on the respective pests, their environment or the crop to be protected against the respective pests, acts on the soil and / or acts on the crop and / or acts on their environment.

[0183] If controlling unwanted vegetation, the formulation of the invention is generally applied to the crop to be protected against infestation by unwanted vegetation, to the soil and / or to the crop and / or to their environment. In one embodiment, the agrochemical composition is applied to the soil.

[0184] In another embodiment, the agrochemical composition is applied to the leaf surface.

[0185] The formulation of the invention is generally applied in a pesticidally effective amount of a dicamba salt. The term "effective amount" means an amount of the dicamba salt sufficient to control the pest species or protect the material and not cause substantial damage to the crop. Such amounts can vary widely and depend on various factors such as the pest species, the crop or material being treated and the climatic conditions.

[0186] When used for plant protection, depending on the type of desired effect, the amount of dicamba salt applied is 0.01 to 2 kg / ha, preferably 0.05 to 1.5 kg / ha, more preferably 0.1 to 1.3 kg / ha, especially 0.2 to 1.2 kg / ha, calculated as dicamba in free acid form.

[0187] Depending on the application method involved, the agrochemical composition can be used on crops to eliminate unwanted vegetation. Examples of suitable crops are as follows:

[0188] Onion (Allium cepa), pineapple (Ananas comosus), peanut (Arachis hypogaea), asparagus (Asparagus officinalis), oat (Avena sativa), beet (Beta vulgaris spec. altissima), Beta vulgaris spec. rapa, rapeseed (Brassica napus var. napus), rutabaga (Brassica napus var. napobrassica), turnip (Brassica rapa var. silvestris), cabbage (Brassica oleracea), black mustard (Brassica nigra), tea plant (Camellia sinensis), safflower (Carthamus tinctorius), pecan (Carya illinoinensis), lemon (Citrus limon), sweet orange (Citrus sinensis), coffee (Coffea arabica) (Coffea canephora, Coffea liberica), cucumber (Cucumis sativus), Bermuda grass (Cynodon dactylon), carrot (Daucus carota), oil palm (Elaeis guineensis), wild strawberry (Fragaria vesca), soybean (Glycine max), upland cotton (Gossypium hirsutum), (tree cotton (Gossypium arboreum), levant cotton (Gossypium herbaceum), Gossypium vitifolium), sunflower (Helianthus annuus), rubber tree (Hevea brasiliensis), barley (Hordeum vulgare), hops (Humulus lupulus), sweet potato (Ipomoea batatas), walnut (Juglans regia), lentil (Lens culinaris), flax (Linum usitatissimum), tomato (Lycopersicon lycopersicum), Malus spec., cassava (Manihot esculenta), alfalfa (Medicago sativa), Musa spec., tobacco (Nicotiana tabacum) (N. rusticarustica)), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pistacia vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Prunus armeniaca, Prunus cerasus, Prunus dulcis and Prunus domestica, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Sinapis alba, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticale, Triticum durum, Vicia faba, Vitis vinifera, Zea mays. Particularly preferred crops are cereals, maize, soybeans, paddy rice, rapeseed, cotton, potatoes, peanuts or permanent crops.

[0189] The compositions according to the invention can also be used in transgenic crops. The term "crop" as used herein thus also includes transgenic crops modified by mutagenesis or genetic engineering, thereby providing new traits to the plant or altering existing traits. The term "transgenic crop" is understood to mean a plant that has been modified by the use of recombinant DNA technology to include inserted DNA sequences that are not native to the genome of the crop species or that exhibit deletions of DNA native to the genome of the species, where the modification cannot be readily obtained by conventional breeding, mutagenesis or natural recombination alone. Typically, a particular transgenic crop is genetically obtained from an ancestral crop plant (the genome of which has been directly treated with recombinant DNA technology) through natural breeding or propagation processes with its genetic modification. Typically, one or more genes are integrated into the genetic material of the transgenic crop to improve certain properties of the crop. Such genetic modifications also include, but are not limited to, targeted post-translational modifications of proteins, oligopeptides or polypeptides, such as amino acid mutations that allow, reduce or promote glycosylation or polymer addition, such as isoprenylation, acetyl farnesylation or PEG moiety attachment.

[0190] Mutagenesis includes random mutagenesis techniques using X-rays or mutagenic chemicals, and also includes directed mutagenesis techniques to create mutations at specific loci in the plant genome. Directed mutagenesis techniques typically use oligonucleotides or proteins such as CRISPR / Cas, zinc finger nucleases, TALENs or meganucleases to achieve a directed effect.

[0191] Genetic engineering typically uses recombinant DNA technology to create modifications in the plant genome that cannot be readily obtained by conventional breeding, mutagenesis or natural recombination in nature. Typically, one or more genes are integrated into the genome of the plant to add or improve traits. These integrated genes are also referred to as transgenes in the art, and plants containing these transgenes are called transgenic plants. Plant transformation methods typically produce several transformation events, which differ in the genomic loci into which the transgene has been integrated. A plant containing a particular transgene at a particular genomic locus is typically described as containing a particular "event", which is referred to by a specific event name. Traits that have been introduced into the plant or modified particularly include herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions such as drought.

[0192] Herbicide tolerance has been created by the use of mutagenesis as well as by the use of genetic engineering. Plants that have become tolerant to acetolactate synthase (ALS) inhibitor herbicides through conventional mutagenesis and breeding methods include plants that can be purchased under a name. Several crops have been made herbicide tolerant through mutagenesis and conventional breeding methods, such as summerrape (Canola, BASF SE, Germany) is tolerant to imidazolinones, such as imazamox, or sunflower (DuPont, USA) is tolerant to sulfonylureas, such as tribenuron-methyl. Genetic engineering methods have been used to make crops, such as soybean, cotton, maize, sugar beet and oilseed rape, tolerant to herbicides, such as glyphosate, imidazolinones and glufosinate, some of which are under development or are available under trademarks or trade names (tolerant to glyphosate, Monsanto, USA), (tolerant to imidazolinones, BASF SE, Germany) and (tolerant to glufosinate, Bayer CropScience, Germany) are available. However, most herbicide tolerance traits have been created using genetic modification.

[0193] Herbicide tolerance has been created to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides, such as bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitor herbicides and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, such as isoxaflutole and mesotrione.

[0194] Transgenes that have been used to confer herbicide tolerance traits include: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621 and goxv247, for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1 and aad-12, for tolerance to dicamba: dmo, for tolerance to oxynil herbicides: bxn, for tolerance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA, for tolerance to ALS inhibitor herbicides: csr1-2, for tolerance to HPPD inhibitor herbicides: hppdPF, W336 and avhppd-03.

[0195] Transgenic maize events containing herbicide tolerance genes are, for example but not limited to, DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHG0JG, HCEM485, VCO- -5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275.

[0196] Transgenic soybean events containing herbicide tolerance genes are, for example but not limited to, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, W62, W98, FG72 and CV127.

[0197] Transgenic cotton events containing herbicide tolerance genes are, for example but not limited to, 19-51a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701, MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40.

[0198] Transgenic canola events containing herbicide tolerance genes are, for example but not limited to, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1, MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2 and RF3.

[0199] Insect resistance is mainly created by transferring bacterial genes of insecticidal proteins into plants. Such plants are capable of synthesizing one or more insecticidal proteins, especially those known in the genus Bacillus of bacteria, particularly Bacillus thuringiensis, such as δ-endotoxins, for example CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c; vegetative insecticidal proteins (VIPs), for example VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins that colonize nematodes of bacteria, for example Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, spider toxins, wasp toxins or other insect-specific neurotoxins; toxins produced by fungi, such as streptomycete toxins, lectins, such as pea or barley lectins; agglutinins; protease inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatins or papain inhibitors; ribosome-inactivating proteins (RIPs), such as ricin, maize RIP, abrin, luffin, saporin or bryodin; steroid metabolic enzymes, such as 3-hydroxy steroid oxidase, ecdysteroid-IDP-glycosyltransferase, cholesterol oxidase, ecdysone inhibitor or HMG-CoA-reductase; ion channel blockers, such as sodium or calcium channel blockers; juvenile hormone esterase; diuretic hormone receptor (helicokinin receptor); stilbene synthase, bibenzyl synthase, chitinase or glucanase. In the present invention, these insecticidal proteins or toxins are also explicitly understood to include pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by new combinations of protein domains (see, for example, WO 02 / 015701). Further examples of such toxins or transgenic crops capable of synthesizing such toxins are disclosed in, for example, EP-A374753, WO 93 / 007278, WO 95 / 34656, EP-A 427 529, EP-A 451 878, WO 03 / 18810 and WO 03 / 52073. Methods for producing such transgenic crops are well known to those skilled in the art and are described in, for example, the disclosures mentioned above. These insecticidal proteins contained in transgenic crops confer resistance on the crops that produce these proteins against pests from all taxa of arthropods, especially against beetles (Coleoptera), dipteran insects (Diptera) and moths (Lepidoptera) and against nematodes (Nematoda).Transgenic crops capable of synthesizing one or more insecticidal proteins are described, for example, in the disclosures mentioned above, some of which are commercially available, such as. (Maize cultivar producing Cry1Ab toxin) Plus (Maize cultivar producing Cry1Ab and Cry3Bb1 toxins) (Maize cultivar producing Cry9c toxin) RW (Maize cultivar producing Cry34Ab1, Cry35Ab1 and enzyme phosphinothricin-N-acetyltransferase [PAT]) 33B (Cotton cultivar producing Cry1Ac toxin) I (Cotton cultivar producing Cry1Ac toxin) II (Cotton cultivar producing Cry1Ac and Cry2Ab2 toxins) (Cotton cultivar producing VIP toxin) (Potato cultivar producing Cry3A toxin); Bt- Bt11 from Syngenta Seeds SAS, France (such as CB) and Bt176 (Maize cultivar producing Cry1Ab toxin and PAT enzyme), MIR604 from Syngenta Seeds SAS, France (Maize cultivar producing a modified form of Cry3A toxin, see WO 03 / 018810), MON 863 from Monsanto Europe S.A., Belgium (Maize cultivar producing Cry3Bb1 toxin), IPC531 from Monsanto Europe S.A., Belgium (Cotton cultivar producing a modified form of Cry1Ac toxin) and 1507 from Pioneer Overseas Corporation, Belgium (Maize cultivar producing Cry1F toxin and PAT enzyme).

[0200] However, genes from plant sources have also been transferred to other plants, especially genes encoding protease inhibitors, such as CpTI and pinII. Another approach uses transgenes to produce double-stranded RNA in plants to target and down-regulate insect genes. An example of such a transgene is dvsnf7.

[0201] Transgenic maize events containing genes or double-stranded RNAs encoding insecticidal proteins are, for example but not limited to, Bt10, Bt11, Bt176, MON801, MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351, MIR162, DBT418, and MZIR098.

[0202] Transgenic soybean events containing genes encoding insecticidal proteins are, for example but not limited to, MON87701, MON87751, and DAS-81419.

[0203] Transgenic cotton events containing genes encoding insecticidal proteins are, for example but not limited to, SGK321, MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, Event1, COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119, and SGK321.

[0204] Yield has been increased by using the transgenic athb17 (present in maize event MON87403) to increase ear biomass or by using the transgenic bbx32 (present in soybean event MON87712) to enhance photosynthesis.

[0205] Crops with altered oil content have been created by using the transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A, and fatb1-A. Soybean events containing at least one of these genes are: 260-05, MON87705, and MON87769.

[0206] Tolerance to abiotic conditions, particularly drought tolerance, has been created by using the transgenic cspB contained in maize event MON87460 and by using the transgenic Hahb-4 contained in soybean event IND- -5.

[0207] Traits are typically combined by combining genes in transformation events or by combining different events in breeding processes. Preferred combinations of traits are herbicide tolerance to different classes of herbicides, insect resistance to different classes of insects, especially tolerance to Lepidoptera and Coleoptera insects, combinations of herbicide tolerance with one or more types of insect resistance, combinations of herbicide tolerance with increased yield, and combinations of herbicide tolerance and tolerance to abiotic conditions.

[0208] Plants containing single or stacked traits, as well as the genes and events providing these traits, are well known in the art. For example, detailed information on mutagenesis or integration of genes and respective events can be obtained from the web pages of the institutions "International Service for the Acquisition of Agri-biotech Applications (ISAAA)" (http: / / www.isaaa.org / gmapprovaldatabase) and "Center for Environmental Risk Assessment (CERA)" (http: / / cera-gmc.org / GMCropDatabase), as well as in patent applications such as EP3028573 and WO2017 / 011288.

[0209] Use of the formulations according to the invention on crops may result in crop-specific effects for crops containing specific genes or events. These effects may relate to altered growth behavior or altered tolerance to biotic or abiotic stress factors. These effects may in particular include increased yield, enhanced resistance or tolerance to insects, nematodes, fungi, bacteria, mycoplasmas, viruses or viroid pathogens, and early vigor, early or delayed maturity, cold or heat tolerance, and altered amino acid or fatty acid profiles or contents.

[0210] Furthermore, crops that are capable of synthesizing one or more proteins by means of recombinant DNA technology to enhance the resistance or tolerance of these crops to bacterial, viral or fungal pathogens are also covered. Examples of such proteins are the so-called "pathogenesis-related proteins" (PR proteins, see for example EP-A 392 225), crop disease resistance genes (e.g. potato cultivars expressing a resistance gene against Phytophthora infestans derived from the wild Mexican potato Solanum bulbocastanum), or T4-lysozyme (e.g. potato cultivars capable of synthesizing these proteins with increased resistance to bacteria such as Erwinia amylovora). Methods for producing such transgenic crops are known to the person skilled in the art and are described in the publications mentioned above, for example.

[0211] In addition, crops are also covered which are capable of synthesizing one or more proteins by using recombinant DNA technology to increase productivity (e.g., biomass yield, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of these crops.

[0212] In addition, crops are also covered which contain altered amounts of ingredients or new ingredients specifically for improving human or animal nutrition by using recombinant DNA technology, such as oilseed crops that produce health-promoting long-chain ω-3 fatty acids or unsaturated ω-9 fatty acids (e.g., rape, Dow AgroSciences, Canada).

[0213] In addition, crops are also covered which contain altered amounts of ingredients or new ingredients specifically for improving raw material production by using recombinant DNA technology, such as potatoes that produce higher amounts of amylopectin (e.g., potato, BASF SE, Germany).

[0214] In addition, it has been found that the agrochemical composition is also suitable for defoliation and / or desiccation of crop parts, crops such as cotton, potato, rape, sunflower, soybean or field beans, especially cotton. As a desiccant, the agrochemical composition according to the invention is particularly suitable for desiccating crops such as potato, rape, sunflower and soybean, as well as the aerial parts of cereals. This enables these important crops to be harvested entirely mechanically.

[0215] Also of economic importance is the promotion of harvesting, in citrus fruits, olives and other species and varieties of pomes, drupes and nuts, which can be achieved by concentrating cracking within a certain time or reducing the attachment to the tree. The same mechanism, i.e., promoting the development of abscission tissue between the fruit part or leaf part and the shoot part of the crop, is also essential for the controlled defoliation of useful crops, especially cotton.

[0216] In addition, shortening the time interval between the maturation of individual cotton crops improves the fiber quality after harvesting.

[0217] The unwanted vegetation to be controlled by the uses and methods of the present invention is, for example, economically important monocotyledonous and dicotyledonous harmful plants, such as broad-leaved weeds, grass weeds or sedges. The active compound is also effective against perennial weeds that germinate from rhizomes, root stocks and other perennial organs and are difficult to control. Specific examples of some representatives of the monocotyledonous and dicotyledonous weed flora that can be controlled by the uses and methods of the present invention are mentioned, and the listing is not limited to specific species.

[0218] Examples of weed species on which the herbicidal composition acts effectively are, among monocotyledonous weed species, Avena spp., Alopecurus spp., Apera spp., Brachiaria spp., Bromus spp., Digitaria spp., Lolium spp., Echinochloa spp., Leptochloa spp., Fimbristylis spp., Panicum spp., Phalaris spp., Poa spp., Setaria spp. and annual sedges, and, among perennial species, Agropyron, Cynodon, Imperata and Sorghum and perennial sedges. In the case of dicotyledonous weed species, the spectrum of action extends to the following genera: for example, among annual plants, Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp., Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharbitis spp., Polygonum spp., Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp., Eclipta spp., Sesbania spp., Aeschynomene spp. and Viola spp., Xanthium spp., and, in the case of perennial weeds, Convolvulus, Cirsium, Rumex and Artemisia. In one embodiment, the unwanted vegetation belongs to the genus Nasturtium, preferably Nasturtium officinale.

[0219] The formulations of the present invention are capable of very effectively controlling unwanted vegetation in non-crop areas, especially at high application rates. They combat broad-leaved weeds and grass weeds in crops such as wheat, rice, corn, soybeans and cotton, without causing any significant damage to the crops. This effect is mainly observed at low application rates.

[0220] The formulations of the present invention are generally applied to plants by spraying the leaves. Here, for example, water can be used as a carrier and applied by conventional spraying techniques using a spray liquid volume of about 50 to 1000 l / ha (for example 50 to 100 l / ha). Application can also involve low volume or ultra-low volume methods, or the use of microparticles.

[0221] The application of the formulations of the present invention can be carried out before, during and / or after the emergence of the undesired vegetation, preferably during and / or after.

[0222] The formulations of the present invention can be applied pre-emergence or post-emergence, or together with the plant propagation material of the crop. The agrochemical composition can also be applied by applying the plant propagation material of the crop pre-treated with the agrochemical composition. If certain crops have a lower tolerance to salts of dicamba or other active compounds, the following application techniques can be used: wherein the herbicide composition is sprayed by means of a spraying device so that they come into contact as little as possible with the leaves of the sensitive crop, while the active compounds reach the leaves of the undesired plants growing below or the bare soil surface (post-directed, lay-by).

[0223] Another advantage of the present invention is that the application rate of salts of dicamba can be reduced, thereby saving costs and time. This is achieved by minimizing the primary and secondary loss situations as defined above.

[0224] In a further aspect, the present invention relates to a method for reducing the formation of droplets in an aqueous composition containing salts of dicamba. The method comprises the step of contacting the salts of dicamba or a formulation of the salts of dicamba with solvent b), water and optionally an additional component selected from additive d1), additive d2) and solvent e). Alternatively, the method comprises the step of diluting a formulation of the salts of dicamba, solvent b), water and optionally an additional component selected from additive d1), additive d2) and solvent e) with water. The present invention also relates to the use of solvent b) or a combination of solvent b) with at least one component selected from additives d1) and d2) and solvent e) for reducing the formation of droplets during the spraying of an aqueous formulation containing salts of dicamba.

[0225] The reduction of fine droplets can be measured by determining the "fine droplet ratio". The "fine droplet ratio" can be determined by quantifying, at 20 °C, the fraction of fine droplets with an average diameter below 105 μm, such as below 100 μm, vs. the fraction of larger droplets with a diameter greater than 100 μm, within the aqueous composition. When sprayed through a conventional agricultural sprayer, a higher fine droplet ratio results in a less efficient application of the solution to the target crop.

[0226] The fine droplet ratio is typically measured with a flat nozzle, such as an AIXR nozzle ("TeeJet Flat Spray Tip") or a TTI nozzle ("Turbo TeeJet Induction Flat Spray Tip"), at a pressure of 2.76 bar. The reduction of spray drift is typically measured relative to the same composition without additives.

[0227] The term "reduction of fine droplet formation" generally refers to the comparison of the fine droplet formation of an aqueous composition containing a dicamba salt and solvent b) or a combination of solvent b) with at least one component selected from additives d1) and d2) and solvent e), and water, with the fine droplet formation of an aqueous composition 2) containing a dicamba salt, water but no solvent b), additives d1) and d2), and solvent e). This reduction can be at least 10%, preferably at least 20%.

[0228] In another aspect, the present invention relates to a method for reducing the vapor pressure of an aqueous composition containing a dicamba salt. The method comprises the step of contacting the dicamba salt or a formulation of the dicamba salt with solvent b), water, and optionally an additional component selected from additive d1), additive d2), and solvent e). Alternatively, the method comprises the step of diluting a formulation of the dicamba salt, solvent b), water, and optionally an additional component selected from additive d1), additive d2), and solvent e) with water. The vapor pressure is typically measured at 20 °C in a closed system under thermodynamic equilibrium. It can be measured according to DIN EN 13016-1:2018-06.

[0229] The term "reduction of vapor pressure" generally refers to the comparison of the vapor pressure of an aqueous composition containing a dicamba salt and solvent b) or a combination of solvent b) with at least one component selected from additives d1) and d2) and solvent e), and water, with the vapor pressure of an aqueous composition 2) containing a dicamba salt, water but no solvent b), additives d1) and d2), and solvent e). This reduction can be at least 10%, preferably at least 20%.

[0230] The present invention also relates to an adjuvant composition containing solvent b), at least one of additive d1) or additive d2), and optionally solvent e); and to the use of said adjuvant composition for improving the stability of an aqueous formulation of a dicamba salt, in particular for increasing the solubility of a minor component of the dicamba salt, in particular dicamba-K as defined above.

[0231] The adjuvant composition is generally water-free. Usually, the water content of the adjuvant composition is at most 1% by weight, preferably at most 0.5% by weight, more preferably at most 0.1% by weight, based on the total weight of the adjuvant composition.

[0232] The adjuvant composition generally does not contain pesticides, and is particularly preferably free of dicamba salts. The adjuvant composition can be added to the dicamba salt during the production of an aqueous formulation or in a tank mix shortly before application. The adjuvant composition is generally water-free. However, it may contain water at a concentration of at most 60% by weight, preferably not more than 50% by weight, particularly not more than 40% by weight or 20% by weight, especially not more than 10% by weight, based on the total weight of the adjuvant composition.

[0233] The concentration of additive d) in the adjuvant composition can be 5 to 95% by weight, preferably 10 to 90% by weight, based on the total weight of the composition. The total concentration of solvents b) and e) in the adjuvant composition can be 5 to 95% by weight, preferably 10 to 90% by weight, based on the total weight of the composition. In one set of embodiments of the adjuvant composition, additive d) comprises at least one additive d1) as the main component, i.e., additive d1) is the only additive d) or accounts for more than 50% by weight of all additive d). In another set of embodiments of the adjuvant composition, additive d) comprises at least one additive d2) as the main component, i.e., additive d2) is the only additive d) or accounts for more than 50% by weight of all additive d).

[0234] The adjuvant composition may comprise a co-solvent. Suitable co-solvents are water-miscible up to at least a co-solvent / water ratio of 1:1, preferably at least 2:1, more preferably at least 4:1. Suitable co-solvents are alcohols such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; diols; DMSO; ketones such as heptanone, cyclohexanone; esters such as carbonates, fatty acid esters, γ-butyrolactone; fatty acids; phosphonates; amines; amides such as fatty acid dimethylamide; and mixtures thereof. In one embodiment, the co-solvent is γ-butyrolactone. The concentration of the co-solvent in the adjuvant can be at least 1% by weight, preferably at least 2% by weight, more preferably at least 4% by weight, most preferably at least 5% by weight, based on the total weight of the agrochemical composition. The concentration of the co-solvent in the agrochemical formulation can be 1 to 20% by weight, preferably 1 to 10% by weight, more preferably 2 to 8% by weight, most preferably 4 to 7% by weight.

[0235] In one embodiment, the adjuvant composition comprises a solvent b) and an additive d1). In a particular embodiment, the agrochemical composition comprises N-octylpyrrolidone and an additive d1), preferably wherein the additive d1) is as defined in embodiment PA-1 or PA-2, more preferably wherein the additive d1) is as defined in embodiment PA-2. In another embodiment, the adjuvant composition comprises N-butylpyrrolidone and an additive d1), preferably wherein the additive d1) is as defined in embodiment PA-1 or PA-2, more preferably wherein the additive d1) is as defined in embodiment PA-2. In another embodiment, the adjuvant composition comprises N-dodecylpyrrolidone and an additive d1), preferably wherein the additive d1) is as defined in embodiment PA-1 or PA-2, more preferably wherein the additive d1) is as defined in embodiment PA-2.

[0236] In one embodiment, the adjuvant composition comprises a solvent b), a C3-C6-lactone and an additive d1). In another embodiment, the adjuvant composition comprises γ-butyrolactone and an additive d1), preferably wherein the additive d1) is as defined in embodiment PA-1 or PA-2, more preferably wherein the additive d1) is as defined in embodiment PA-2. In another embodiment, the adjuvant composition comprises ε-caprolactone and an additive d1), preferably wherein the additive d1) is as defined in embodiment PA-1 or PA-2, more preferably wherein the additive d1) is as defined in embodiment PA-2.

[0237] In one embodiment, the adjuvant composition comprises a solvent b) and an additive d2). In another embodiment, the adjuvant composition comprises N-octylpyrrolidone and an additive d2), wherein the additive d2) is preferably a hyperbranched polycarbonate linked to a polyethylene glycol mono-C1-C 18 -alkyl ether, more preferably wherein the hyperbranched polycarbonate is linked to polyethylene glycol monomethyl ether, and most preferably wherein the additive d2) is a hyperbranched polycarbonate linked to polyethylene glycol monomethyl ether via a linker.

[0238] In another embodiment, the adjuvant composition comprises N-butylpyrrolidone and an additive d2), wherein the additive d2) is preferably a hyperbranched polycarbonate linked to a polyethylene glycol mono-C1-C 18 -alkyl ether, more preferably wherein the hyperbranched polycarbonate is linked to polyethylene glycol monomethyl ether, and most preferably wherein the additive d2) is a hyperbranched polycarbonate linked to polyethylene glycol monomethyl ether via a linker.

[0239] In another embodiment, the adjuvant composition comprises N-dodecylpyrrolidone and an additive d2), wherein the additive d2) is preferably a hyperbranched polycarbonate linked to a polyethylene glycol mono-C1-C 18Hyperbranched polycarbonates on - alkyl ethers, more preferably where the hyperbranched polycarbonate is attached to methoxypolyethylene glycol, and most preferably where additive d2) is a hyperbranched polycarbonate attached to methoxypolyethylene glycol via a linking moiety.

[0240] In another embodiment, the adjuvant composition comprises solvent b), a C3 - C6 - lactone, and additive d2), where additive d2) is preferably a hyperbranched polycarbonate attached to a polyethylene glycol mono - C1 - C 18 - alkyl ether, more preferably where the hyperbranched polycarbonate is attached to methoxypolyethylene glycol, and most preferably where additive d2) is a hyperbranched polycarbonate attached to methoxypolyethylene glycol via a linking moiety.

[0241] In another embodiment, the adjuvant composition comprises solvent b), γ - butyrolactone, and additive d2), where additive d2) is preferably a hyperbranched polycarbonate attached to a polyethylene glycol mono - C1 - C 18 - alkyl ether, more preferably where the hyperbranched polycarbonate is attached to methoxypolyethylene glycol, and most preferably where additive d2) is a hyperbranched polycarbonate attached to methoxypolyethylene glycol via a linking moiety.

[0242] The adjuvant composition may further comprise adjuvants. Suitable adjuvants are as defined above for agrochemical compositions.

[0243] The present invention also relates to the use of solvent b), or a combination of solvent b) with at least one component selected from additives d1) and d2) and solvent e), or the adjuvant composition for increasing the solubility of dicamba salts in aqueous formulations; and to a method for increasing the solubility of dicamba salts in aqueous formulations, which comprises the step of incorporating solvent b) or a combination of solvent b) with at least one component selected from additives d1) and d2) and solvent e) or the adjuvant composition into an aqueous formulation of a dicamba salt.

[0244] The present invention also relates to the use of solvent b), or a combination of solvent b) with at least one component selected from additives d1) and d2) and solvent e), or the adjuvant composition for increasing the solubility of by - products of dicamba salts in aqueous formulations; and to a method for increasing the solubility of by - products of dicamba salts in aqueous formulations, which comprises the step of incorporating solvent b) or a combination of solvent b) with at least one component selected from additives d1) and d2) and solvent e) or the adjuvant composition into an aqueous formulation of a dicamba salt.

[0245] As used herein, the term "increased solubility" refers to an increase in the maximum concentration of the dicamba salt or a by-product of the dicamba salt that can be dissolved in a specified amount of an aqueous agrochemical composition as compared to the same agrochemical formulation without an additive. The solubility of the dicamba salt or the by-product of the dicamba salt is typically measured at 20 °C at equilibrium.

[0246] The formulations and adjuvant compositions of the present invention have several advantages. The formulations of the present invention, particularly the SL formulations of the dicamba salt, and the co-formulations, particularly their mixtures with glyphosate and / or glufosinate, have a low vapor pressure and a reduced droplet ratio. The formulations of the present invention can be mixed with glyphosate and / or glufosinate and / or their salts, or with formulations of glyphosate and / or glufosinate salts, thereby obtaining a chemically and physically stable co-formulated product of the dicamba salt and glyphosate and / or glufosinate. The formulations enable the production of aqueous formulations with a high loading of the respective dicamba salts in a dissolved state, which tolerate a significant amount of the minor by-products of the dicamba manufacturing process. Thus, they can cope with different product qualities of the dicamba salt without the risk of forming irreversible precipitates. The aqueous formulations of the present invention can contain a significant amount of the by-products but still remain stable, homogeneous, and transparent, and the by-products remain dissolved in the liquid agrochemical composition. At the same time, the formulations are safe for the applicator and have high biological efficacy.

[0247] The following examples illustrate the present invention. Examples

[0248] The following ingredients were used to prepare the agrochemical compositions of the examples.

[0249] Dicamba-K-A: Potassium salt of dicamba, 95.3% purity

[0250] Dicamba-K-B: Potassium salt of dicamba, 99.9% purity

[0251] Dicamba-K-C: Potassium salt of dicamba, 93.0% purity

[0252] By-products of dicamba materials: 3,5-dichloro-2-methoxybenzoic acid, 3,6-dichloro-2-hydroxybenzoic acid, 3,5-dichloro-2-hydroxybenzoic acid, 3-chloro-2,6-dimethoxybenzoic acid, 3,4-dichloro-2-methoxy-benzoic acid, 3,4-dichloro-2-hydroxybenzoic acid, 3,5-dichloro-4-methoxybenzoic acid, and their potassium salts.

[0253] Dicamba-BAPMA: Salt of dicamba with 0.39 moles of N,N-bis-(3-aminopropyl)methylamine, which contains 4-14 wt% by-products relative to dicamba, including 0.8-1.6 wt% of 3,5-dichloro-2-hydroxybenzoic acid and 0.5 to 3.5% of 3,6-dichloro-2-hydroxybenzoic acid relative to dicamba.

[0254] Dicamba-DGA: The salt of dicamba with 1.0 mole of N-(2-(2-hydroxyethoxy)ethyl)amine, which contains 4-14% by weight of by-products relative to dicamba, including 0.8-1.6% by weight of 3,5-dichloro-2-hydroxybenzoic acid and 0.5 to 3.5% of 3,6-dichloro-2-hydroxybenzoic acid relative to dicamba.

[0255] Dicamba-SL: An aqueous solution of 600 g / l of dicamba N,N-bis-(3-aminopropyl)methylammonium salt.

[0256] Polymer A: A polyalkylene oxide block copolymer of formula (I), where m is from 50 to 60, and n, p are independently from 45 to 55.

[0257] Polymer B: A polyalkylene oxide block copolymer of formula (I), where m is from 25 to 35, and n, p are independently from 70 to 80.

[0258] Polymer C: A hyperbranched polycarbonate linked to methyl polyethylene glycol, prepared as described in Synthesis Example 5 of WO2010130599

[0259] Solvent A: n-Propyl lactate

[0260] Solvent B: N-(n-butyl)pyrrolidone

[0261] Solvent C: N-(n-octyl)pyrrolidone

[0262] Solvent D: N-(n-dodecyl)pyrrolidone

[0263] Solvent E: γ-Butyrolactone

[0264] Solvent F: N-(tert-butyl)pyrrolidone

[0265] Example-1:

[0266] Manufacture a soluble concentrate (SL-1) of dicamba-K-A. For this purpose, the following compounds are loaded into a container in the order and amounts given in Table A. The resulting mixture is then stirred until a clear and homogeneous liquid is obtained.

[0267] Table A: Components of SL-1 in [g]

[0268] Compound Amount Dicamba-K-A 56.9 <![CDATA[Softened H2O]]> 46.75 Solvent B 6.68 Solvent E 6.68 Polymer A 6.68

[0269] Example 2:

[0270] The production of soluble concentrates SL-2 to SL-9 is similar to the procedure of Example-1. The amounts of the ingredients are summarized in Table B. All amounts are given in [g].

[0271] Table B: Components of SL-2 to SL-9 in [g]

[0272] Compound SL-2 SL-3 SL-4 SL-5 SL-6 SL-7 SL-8 SL-9 Dicamba-K-A 56.66 56.66 56.66 56.66 56.66 56.66 56.66 56.66 <![CDATA[H2O (软化) > 46.75 46.75 46.75 46.75 46.75 46.75 46.75 46.75 Solvent B - - 6.68 - - 6.68 - - Solvent C 6.68 - - 6.68 - - 6.68 - Solvent D - 6.68 - - 6.68 - - 6.68 Solvent E 6.68 6.68 6.68 6.68 6.68 6.68 6.68 6.68 Polymer A 6.68 6.68 - - - - - - Polymer B - - 6.68 6.68 6.68 - - - Polymer C - - - - - 6.68 6.68 6.68

[0273] Example - 3:

[0274] All soluble concentrates SL-1 to SL-9 were analyzed by visual inspection after preparation. SL-1 to SL-9 formed clear solutions containing dicamba-K-A.

[0275] Example - 4 (comparative example)

[0276] The comparative soluble concentrate SL-C1 was prepared by mixing 66 wt% water and 44 wt% dicamba-K-A. Dicamba-K-A contained the following by-products within the experimentally determined concentrations and concentration ranges provided in parentheses. These values relate to the free acids of the respective by-products relative to the free acid of dicamba: 3,5-dichloro-2-methoxybenzoic acid (10 to 70 g / kg), 3,6-dichloro-2-hydroxybenzoic acid (5 to 30 g / kg), 3,5-dichloro-2-hydroxybenzoic acid (0.5 to 25 g / kg).

[0277] The mixture formed a turbid liquid, full of suspended matter, which did not dissolve in water and settled during storage.

[0278] Example - 5:

[0279] The droplet ratio properties of diluted soluble concentrates SL-1 to SL-9 mixed with glyphosate were analyzed. For this purpose, 1.22 liters of a soluble concentrate selected from SL-1 to SL-14 was mixed with 2.07 liters of a soluble concentrate containing 540 g / l potassium glyphosate (hereinafter "glyphosate-K"), and the mixture was diluted with water to a total volume of 94 liters. The resulting spray solution was then sprayed at a pressure of 2.76 bar using an AIXR nozzle ("TeeJet Flat Spray Tip") or a TTI nozzle ("Turbo TeeJet Induction Flat SprayTip"). The droplet size distribution was measured using a Sympatec Helos KF laser diffraction device. The measurement was carried out in 31 size classes from 18 to 3500 μm. The measurement was carried out at an angle of 0° at a distance of 30.5 cm from the nozzle. The analysis of the data was based on 10 measurements collected in two runs. Clean the lens between them if necessary.

[0280] For comparison, a spray solution was prepared by mixing 0.93 liters of an aqueous soluble concentrate (SL-C2) containing 754 g / L of dicamba N,N-bis-(3-aminopropyl) methylammonium) with 2.07 liters of a soluble concentrate containing 540 g / L of potassium glyphosate and diluting with water to a total volume of 94 liters. Table D shows the droplet fractions for different nozzle types and the test soluble concentrates SL-1 to SL-10 compared to SL-C2.

[0281] The results are summarized in Table C.

[0282] Table C: Measurement of <100 μm droplets of SL-1 to SL-9 and SL-C2 after mixing with potassium glyphosate and dilution with water

[0283]

[0284] Example 6:

[0285] The production of soluble concentrates SL-10 to SL-32 was similar to Example-1. The amounts of the components are summarized in Tables D-1 to D-3.

[0286] Table D-1: Components of SL-10 to SL-17 in [g]

[0287] Compound SL-10 SL-11 SL-12 SL-13 SL-14 SL-15 SL-16 SL-17 Dicamba-K-A 736.1 736.1 736.1 736.1 736.1 736.1 736.1 736.1 <![CDATA[H2O (软化) > 310.1 281.9 366.5 338.3 422.9 394.7 338.3 394.7 Solvent B 56.4 84.6 56.4 84.6 56.4 84.6 28.2 28.2 Polymer C 197.4 197.4 141.0 141.0 84.6 84.6 197.4 141.0

[0288] Table D-2: Components of SL-18 to SL-25 in [g]

[0289] Compound SL-18 SL-19 SL-20 SL-21 SL-22 SL-23 SL-24 SL-25 Dicamba-K-A 736.1 736.1 736.1 736.1 736.1 736.1 736.1 736.1 <![CDATA[H2O (软化) > 451.1 310.1 281.9 253.7 253.7 310.1 366.5 338.3 Solvent B 28.2 28.2 56.4 84.6 112.8 112.8 112.8 141.0 Polymer C 84.6 225.6 225.6 225.6 197.4 141.0 84.6 84.6

[0290] Table D-3: Components of SL-26 to SL-32 in [g]

[0291] Compound SL-26 SL-27 SL-28 SL-29 SL-30 SL-31 SL-32 Dicamba-K-A 736.1 736.1 736.1 736.1 736.1 736.1 736.1 <![CDATA[H2O (软化) > 451.1 422.9 394.7 366.5 338.3 366.5 479.3 Solvent B 84.6 112.8 141.0 169.2 197.4 197.4 84.6 Polymer C 28.2 28.2 28.2 28.2 28.2 - -

[0292] Example 7:

[0293] The production of soluble concentrates SL-33 to SL-42 was similar to Example-1. The amounts of the components are summarized in Tables E-1 and E-2.

[0294] Table E-1: Components of SL-33 to SL-37 in [g]

[0295] Compound SL-33 SL-34 SL-35 SL-36 SL-37 Dicamba-K-A [g] - - Dicamba-K-C [g] 756.3 756.3 755.9 756.3 756.3 Solvent A [g] 16.92 56.4 - 16.92 56.4 Solvent B [g] 50.76 112.8 56.4 50.76 112.8 Solvent E [g] 16.92 - - 16.92 - Polymer B [g] - - 141.0 84.6 28.2 Polymer C [g] 84.6 28.2 - - - Water 389.5 361.27 347.0 389.5 361.27 Density at 20 °C [g / ml] 1.315 1.315 N.A. 1.314 1.328

[0296] Table E-2: Components of SL-38 to SL-42 in [g]

[0297] Compound SL-38 SL-39 SL-40 SL-41 SL-42 Dicamba-K-B [g] 703 703 703 703 703 Solvent A [g] 16.92 56.4 - 16.92 56.4 Solvent B [g] 50.76 112.8 56.4 50.76 112.8 Solvent E [g] 16.92 - - 16.92 - Polymer B [g] - - 141.0 84.6 28.2 Polymer C [g] 84.6 28.2 - - - Water 389.5 361.27 347.0 389.5 361.27 Density at 20 °C [g / ml] 1.305 1.305 N.A. 1.305 1.294

[0298] Example 8:

[0299] Analyze the volatility of soluble concentrates SL-33 to SL-42 in the presence of glyphosate-K. To this end, 0.94 liters of a soluble concentrate selected from SL-33 to SL-42 is mixed with 2.07 liters of a soluble concentrate containing 540 g / l of potassium glyphosate, and the mixture is diluted with water to a total volume of 94 liters. The sample is further diluted with water to ensure that the amount of active ingredient per unit area in the test tube is similar to the amount obtained by spraying the active ingredient in the field at the recommended application rate. The sample is then incubated in a glass tube contained in a water bath. The sample is incubated at 70 °C for 24 hours. The volatilized sample material is continuously removed from the tube through an air duct. The residual amount of dicamba is determined relative to the applied amount. The reported volatility is [1-(residual amount / applied amount)], expressed as a percentage. The results are summarized in Table F below.

[0300] Table F: Volatility of samples SL-33 to SL-42 measured in a Büchi Multivapor P-12

[0301] n.m. = not measured

[0302] Example 9:

[0303] The production of soluble concentrates SL-43 to SL-51 is similar to the procedure of Example-1. The amounts of ingredients and the properties of the formulations are summarized in Table G.

[0304] The cold storage stability (cold stability) of the formulations is evaluated by storing the formulations at -5 °C, -10 °C, and -20 °C for up to 21 days. The crystallization condition of the formulations is visually inspected. The stability is rated according to the following grades:

[0305] 1 No crystallization or only trace amounts within 21 days at -20 °C, which redissolve upon warming to ambient temperature

[0306] 2 No crystallization or only trace amounts within 21 days at -10 °C, which redissolve upon warming to ambient temperature but crystallize within 14 days at -20 °C

[0307] 3 No crystallization or only trace amounts within 21 days at -5 °C, which redissolve upon warming to ambient temperature but crystallize within 14 days at -10 °C

[0308] 4 Crystallization within 17 days at -5 °C. The crystallization is irreversible

[0309] 5 Crystallization within 3 days at -5 °C. The crystallization is irreversible

[0310] The warm storage stability (stability (warm)) of the formulations is evaluated by storing the formulations at +54 °C for 14 days and then determining the amount of dicamba relative to the value before storage by means of HPLC. The value is given as % recovery.

[0311] Table G: Soluble concentrates SL-43 to SL-51

[0312]

[0313] 1) Dicamba contains 1.2 wt% of 3,5-dichloro-2-hydroxybenzoic acid

[0314] 2) Dicamba contains 1.5 wt% of 3,5-dichloro-2-hydroxybenzoic acid

[0315] For comparison, a soluble concentrate dicamba-BAPMA SLC3 was prepared by the procedure of Example-1, which contains 536.6 g of dicamba-BAPMA, 143 g of potassium carbonate and water added to 1 L. The refrigerated stability rating was 4.

[0316] Example 10

[0317] The volatility of soluble concentrates SL-47 and SLC-3 was analyzed by the procedure of Example 8, except that they were measured by themselves without mixing with the SL of glyphosate. The results are summarized in Table H below. Table H: Volatility of samples SL-47 and SLC-3 measured in Büchi Multivapor P-12

[0318] Soluble concentrate SL-47 SLC-3 Volatility [%] 3.9 4.5

[0319] Example 11

[0320] The droplet ratio properties of diluted soluble concentrates LS-C3, SL-47 and SL-48 were analyzed by the procedure of Example 5 using an AIXR nozzle, except that these formulations were measured by themselves without mixing with the SL of glyphosate. The results are summarized in Table I below.

[0321] Table I: Droplet ratios of samples SL-47 and SLC-3

[0322]

[0323] Example 12:

[0324] The production of soluble concentrates SL-52 to SL-53 and the comparative soluble concentrate SLC-4 was similar to the procedure of Example-1. The amounts of the ingredients and the properties of the formulations are summarized in Table K. The stability was evaluated as described for Example 8.

[0325] Table K: Soluble concentrates SLC-4, SL-52 to SL-59

[0326]

[0327] 1) Dicamba contains 1.2% by weight of 3,5-dichloro-2-hydroxybenzoic acid

[0328] 2) Storage is carried out only at -5°C. None of the soluble concentrates showed crystallization within 28 days, except for SLC-4. Therefore, the cold storage stability can be even better, as only slight turbidity was observed after 5 days of storage at -10°C.

[0329] 3) The formulation initially forms a clear solution, in which precipitation occurs within 24 hours

[0330] 4) % recovery

[0331] 5) All formulations are almost clear and remain clear during storage at -5°C, -10°C and -20°C for more than 2 days.

Claims

1. A water-based SL formulation of dicamba, which contains a) Dicamba in the form of a dicamba salt, wherein the amount of dicamba in the formulation calculated as the free acid is in the range of 350 to 850 g / L, b) An organic solvent selected from N-C3-C6-alkylpyrrolidones, wherein the amount of N-C3-C6-alkylpyrrolidone in the formulation is in the range of 10 to 200 g / l, and Water in the range of 10 to 60% by weight.

2. The water-based SL formulation according to claim 1, wherein the organic solvent is selected from N-C3-C6-alkylpyrrolidones, wherein the C3-C6-alkyl is straight-chain.

3. The water-based SL formulation according to claim 2, wherein the organic solvent comprises n-butylpyrrolidone.

4. The water-based SL formulation according to any one of the preceding claims 1, wherein the amount of N-C3-C6-alkylpyrrolidone in the formulation is in the range of 20 to 100 g / l.

5. The water-based SL formulation according to claim 2, wherein the amount of N-C3-C6-alkylpyrrolidone in the formulation is in the range of 20 to 100 g / l.

6. The water-based SL formulation according to claim 3, wherein the amount of N-C3-C6-alkylpyrrolidone in the formulation is in the range of 20 to 100 g / l.

7. The water-based SL formulation according to claim 4, wherein the amount of N-C3-C6-alkylpyrrolidone in the formulation is in The range of 25 to 60 g / l.

8. The water-based SL formulation according to claim 5, wherein the amount of N-C3-C6-alkylpyrrolidone in the formulation Is in the range of 25 to 60 g / l.

9. The water-based SL formulation according to claim 6, wherein the amount of N-C3-C6-alkylpyrrolidone in the formulation Is in the range of 25 to 60 g / l.

10. The water-based SL formulation according to any one of the preceding claims 1 to 9, which further contains at least one minor component of dicamba selected from 3,5-dichloro-2-methoxybenzoic acid, 3,6-dichloro-2-hydroxybenzoic acid, 3,5-dichloro-2-hydroxybenzoic acid, 3-chloro-2,6-dimethoxybenzoic acid, 3,4-dichloro-2-methoxybenzoic acid, 3,4-dichloro-2-hydroxybenzoic acid and / or 3,5-dichloro-4-methoxybenzoic acid.

11. The water-based SL formulation according to claim 10, wherein the total concentration of all minor components is in the range of 1 to 20% by weight, based on the total weight of dicamba contained in the water-based SL formulation.

12. The water-based SL formulation according to claim 10, wherein the minor component comprises a dichloro-2-hydroxybenzoic acid compound selected from 3,6-dichloro-2-hydroxybenzoic acid, 3,5-dichloro-2-hydroxybenzoic acid and 3,4-dichloro-2-hydroxybenzoic acid and combinations thereof.

13. The water-based SL formulation according to claim 11, wherein the minor component comprises a dichloro-2-hydroxybenzoic acid compound selected from 3,6-dichloro-2-hydroxybenzoic acid, 3,5-dichloro-2-hydroxybenzoic acid and 3,4-dichloro-2-hydroxybenzoic acid and combinations thereof.

14. An aqueous SL formulation according to any one of the preceding claims 1 to 9 and 11 to 13, wherein the dicamba salt is a salt of dicamba with a water-miscible organic amine having at least one amino group.

15. An aqueous SL formulation according to claim 10 above, wherein the dicamba salt is a salt of dicamba with a water-miscible organic amine having at least one amino group.

16. An aqueous SL formulation according to claim 14, wherein the water-miscible organic amine is selected from mono-C2-C4-alkanolamines, N,N-bis(C2-C4-alkanol)amines, N-(di-C2-C4-alkyleneglycol)amines, and N-(amino-C2-C4-alkyl)-C1-C2-alkylamines, N,N-bis(amino-C2-C4-alkyl)-C1-C2-alkylamines, N-(N’,N’-di-C1-C2-alkylamino-C2-C4-alkyl)-C1-C2-alkylamines.

17. An aqueous SL formulation according to claim 15, wherein the water-miscible organic amine is selected from mono-C2-C4-alkanolamines, N,N-bis(C2-C4-alkanol)amines, N-(di-C2-C4-alkyleneglycol)amines, and N-(amino-C2-C4-alkyl)-C1-C2-alkylamines, N,N-bis(amino-C2-C4-alkyl)-C1-C2-alkylamines, N-(N’,N’-di-C1-C2-alkylamino-C2-C4-alkyl)-C1-C2-alkylamines.

18. An aqueous SL formulation according to claim 16 or 17, wherein the water-miscible organic amine is selected from N-(di-C2-C4-alkyleneglycol)amines and N,N-bis(amino-C2-C4-alkyl)-C1-C2-alkylamines.

19. An aqueous SL formulation according to claim 18, wherein the water-miscible organic amine is N,N-bis(3-aminopropyl)methylamine.

20. An aqueous SL formulation according to claim 18, wherein the water-miscible organic amine is diethanolamine.

21. An aqueous SL formulation according to any one of claims 15 to 17, 19, and 20, which further contains an inorganic buffer as component c).

22. An aqueous SL formulation according to claim 21, wherein the inorganic buffer is an alkali metal carbonate.

23. An aqueous SL formulation according to claim 22, wherein the inorganic buffer is potassium carbonate.

24. An aqueous SL formulation according to any one of claims 15 to 17, 19, 20, 22, and 23, which has a pH value in the range of 6.0 to 11.0 measured at 20 °C and 1 bar.

25. An aqueous SL formulation according to any one of the preceding claims 1 to 9 and 11 to 13, wherein the dicamba salt is the potassium salt of dicamba.

26. An aqueous SL formulation according to claim 10, wherein the dicamba salt is the potassium salt of dicamba.

27. An aqueous SL formulation according to claim 25, wherein the dicamba salt contains at least one polymeric additive d), which is selected from d1) a polyalkylene oxide block copolymer of formula (I) R 1 O(EO) n (PO) m (EO) p R 2 (I), wherein EO is CH2CH2O; PO is CH2CH(CH3)O; R 1 、R 2 is H or C1-C3-alkyl; n and p are independently natural numbers from 10 to 250; and m is a natural number from 10 to 100; and d2) a hyperbranched polycarbonate which is attached to a linear polymer comprising polyethylene oxide.

28. The aqueous SL formulation according to claim 26, wherein the dicamba salt contains at least one polymer additive d) selected from d1) a polyalkylene oxide block copolymer of formula (I) R 1 O(EO) n (PO) m (EO) p R 2 (I), wherein EO is CH2CH2O; PO is CH2CH(CH3)O; R 1 、R 2 is H or C1-C3-alkyl; n and p are independently natural numbers from 10 to 250; and m is a natural number from 10 to 100; and d2) a hyperbranched polycarbonate which is attached to a linear polymer comprising polyethylene oxide.

29. The aqueous SL formulation according to claim 27, wherein n and p are independently natural numbers from 20 to 200, and m is a natural number from 20 to 70.

30. The aqueous SL formulation according to claim 28, wherein n and p are independently natural numbers from 20 to 200, and m is a natural number from 20 to 70.

31. The aqueous SL formulation according to any one of claims 27 to 30, which comprises additive d1), wherein the ratio (n + p) / m in formula I is from 1:1 to 10:

1.

32. An aqueous SL formulation according to any one of claims 27 to 30, which comprises additive d2), wherein the hyperbranched polycarbonate is attached to a polyethylene glycol-mono-C1-C 18 -alkyl ether.

33. The aqueous SL formulation according to claim 32, wherein the polyethylene glycol-mono-C1-C 18 -alkyl ether is polyethylene glycol monomethyl ether.

34. The aqueous SL formulation according to any one of claims 27 to 30 and 33, which comprises additive d2), wherein the hyperbranched polycarbonate contains a polyether alcohol based on an alcohol having at least 3 OH groups and 1 to 30 molecules of alkylene oxide.

35. The aqueous SL formulation according to claim 32, which comprises additive d2), wherein the hyperbranched polycarbonate contains a polyether alcohol based on an alcohol having at least 3 OH groups and 1 to 30 molecules of alkylene oxide.

36. The aqueous SL formulation according to claim 34, wherein the polyether alcohol is based on an alcohol having at least 3 OH groups and 5 to 20 molecules of propylene oxide.

37. The aqueous SL formulation according to claim 35, wherein the polyether alcohol is based on an alcohol having at least 3 OH groups and 5 to 20 molecules of propylene oxide.

38. The aqueous SL formulation according to any one of claims 27 to 30, 33 and 35 to 37, which contains a second solvent e) selected from C1-C6-alkyl lactates, C3-C6-lactones and mixtures thereof.

39. The aqueous SL formulation according to claim 38, wherein the second solvent e) is a C3-C6-lactone.

40. The aqueous SL formulation according to claim 39, wherein the second solvent e) is γ-butyrolactone.

41. The aqueous SL formulation according to any one of claims 27 to 30, 33, 35 to 37, 39 and 40, wherein the concentration of solvent b) and e) and the sum of all additives d1) and d2) is in the range of 1 to 35% by weight, based on the total weight of the aqueous SL formulation.

42. An aqueous co-formulation which comprises an aqueous SL formulation according to any one of the preceding claims 1 to 41, and further comprises glyphosate and / or glufosinate and / or pyroxasulfone.

43. A method for producing an aqueous SL formulation as described in any one of claims 1 to 41 above, which comprises the step of mixing a dicamba salt with water and at least one solvent b).

44. A method for controlling unwanted vegetation and / or regulating plant growth, wherein an aqueous SL formulation or an aqueous co-formulation as described in any one of claims 1 to 42 is allowed to act on respective pests, their environment or a crop to be protected from respective pests, on the soil and / or on the crop and / or on their environment.

45. An adjuvant composition for enhancing the stability of an aqueous SL formulation of a dicamba salt to prevent precipitate formation, which comprises a mixture of a solvent b) as described in any one of claims 1 to 3 and at least one of additives d1) and d2) as described in any one of claims 27 to 33.

46. Use of a solvent b) as described in any one of claims 1 to 3 for reducing the sensitivity of an aqueous SL formulation of a dicamba salt to precipitate formation.

47. The use according to claim 46, wherein it is for reducing the sensitivity of an aqueous SL formulation of a dicamba salt to precipitate formation during low-temperature storage.

48. Use of a solvent b) as described in any one of claims 1 to 3 or a combination of a solvent b) and at least one additional component selected from additives d1) and d2) and a solvent e) as described in any one of claims 27 to 40 for reducing droplet formation when spraying an aqueous dilution of a formulation of a dicamba salt.

49. A method for reducing droplet formation when spraying an aqueous spray solution obtained by diluting a formulation of a dicamba salt with water, wherein the method comprises the step of incorporating a solvent b) as described in any one of claims 1 to 3 or a combination of a solvent b) and at least one component selected from additives d1) and d2) and a solvent e) as described in any one of claims 27 to 40 into the formulation or into the aqueous spray solution.

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