Use of a solvent composition in agrochemical formulations and corresponding agrochemical formulations

Abstract

The present invention relates to the use of a particular composition as solvent in agrochemical formulations and to the agrochemical formulation itself.

Description

[0001] USE OF A SOLVENT COMPOSITION IN AGROCHEMICAL FORMULATIONS AND CORRESPONDING AGROCHEMICAL FORMULATIONS

[0002] The present invention relates to the use of solvent compositions, comprising a sulfoxide and a mixture of specific esters, in agrochemical formulations, and to such agrochemical formulations.

[0003] Agriculture uses many agricultural materials such as fertilisers or pesticides, for example insecticides, herbicides or fungicides. They are also referred to as active plant-protection products or active materials or active substances. Agricultural materials are generally products in pure or highly concentrated form.

[0004] In general, agricultural materials are not employed as pure substances, but depending on the field of application and the desired physical constituency of the use form, they are generally formulated with other ingredients.

[0005] Independently of the type of formulation and of whether the formulation comprises one or more agricultural materials, one attempts, in particular in the field of agriculture, to achieve as high an agricultural material concentration as possible of the respective formulation since a high concentration of the agricultural materials allows the volumes to be applied to be reduced and, as a consequence, entails savings with regard to the adjuvant materials applied and with regard to packaging and logistics. Highly-concentrated stable formulations and coformulations with environmentally friendly adjuvants are therefore of interest.

[0006] Frequently, such formulations comprise combinations of different agricultural materials instead of individual agricultural materials in order to jointly utilize the properties of the individual agricultural materials upon application, or else because the individual agricultural materials are synergistic in combination, i.e. produce superadditive increases in activity.

[0007] In the application of products for agricultural use, it is widely known to combine two or more agricultural materials having a different mechanism of action and / or different biological target, to broaden the action range of the mixture with respect to ones of the agricultural materials used individually and for example to prevent the occurrence of resistance phenomena from the harmful organisms or species, phenomena which over time tend to reduce the effectiveness of the pesticide products used.

[0008] Depending on the respective physico-chemical characteristics of the various agricultural materials and their loading in the targeted formulation, it can be very challenging to identify suitable co-formulants to obtain a chemically and physically stable formulation.

[0009] For agricultural materials with a low or relatively low water solubility, the use of appropriate solvents is especially interesting to prepare concentrated liquid formulations, in the form of emulsifiable concentrates (EC), concentrated emulsions in water (EW), microemulsions (ME), suspoemulsions (SE), suspension concentrates (SC), oil dispersions (OD), dispersible concentrates (DC). More details on the definitions of above-mentioned formulations can be found in the “Guidance document for the generation of data on the physical, chemical and technical properties of plant protection products under regulation (EC) N° 1107 / 2009 of the EU parliament and council on placing plant protection products on the market”.

[0010] Such concentrated formulations of agricultural materials are generally diluted prior to agricultural use. The dilution effected by the farmer can be performed by mixing the agrochemical formulation with water.

[0011] Depending on the characteristics of the concentrated formulation, the diluted formulation may be in the form of a solution, an emulsion, a suspension, or a suspo- emulsion.

[0012] Furthermore, the agrochemical formulations generally comprise compounds that enable these physical forms to be obtained. They may be, for example, surfactants, polymers, solvents, mineral supports and / or dispersants. Quite often, these compounds do not have any active nature, but intermediary nature that aids formulation. It is thus often desired to limit their amounts in order to limit the costs and / or any harm to the environment.

[0013] In addition, certain solid agricultural materials are often difficult to formulate. For certain agricultural materials, it is difficult to produce concentrated formulations that are easy for the farmer to dilute, stable and free of substantial drawbacks (real or perceived) with regard to safety, toxicity and / or ecotoxicity. For certain agricultural materials, it is difficult to formulate at relatively high concentrations with sufficient stability. In particular, it is necessary to avoid the appearance of crystals, in particular at low temperature and / or during dilution and / or during storage of the dilute composition, in particular at low temperature. The crystals may have harmful effects, especially blocking the filters of the devices used for spreading the dilute composition, blocking the spraying devices, reducing the overall activity of the formulation, creating unnecessary problems of waste-management procedures for removing the crystals, and / or causing poor distribution of the agricultural material(s) on the agricultural field.

[0014] The use of solvent systems based on a single solvent such as N- methylpyrrolidone (NMP) is known. This solvent enables the dissolution of a large number of agricultural materials, and avoids the formation of crystals, but it is, however known as presenting hazards, especially for the operatives and users handling it.

[0015] The agrochemical industry is looking for solvent compositions having properties that are satisfactory for agricultural application, like for example, good solubilisation efficiency for agricultural materials as well as low miscibility with water. In addition, the cost of the solvent compositions should generally be modest, and preferably they should have a favourable toxicology and / or eco toxicology profile, in particular low toxicity and / or low hazard potential, and / or low volatility (low VOC - volatile organic compounds). From a regulatory side, the solvents toolbox is increasingly shrinking due to re-classifications of classical, versatile solvents, such as NMP or dimethyl acetamide for example.

[0016] Thus, there is a continuous need for providing solvent systems for agricultural use that: have a great modularity, i.e. the ability to be used for a large number of agricultural materials, have a potential for solubilisation of significant quantities of agricultural materials, have a high compatibility with several agricultural materials combined together, for example in order to enable an enhanced biological efficacy, avoid the appearance of crystals, even under rigorous conditions, and / or generally present a good safety profile, with no or low hazard classification and / or ecotoxicology, even for complex associations of agricultural materials (e.g., at high loading) or for hydrophobic materials. These objectives are preferably achieved with the present invention, which is directed to the use of particular solvent compositions, comprising a sulfoxide (in particular dimethyl sulfoxide (DMSO)) and a mixture of specific esters, in agrochemical formulations, and to the corresponding agrochemical formulations.

[0017] In the present description, and unless otherwise indicated:

[0018] - the expression "at least one" is equivalent to the expression "one or more" and can be replaced therewith;

[0019] - the expression “greater than” is intended to mean an open range which is strictly greater, and therefore that the limit is not included.

[0020] The term solvent may especially denote a product that is liquid at the usage temperature, which may contribute to rendering a solid substance liquid, or to preventing / retarding the solidification or crystallisation of material in a liquid form. It may generally have a melting point less than or equal to 20 °C, in particular 5 °C, for example 0 °C.

[0021] A first embodiment (A) of the invention is the use, as a solvent in an agrochemical (agriculture) formulation, of a composition (also called solvent composition or solvent blend) comprising:

[0022] (i) a sulfoxide and

[0023] (ii) a mixture (also called blend) of dimethyl glutarate, at least one (in particular only one) ester of succinic acid and at least one (in particular only one) ester of adipic acid, in the absence or substantial absence of other organic solvents.

[0024] Particularly, this first embodiment (A) of the invention relates to the use, as a solvent in an agrochemical formulation, of a composition (also called solvent composition or solvent blend) comprising:

[0025] (i) a sulfoxide in an amount ranging from 20 to 60 %, in particular from 30 to 55 %, for instance from 30 to 40 %, by weight with respect to the total weight of the composition, and

[0026] (ii) a mixture (also called blend), in an amount ranging from 40 to 80 %, in particular from 45 to 70 %, for instance from 60 to 70 %, by weight with respect to the total weight of the composition, of dimethyl glutarate, at least one (in particular only one) ester of succinic acid and at least one (in particular only one) ester of adipic acid, in the absence or substantial absence of other organic solvents.

[0027] In the present description, in particular of the first embodiment of the invention, the expression “in the substantial absence of other organic solvents” preferably means that no other organic solvent (than the sulfoxide and the mixture (ii), i.e. than the sulfoxide andthe dimethyl glutarate, the at least one ester of succinic acid and the at least one ester of adipic acid) in an amount of at least 1 %, in particular greater than 0.5 %, for example greater than 0.1 %, or even greater than 0.5 %, by weight with respect to the total weight of the composition, is used.

[0028] More particularly, the use according to this first embodiment can be carried out in the absence of other organic solvents.

[0029] The use according to this first embodiment can be carried out in the absence or substantial absence of inorganic solvents, with the exception, generally, of water.

[0030] In a preferred variant of the first embodiment (A) of the invention, the said composition (also called solvent composition or solvent blend) comprises (ii) a mixture (also called blend) of dimethyl glutarate, dimethyl succinate and dimethyl adipate.

[0031] Preferably, in this variant, the said mixture (also called blend) (ii) comprises 55 to 75 % of dimethyl glutarate, 15 to 30 % of dimethyl succinate and 8 to 20 % of dimethyl adipate, by weight with respect to the total weight of the mixture (ii).

[0032] For instance, in this variant, the said mixture (ii) comprises 60 to 70 % of dimethyl glutarate, 20 to 25 % of dimethyl succinate and 9 to 15 % of dimethyl adipate, by weight with respect to the total weight of the mixture (ii).

[0033] Rhodiasolv® RPDE, marketed by Syensqo, is an example of blend (ii).

[0034] Moreover, in this preferred variant of the first embodiment (A) of the invention, the said composition (also called solvent composition or solvent blend) may comprise (i) a sulfoxide in an amount ranging from 20 to 50 %, preferably ranging from 25 to 45 %, in particular ranging from 30 to 40 %, by weight with respect to the total weight of said composition.

[0035] And, in this variant, the said composition (also called solvent composition or solvent blend) may comprise (ii) a mixture (also called blend) of dimethyl glutarate, dimethyl succinate and dimethyl adipate, in an amount ranging from 50 to 80 %, preferably ranging from 55 to 75 %, in particular ranging from 60 to 70 %, by weight with respect to the total weight of said composition.

[0036] In the first embodiment (A) of the invention, and particularly in its preferred variant, the sulfoxide is preferably dimethyl sulfoxide (DMSO).

[0037] A second embodiment (B) of the invention is the use, as a solvent in an agrochemical (agriculture) formulation, of a composition comprising:

[0038] (i) a sulfoxide in an amount ranging from 30 to 60 %, in particular from 30 to 40 %, by weight with respect to the total weight of the composition, and

[0039] (ii) a mixture of dimethyl glutarate, at least one (in particular only one) ester of succinic acid and at least one (in particular only one) ester of adipic acid.

[0040] In this second embodiment (B) of the invention, the said composition (also called solvent composition or solvent blend) may comprise (ii) a mixture (also called blend) of dimethyl glutarate, at least one (in particular only one) ester of succinic acid and at least one (in particular only one) ester of adipic acid in an amount ranging from 40 to 70 %, in particular from 60 to 70 %, by weight with respect to the total weight of the composition.

[0041] In a preferred variant of the second embodiment (B) of the invention, the said composition (also called solvent composition or solvent blend) comprises (ii) a mixture (also called blend) of dimethyl glutarate, dimethyl succinate and dimethyl adipate.

[0042] Preferably, in this variant, the said mixture (also called blend) (ii) comprises 55 to 75 % of dimethyl glutarate, 15 to 30 % of dimethyl succinate and 8 to 20 % of dimethyl adipate, by weight with respect to the total weight of the mixture (ii).

[0043] For instance, in this variant, the said mixture (ii) comprises 60 to 70 % of dimethyl glutarate, 20 to 25 % of dimethyl succinate and 9 to 15 % of dimethyl adipate, by weight with respect to the total weight of the mixture (ii).

[0044] Rhodiasolv® RPDE, marketed by Syensqo, is an example of blend (ii).

[0045] Moreover, in this preferred variant of the second embodiment (B) of the invention, the said composition (also called solvent composition or solvent blend) may comprise (i) a sulfoxide in an amount ranging from 30 to 50 %, preferably ranging from 30 to 45 %, in particular ranging from 30 to 40 %, by weight with respect to the total weight of said composition. And, in this variant, the said composition (also called solvent composition or solvent blend) may comprise (ii) a mixture (also called blend) of dimethyl glutarate, dimethyl succinate and dimethyl adipate, in an amount ranging from 50 to 70 %, preferably ranging from 55 to 70 %, in particular ranging from 60 to 70 %, by weight with respect to the total weight of said composition.

[0046] Generally, the second embodiment (B) of the invention can be carried out with at least one other organic solvent or in the absence or substantial absence of other organic solvents.

[0047] The use according to the second embodiment (B) of the invention can be carried out in the absence or substantial absence of inorganic solvents, with the exception, generally, of water, or with inorganic solvent(s).

[0048] In the second embodiment (B) of the invention, and particularly in its preferred variant, the sulfoxide is preferably dimethyl sulfoxide (DMSO).

[0049] Generally, in the use according to the invention, in particular in the first (A) and second (B) embodiments of the invention and their preferred variants, the said composition as described above ((i) + (ii)), may represent from 10 to 99 % by weight, preferentially from 20 to 95 % by weight, in particular from 30 to 90 % by weight, for instance from 30 to 80 % by weight, relative to the total weight of the agrochemical formulation.

[0050] The use according to the present invention, in particular the first (A) and second (B) embodiments of the invention and their preferred variants, may be preferably carried out in the presence of at least one emulsifier.

[0051] Emulsifiers are known as being agents intended to facilitate emulsification after the formulation is placed in the presence of water, and / or stabilisation (over time and / or in temperature) of the emulsion, for example by avoiding separation of the phases.

[0052] The use according to the present invention, in particular the first (A) and second (B) embodiments of the invention and their preferred variants, may be carried out in the presence of water. It has been surprisingly found the solvent compositions ((i) + (ii)) used according to the invention have a great solubilization efficiency. In particular, they preferably present a good modularity, a good potential for solubilization of significant quantities of agricultural materials (active ingredients), and a high compatibility with several agricultural materials combined together (association of agricultural materials, also called “combo”), in order for example to enable an enhanced biological efficacy.

[0053] They show advantageously excellent solubilization performances on a wide range of agricultural materials, such as pesticides, and more particularly fungicides, herbicides, and combos of such agricultural materials, which may it possible to reach high agriculture material (in particular key active ingredient) concentrations in agrochemical formulations (particularly in the form of emulsifiable concentrates (EC) for example) that are stable on ageing even at low temperature.

[0054] Further, it has been noted that the specific solvent compositions used according to the invention can preferably guarantee good performances at dilution, even for high loading formulations, and avoid / retard the appearance of crystals, even under rigorous conditions.

[0055] In addition, the specific solvent compositions used according to the invention present a good safety profile, advantageously with no or low hazard classification and ecotoxicology.

[0056] Moreover, it has been surprisingly found that the specific solvent compositions used according to the invention, forming by the specific combination of (i) dimethyl sulfoxide (DMSO) and (ii) a particular mixture of esters, preferably show a synergetic effect in comparison with each solvent alone (i.e. in comparison with DMSO alone or with the mixture (ii) alone), in terms of solubilization (of agriculture materials or combo of agriculture materials) performance, and / or in terms of stability in particular at low temperature. For example, the use of DMSO alone results in high crystallization issues for agrochemical formulations stored or used in particular at low temperatures, for example at 0 °C and below.

[0057] Furthermore, the above-mentioned performances and properties are advantageously obtained without using other organic solvent(s) in addition to dimethyl sulfoxide and the particular mixture (ii) of esters, as especially mentioned in the first (A) embodiment of the invention (and in the third (A’) embodiment of the invention as described below). A subject-matter of the invention is also the use, as a solvent, of the composition (also called solvent composition or solvent blend) as defined above in the first embodiment (A) of the invention, and in particular in its preferred variant, in the absence or substantial absence of other organic solvents, for preparing an agrochemical (agriculture) formulation or for the solubilization of agriculture material(s) in an agrochemical (agriculture) formulation.

[0058] Another subject matter the invention is also the use, as a solvent, of the composition (also called solvent composition or solvent blend) as defined above in the second embodiment (B) of the invention, and in particular in its preferred variant, in the absence or substantial absence of other organic solvents, for preparing an agrochemical (agriculture) formulation or for the solubilization of agriculture material(s) in an agrochemical (agriculture) formulation.

[0059] The present invention is also relative to an agrochemical (agriculture) formulation comprising at least one agricultural material and, as solvent, the composition (also called solvent composition or solvent blend) comprising (i) a sulfoxide and a mixture (also called blend) (ii) as described above, in accordance with embodiments (A’) or (B’) below. It can comprise optionally at least one emulsifier, preferably a surfactant, and optionally water.

[0060] Preferably, the agrochemical formulation according to the invention is an agrochemical formulation with a high concentration of agricultural material(s). The use of concentrated formulations is in particular advantageous for economic reasons (by making it possible to reduce the total weight of the formulations, and consequently their transport costs), the concentrated formulation then being generally diluted to the desired concentration by the final user.

[0061] An “agrochemical (or agriculture) formulation” is intended to denote a composition which, either use in its concentrated form or in dilution in water to a targeted use rate, causes or provides a beneficial and / or a useful effect in agriculture and / or provides a biological activity in a seed, a plant, soil, for example to seeds to control pests and / or to regulate the growth of plants and / or to induce the defense response in plants and / or to enhance metabolic and physiological processes within plants and soils. The agrochemical formulation is for example described in T.Tadros (ed.), Encyclopedia of Colloid and Interface Science, Springer-Verlag Berlin Heidelberg, 2013, pp. 3-80.

[0062] According to the invention, the “agrochemical (or agriculture) formulation” is generally a composition comprising the composition (i) + (ii), as solvent, and at least one agricultural material (preferably at least one pesticide), optionally at least one emulsifier, and optionally water.

[0063] As mentioned previously, agriculture uses many agricultural materials. They are also referred to as active plant-protection products or active materials or active substances.

[0064] As used herein, the term “agricultural material” means an active ingredient (“active”) used in particular to the practice of farming, including cultivation of the soil for the growing of crops. However, the use of agricultural materials is not limited to application to crops. Agricultural materials may be applied to any surface, e.g., for the purpose of cleaning or aiding or inhibiting growth of a living organism. Other noncrop applications include, but are not limited to, application to an animal, e.g. livestock, application to turf and ornamentals, and application to railroad weed.

[0065] Agricultural materials are generally products in pure or highly concentrated form, generally not soluble in water and known to the person skilled in the art.

[0066] Depending on the water solubility of the agricultural materials and their loading in the targeted formulation, it can be very challenging to identify suitable solvents to obtain a chemically and physically stable formulation.

[0067] For agricultural materials with a low or relatively low water solubility, the use of appropriate solvents is therefore interesting to prepare concentrated liquid formulations. Such concentrated formulations of agricultural materials can generally be diluted prior to agricultural use. The dilution effected by the farmer is generally performed by mixing the agrochemical formulation with water.

[0068] Preferably, the agricultural materials are water-insoluble agricultural materials, at 20°C and at atmospheric pressure (i.e., 1.013xl05Pa).

[0069] Generally, the agricultural materials are soluble in water to no more than lOOg / L, even more preferentially no more than 20 g / L, in particular no more than 5 g / L, for instance no more than 1 g / L and even no more than 0.2 g / L, at 20°C and at atmospheric pressure (i.e., 1.013xl05Pa).

[0070] Preferably, the agricultural materials are chosen from pesticides, nutrients, biostimulants, plant growth regulators, and mixtures thereof. Advantageously, the agrochemical formulation according to the invention may comprise at least one pesticide.

[0071] The agrochemical formulation may comprise only one pesticide or (a combination of different pesticides (for instance two or three pesticides).

[0072] For example, these pesticides may be chosen from herbicides, fungicides, insecticides, acaricides, algicides, molluscicides, miticides, nematicides, biocides and rodenticides.

[0073] The person skilled in the art is familiar with such pesticides. Specific examples of pesticides can be found in the book “Sittig’s handbook of Pesticides and Agricultural Chemicals”, 2ndedition, William Andrew Publishing, 2015.

[0074] A third embodiment (A’) of the invention is an agrochemical (agriculture) formulation comprising: a) at least one agricultural material, b) the composition, as solvent, as defined above in the first embodiment (A) of the invention, said formulation being free or substantially free of other organic solvents.

[0075] This third embodiment (A’) of the invention is then an agrochemical formulation comprising: a) at least one agricultural material, b) a composition, as solvent, comprising:

[0076] (i) a sulfoxide and

[0077] (ii) a mixture (also called blend) of dimethyl glutarate, at least one (in particular only one) ester of succinic acid and at least one (in particular only one) ester of adipic acid, said formulation being free or substantially free of other organic solvents.

[0078] Particularly, in the agrochemical formulation according to this third embodiment (A’) of the invention, the said composition, as solvent, can comprise:

[0079] (i) a sulfoxide in an amount ranging from 20 to 60 %, in particular from 30 to 55 %, for instance from 30 to 40 %, by weight with respect to the total weight of said composition, and

[0080] (ii) a mixture (also called blend), in an amount ranging from 40 to 80 %, in particular from 45 to 70 %, for instance from 60 to 70 %, by weight with respect to the total weight of the said composition, of dimethyl glutarate, at least one (in particular only one) ester of succinic acid and at least one (in particular only one) ester of adipic acid, said formulation being free or substantially free of other organic solvents.

[0081] In the present description, in particular of the third embodiment of the invention, the expression “substantially free of other organic solvents” preferably means that no other organic solvent (than the sulfoxide and the mixture (ii), i.e. than the sulfoxide and the dimethyl glutarate, the at least one ester of succinic acid and the at least one ester of adipic acid) in an amount of at least 1 %, in particular greater than 0.5 %, for example greater than 0.1 %, or even greater than 0.5 %, by weight with respect to the total weight of the said composition ((i) and (ii)), is present in the agrochemical formulation.

[0082] More particularly, the agrochemical formulation according to this third embodiment can be free of other organic solvents.

[0083] The agrochemical formulation according to this third embodiment can be free or substantially free of inorganic solvents, with the exception, generally, of water.

[0084] In a preferred variant of the third embodiment (A’) of the invention, the said composition, as solvent, contained in the agrochemical formulation, comprises (ii) a mixture (also called blend) of dimethyl glutarate, dimethyl succinate and dimethyl adipate.

[0085] Preferably, in this variant, the said mixture (also called blend) (ii) comprises 55 to 75 % of dimethyl glutarate, 15 to 30 % of dimethyl succinate and 8 to 20 % of dimethyl adipate, by weight with respect to the total weight of the mixture (ii).

[0086] For instance, in this variant, the said mixture (ii) comprises 60 to 70 % of dimethyl glutarate, 20 to 25 % of dimethyl succinate and 9 to 15 % of dimethyl adipate, by weight with respect to the total weight of the mixture (ii).

[0087] Rhodiasolv® RPDE, marketed by Syensqo, is an example of blend (ii).

[0088] Moreover, in this preferred variant of the third embodiment (A’) of the invention, the said composition, as solvent, contained in the agrochemical formulation, may comprise (i) a sulfoxide in an amount ranging from 20 to 50 %, preferably ranging from 25 to 45 %, in particular ranging from 30 to 40 %, by weight with respect to the total weight of said composition. And, in this variant, the said composition, as solvent, contained in the agrochemical formulation, may comprise (ii) a mixture (also called blend) of dimethyl glutarate, dimethyl succinate and dimethyl adipate, in an amount ranging from 50 to 80 %, preferably ranging from 55 to 75 %, in particular ranging from 60 to 70 %, by weight with respect to the total weight of said composition.

[0089] In the third embodiment (A’) of the invention, and particularly in its preferred variant, the sulfoxide is preferably dimethyl sulfoxide (DMSO).

[0090] A fourth embodiment (B’) of the invention is an agrochemical (agriculture) formulation comprising: a) at least one agricultural material, b) the composition, as solvent, as defined above in the second embodiment (B) of the invention.

[0091] This fourth embodiment (B’) of the invention is then an agrochemical formulation comprising: a) at least one agricultural material, b) a composition, as solvent, comprising:

[0092] (i) a sulfoxide in an amount ranging from 30 to 60 %, in particular from 30 to 40 %, by weight with respect to the total weight of said composition, and

[0093] (ii) a mixture (also called blend) of dimethyl glutarate, at least one (in particular only one) ester of succinic acid and at least one (in particular only one) ester of adipic acid.

[0094] In this fourth embodiment (B) of the invention, the said composition, as solvent, contained in the agrochemical formulation, may comprise (ii) a mixture (also called blend) of dimethyl glutarate, at least one (in particular only one) ester of succinic acid and at least one (in particular only one) ester of adipic acid in an amount ranging from 40 to 70 %, in particular from 60 to 70 %, by weight with respect to the total weight of said composition.

[0095] In a preferred variant of the fourth embodiment (B’) of the invention, the said composition, as solvent, contained in the agrochemical composition, comprises (ii) a mixture (also called blend) of dimethyl glutarate, dimethyl succinate and dimethyl adipate. Preferably, in this variant, the said mixture (also called blend) (ii) comprises 55 to 75 % of dimethyl glutarate, 15 to 30 % of dimethyl succinate and 8 to 20 % of dimethyl adipate, by weight with respect to the total weight of the mixture (ii).

[0096] For instance, in this variant, the said mixture (ii) comprises 60 to 70 % of dimethyl glutarate, 20 to 25 % of dimethyl succinate and 9 to 15 % of dimethyl adipate, by weight with respect to the total weight of the mixture (ii).

[0097] Rhodiasolv® RPDE, marketed by Syensqo, is an example of blend (ii).

[0098] Moreover, in this preferred variant of the fourth embodiment (B’) of the invention, the said composition, as solvent, contained in the agrochemical formulation, may comprise (i) a sulfoxide in an amount ranging from 30 to 50 %, preferably ranging from 30 to 45 %, in particular ranging from 30 to 40 %, by weight with respect to the total weight of said composition.

[0099] And, in this variant, the said composition, as solvent, contained in the agrochemical formulation, may comprise (ii) a mixture (also called blend) of dimethyl glutarate, dimethyl succinate and dimethyl adipate, in an amount ranging from 50 to 70 %, preferably ranging from 55 to 70 %, in particular ranging from 60 to 70 %, by weight with respect to the total weight of said composition.

[0100] Generally, the agrochemical formulation according to the fourth embodiment (B’) of the invention can comprise at least one other organic solvent or can be free or substantially free of other organic solvents.

[0101] The agrochemical formulation according to the fourth embodiment (B’) of the invention can be free or substantially free of inorganic solvents, with the exception, generally, of water, or can comprise inorganic solvent(s).

[0102] In the fourth embodiment (B’) of the invention, and particularly in its preferred variant, the sulfoxide is preferably dimethyl sulfoxide (DMSO).

[0103] Generally, the said composition ((i) + (ii)) as described above, comprised as solvent in the agrochemical formulation according to the invention, in particular in the third (A’) and fourth (B’) embodiments of the invention and their preferred variants, may represent from 9 to 99 % by weight, preferentially from 20 to 95 % by weight, in particular from 30 to 90 % by weight, for instance from 30 to 80 % by weight, relative to the total weight of the agrochemical formulation. Within the context of the invention, it is possible to combine several agricultural materials in one agrochemical formulation.

[0104] Generally, the amount of agricultural material(s) in the agrochemical formulation may range from 0.01 to 90 % by weight, preferentially from 0.1 to 80 % by weight; more preferentially from 0.5 to 70 % by weight; better from 1 to 65 % by weight, in particular from 5 to 60 % by weight, and for instance from 10 to 60 % by weight, relative to the total weight of the agrochemical formulation.

[0105] According to an implementation of the invention (concentrated composition), the total content of agricultural material(s) in the agrochemical formulation may range from 5 to 90 % by weight, preferentially from 5 to 70 % by weight, in particular from 5 to 60 % by weight, and for instance from 10 to 60 % by weight, relative to the total weight of the agrochemical formulation.

[0106] According to another implementation of the invention (diluted composition), the total content of agricultural material(s) in the agrochemical formulation may range from 0.01 to 3 % by weight, preferentially from 0.05 to 2 % by weight, and in particular from 0.1 to 1% by weight, relative to the total weight of the agrochemical formulation.

[0107] The agrochemical formulation according to the invention, in particular the third (A’) and fourth (B’) embodiments of the invention and their preferred variants, may preferably comprise at least one emulsifier.

[0108] Emulsifiers are known as being agents intended to facilitate emulsification after the formulation is placed in the presence of water, and / or stabilization (over time and / or in temperature) of the emulsion, for example by avoiding separation of the phases.

[0109] The agrochemical formulation according to the invention, in particular the third (A’) and fourth (B’) embodiments of the invention and their preferred variants, may comprise water.

[0110] The agrochemical formulation according to the invention may optionally comprise at least one nutrient.

[0111] Nutrients refer to chemical elements and compounds which are desired or necessary to promote or improve plant growth. Nutrients generally are described as macronutrients or micronutrients. Suitable nutrients for use in the agrochemical formulations according to the invention may be micronutrient compounds, preferably those which are solid at 20 °C or are partially soluble.

[0112] Micronutrients typically refer to trace metals or trace elements, and are often applied in lower doses. Suitable micronutrients include trace elements selected from zinc, boron, chlorine, copper, iron, molybdenum, and manganese.

[0113] The micronutrients may be in a soluble form or included as insoluble solids, and may be in the form of salts or chelates. Preferably, the micronutrient is in the form of a carbonate or oxide.

[0114] Preferably, the micronutrients may be selected from zinc, calcium, molybdenum or manganese, or magnesium. More preferentially micronutrients for use in the agrochemical formulation according to the invention may be selected from zinc oxide, manganese carbonate, manganese oxide, or calcium carbonate.

[0115] The agrochemical formulation according to the present invention may further comprise at least one macronutrient.

[0116] Macronutrients typically refer to those comprising nitrogen, phosphorus, and potassium, and include fertilisers such as ammonium sulphate, and water conditioning agents. Suitable macronutrients include fertilisers and other nitrogen, phosphorus, or sulphur containing compounds, and water conditioning agents.

[0117] Suitable fertilisers include inorganic fertilisers that provide nutrients such as nitrogen, phosphorus, potassium or sulphur. Examples of such fertilisers include: for nitrogen as the nutrient: nitrates and or ammonium salts such as ammonium nitrate, including in combination with urea e.g. as urean type materials, calcium ammonium nitrate, ammonium sulphate nitrate, ammonium phosphates, particularly mono-ammonium phosphate, di-ammonium phosphate and ammonium polyphosphate, ammonium sulphate, and the less commonly used calcium nitrate, sodium nitrate, potassium nitrate and ammonium chloride; for phosphorus as the nutrient: acidic forms of phosphorus such as phosphoric, pyrophosphoric or polyphosphoric acids, but more usually salt forms such as ammonium phosphates, particularly mono-ammonium phosphate, di-ammonium phosphate, and ammonium polyphosphate, potassium phosphates, particularly potassium dihydrogen phosphate and potassium polyphosphate; for sulphur as the nutrient: ammonium sulphate and potassium sulphate, e.g. the mixed sulphate with magnesium.

[0118] The agrochemical formulation according to the invention may optionally comprise at least one biostimulant.

[0119] The term “biostimulant” is preferably intended to mean a compound which may enhance metabolic or physiological processes such as respiration, photosynthesis, nucleic acid uptake, ion uptake, nutrient delivery, or a combination thereof.

[0120] Generally, this is a substance or microorganism that, when applied to seeds, plants or on the rhizosphere, can stimulate natural processes to enhance or benefit nutrient uptake, nutrient use efficiency, tolerance to abiotic stress, or crop quality and yield.

[0121] Non-limiting examples of biostimulants include seaweed extracts (e.g., ascophyllum nodosum), humic acids (e.g., potassium humate), fulvic acids, myoinositol, glycine, and combinations thereof.

[0122] The agrochemical formulation according to the invention may optionally comprise at least one plant growth regulator.

[0123] Plant growth regulators mean active ingredients used to influence the growth characteristics of plants. Examples of plant growth regulators which may be used in the present invention include, but are not limited to: 1 -naphthaleneacetic acid, 1- naphthaleneacetic acid -salt, 1-napthol, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4- DB, 2,4-DEP, 2,3,5-triiodobenzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2- naphthoxyacetic acid, 2-naphthoxyacetic acid sodium salt, 3-chloro-4- hydroxyphenylacetic acid, 3-indoleacetic acid, 4-biphenylacetic acid, 4- chlorophenoxyacetic acid (4-CPA), 4-hydroxyphenylacetic acid, 6- benzylaminopurine, auxindole, a-naphthaleneacetic acid K-salt, B-naphfhoxyacetic acid, p-chlorophenoxyacetic acid, dicamba, dichlorprop, fenoprop, indole-3 -acetic acid (IAA), indole-3 -acetyl-DL-aspartic acid, indole-3 -acetyl-DL-tryptophan, indole-

[0124] 3-acetyl-L-alanine, indole-3 -acetyl-L-valine, indole-3 -butyric acid (IB A), indole-3 - butyric acid K-salt, indole-3 -propionic acid; a-naphthaleneacetic acid, methyl indole- 3 -acetate, naphthaleneacetamide, naphthaleneacetic acid (NAA), phenylacetic acid, picloram, potassium naphthenate, sodium naphthenate, 4-hydroxyphenethyl alcohol,

[0125] 4-CPPU, 6-benzylaminopurine (BA), 6-(Y,Y-dimethylallylamino)purine (2iP), 2-iP- 2HC1, adenine, adenine hemisulfate, benzyladenine, kinetin, meta-topolin, N6- benzoyladenine, N- benzyl-9-(2-tetrahydropyranyl) adenine (BP A), N-(2-chloro-4- pyridyl)-N-phenylurea, gibberellic acid (GA3), gibberellins, gibberellins A4 + A7 (GA n), ethylene and abscisic acid.

[0126] The agrochemical formulation according to the invention may preferably comprise at least one surfactant.

[0127] Advantageously, the surfactants that may be used in the invention are chosen from anionic, non-ionic, cationic, amphoteric or zwitterionic surfactants, and mixtures thereof.

[0128] Preferentially, the surfactants are chosen from anionic surfactants, non-ionic surfactants, and mixtures thereof.

[0129] More preferentially, the surfactants are chosen from anionic surfactants, polyalkoxylated non-ionic surfactants, and mixtures thereof

[0130] The emulsifiers and surfactants that may be used are different from the agricultural materials.

[0131] By way of examples of anionic surfactants, mention may be made without any intended limitation thereto, of:

[0132] - alkylsulfonic acids, arylsulfonic acids, optionally substituted with one or more hydrocarbon groups, and the acid function of which is partly or totally salified, like Cs-Cso alkylsulfonic acids, more particularly C8-C30, preferably C10-C22 alkylsulfonic acids, benzenesulfonic acids, naphthalenesulfonic acids, substituted with one to three C1-C30, preferably C4-C16 alkyl and / or C2-C30, preferably C4-C16 alkenyl groups,

[0133] - mono- or di-esters of alkylsulfosuccinic acids, of which the linear or branched alkyl portion is optionally substituted with one or more linear or branched C2-C4 hydroxylated and / or alkoxylated (preferably ethoxylated, propyxylated, ethopropoxylated) groups,

[0134] - phosphate esters more particularly selected from among those comprising at least one linear or branched, saturated, unsaturated or aromatic hydrocarbon group, comprising 8 to 40 carbon atoms, preferably 10 to 30, optionally substituted with at least one alkoxylated (ethoxylated, propoxylated, ethopropoxylated) group. In addition, they comprise at least one phosphate ester group, mono- or di-esterified such that it is possible to have one or two free or partly or totally salified groups. The preferred phosphate esters are of the type of the mono- and di-esters of phosphoric acid and of alkoxylated (ethoxylated and / or propoxylated) mono-, di- or tri-styrylphenol, or alkoxylated (ethoxylated and / or propoxylated) mono-, di- or trialkylphenol, optionally substituted with one to four alkyl groups; of phosphoric acid and of an alkoxylated (ethoxylated or ethopropoxylated) Cs-Cso, preferably C10-C22 alcohol; of phosphoric acid and of a non-alkoxylated C8-C22, preferably C10-C22 alcohol,

[0135] - sulfate esters obtained from saturated or aromatic alcohols optionally substituted with one or more alkoxylated (ethoxylated, propoxylated, ethopropoxylated) groups, and for which the sulfate functions appear in the free acid form, or are partly or totally neutralised. As an example, mention may be made of sulfate esters more particularly obtained from saturated or unsaturated C8-C20 alcohols, which may comprise 1 to 8 alkoxylated (ethoxylated, propoxylated, ethopropoxylated) units ; sulfate esters obtained from polyalkoxylated phenol, substituted with 1 to 3 saturated or unsaturated C2-C30 hydroxycarbon groups, and in which the number of alkoxylated units is comprised between 2 and 40 ; the sulfate esters obtained from polyalkoxylated mono-, di- or tri-styrylphenol in which the number of alkoxylated units varies from 2 to 40.

[0136] The anionic surfactants may be in the acid form (they are potentially anionic), or in a partly or totally salified form with one counter-ion. The counter-ion may be an alkali metal, such as sodium or potassium, an alkaline earth metal, such as calcium, or moreover even an ammonium ion of formula N(R)4+in which the R groups, either identical or different, represent a hydrogen atom or a C1-C4 alkyl group optionally substituted with an oxygen atom.

[0137] By way of examples of non-ionic surfactants, mention may be made without any intended limitation thereto, of:

[0138] - polyalkoxylated (ethoxylated, propoxylated, ethopropoxylated) phenols substituted with at least one C4-C20, preferably C4-C12 alkyl group, or substituted with at least one alkylaryl group, the alkyl portion of which is a Ci-Ce alkyl. More particularly, the total number of alkloxylated units is comprised between 2 and 100. As an example, mention may be made of polyalkoxylated mono-, di- or tri- (phenylethyl) phenols, or polyalkoxylated nonylphenols. Amongst the ethoxylated and / or propoxylated, sulfated and / or phosphated di- or tri-styrylphenols, mention may be made of ethoxylated di-(phenyl-l-ethyl)phenol, containing 10 oxy ethylene units ; ethoxylated di-(phenyl-l-ethyl)phenol, containing 7 oxy ethylene units ; sulfated ethoxylated di-(phenyl-l-ethyl)phenol, containing 7 oxy ethylene units ; ethoxylated tri-(phenyl-l-ethyl)phenol, containing 8 oxyethylene units ; ethoxylated tri-(phenyl-l- ethyl)phenol, containing 16 oxy ethylene units ; sulfated ethoxylated tri -(phenyl- 1- ethyl)phenol, containing 16 oxy ethylene units ; ethoxylated tri -(phenyl- 1- ethyl)phenol, containing 20 oxy ethylene units ; phosphated ethoxylated tri-(phenyl-l- ethyl) phenol, containing 16 oxy ethylene units,

[0139] - polyalkoxylated (ethoxylated, propyxylated, ethopropoxylated) C6-C22 fatty acids or alcohols. The number of alkoxylated units is comprised between 1 and 60. The term ethoxylated fatty acid includes both the products obtained by ethoxylation of a fatty acid by ethylene oxide as well as those obtained by esterification of a fatty acid by a polyethylene glycol,

[0140] - polyalkoxylated (ethoxylated, propoxylated, ethopropoxylated) triglycerides of vegetable or animal origin. Thus, may be included triglycerides from lard, tallow, ground nut oil, butter oil, cotton seed oil, flax oil, olive oil, palm oil, grapeseed oil, fish oil, soya bean oil, castor oil, rapeseed oil, coprah oil, coconut oil, and comprising a total number of alkoxylated units comprised between 1 and 60. The term ethoxylated triglyceride makes reference both to products obtained by ethoxylation of a triglyceride with ethylene oxide as well as to those obtained by transesterification of a triglyceride with a polyethylene glycol,

[0141] - sorbitan esters, optionally polyalkoxylated (ethoxylated, propoxylated, ethopropoxylated), more particularly the cyclised sorbitol esters of C10-C20 fatty acids such as lauric acid, stearic acid, or oleic acid, and comprising a total number of alkoxylated units comprised between 2 and 50.

[0142] Useful emulsifiers are in particular the following products, all marketed by Syensqo:

[0143] - Soprophor® TSP / 724: a surfactant based on ethopropoxylated tri styrylphenol,

[0144] - Soprophor® 796 / P: a surfactant based on ethopropoxylated tri styrylphenol

[0145] - Soprophor® CY 8: a surfactant based on ethoxylated tri styrylphenol

[0146] - Soprophor® BSU: a surfactant based on ethoxylated tri styrylphenol

[0147] - Soprophor® S / 25: a surfactant based on ethoxylated tri styrylphenol

[0148] - Soprophor® 3D33: a surfactant based on ethoxylated tri styrylphenol phosphate - Soprophor® 4D / 384: a surfactant based on tri styrylphenol ethoxylate sulfate

[0149] - Soprophor® FL: a surfactant based on tri styrylphenol phosphate

[0150] - Alkamuls® RC: a surfactant based on ethoxylated castor oil

[0151] - Alkamuls® OR / 36: a surfactant based on ethoxylated castor oil

[0152] - Alkamuls® V02003: a surfactant based on ethoxylated castor oil

[0153] - Alkamuls® OL40: a surfactant based on ethoxylated sorbitan hexaoleate

[0154] - Alkamuls® 1720: a surfactant based on ethoxylated sorbitan ester.

[0155] - Geronol® TBE724: a surfactant based on ethopropoxylated tri styrylphenol

[0156] - Geronol® TEB25: a mixture of surfactants based on ethoxylated castor oil, calcium dodecyl benzene sulfonate and alkoxylated polymers

[0157] - Rhodacal® 60 / B: a surfactant based on dodecylbenzene sulphonate

[0158] - Rhodacal® 60 / BE: a surfactant based on dodecylbenzene sulphonate.

[0159] The total amount of emulsifier(s) possibly present in the agrochemical formulation may range from 0.05 to 40 % by weight, preferentially from 0.1 to 35 % by weight, more preferentially from 0.5 to 30 % by weight, in particular from 1 to 25 % by weight, for instance from 1 to 5 % by weight, relative to the total weight of the agrochemical formulation.

[0160] The total amount of surfactant(s) possibly present in the agrochemical formulation may range from 0.05 to 40 % by weight, preferentially from 0.1 to 35 % by weight, more preferentially from 0.5 to 30 % by weight, in particular from 1 to 25 % by weight, for instance from 1 to 5 % by weight, relative to the total weight of the agrochemical formulation.

[0161] Generally, the total amount of anionic surfactant(s) possibly present in the agrochemical formulation may range from 0.05 to 40 % by weight, preferentially from 0.1 to 35 % by weight, more preferentially from 0.5 to 30 % by weight, in particular from 1 to 25 % by weight, for instance from 1 to 5 % by weight, relative to the total weight of the agrochemical formulation.

[0162] Generally, the total amount of non-ionic surfactant(s), in particular polyalkoxylated non-ionic surfactant(s), possibly present in the agrochemical formulation may range from 0.05 to 40 % by weight, more preferentially from 0.1 to 35 % by weight, more preferentially from 0.5 to 30 % by weight, in particular from 1 to 25 % by weight, for instance from 1 to 5 % by weight, relative to the total weight of the agrochemical formulation.

[0163] Crystallisation inhibitors may also be present in the agrochemical formulations. Crystallisation inhibitors may be non-polyalkoxylated fatty alcohols or fatty acids, for example mention may be made of the product Alkamuls® OL700 marketed by Syensqo, alkanolamides, polymers.

[0164] Within the context of the invention, the agrochemical formulation may further contain one or more additives different from the ingredients described previously, and which are preferably chosen from viscosity modifying agents, suspending agents, antifoam agents and defoamers, in particular silicone antifoams and defoamers, antirebound agents, anti-leaching agents, penetration adjuvants, inert fillers, in particular mineral fillers, binders, anti-freeze agents, stabilisers, dyes, emetic agents, stickers (adhesion promoters), absorbents, dispersants, disintegration agents, wetting agents, preservatives and / or anti-microbials. Generally, the agrochemical formulation according to the invention contains less than 0.005 %, even less than 0.001 %, by weight of mannosylerythritol lipid, relative to the total weight of the agrochemical formulation; the agrochemical formulation according to the invention does not preferably contain mannosylerythritol lipid.

[0165] Each additive can be optionally present in the agrochemical formulation in an amount ranging from 0 to 20 % by weight, preferably from 0 to 10% by weight, in particular from 0 to 5 % by weight, for instance from 0 to 0.9 % by weight, relative to the total weight of the composition. Each additive can be for instance present in the agrochemical formulation in an amount ranging from 0.1 to 20 % by weight, in particular from 0.1 to 10 % by weight, relative to the total weight of the agrochemical formulation. Each additive can be present in the agrochemical formulation in an amount preferably ranging from 0 to 5 % by weight, notably from 0.1 to 5 % by weight, for instance from 0.1 to 0.9 % by weight, relative to the total weight of the agrochemical formulation. A person skilled in the art will be able to choose these optional additives and their amounts so that they do not harm the properties of the agrochemical formulations used in or in accordance with the present invention. Advantageously, within the context of the invention, the agrochemical formulation is in a liquid form, at 20 °C and at atmospheric pressure (i.e., 1.013 x 105Pa) and may be in the form of a concentrate of agricultural material(s), a diluted concentrate, or a sprayable diluted composition.

[0166] Different types of formulation may be used according to the different agricultural materials. The formulations that it is possible to use depend on the physical form of the agricultural materials (for example solid or liquid) and on its physicochemical properties in the presence of other compounds, such as water.

[0167] For practical reasons (for example for reasons of ease of handling), it may be preferred to use formulations in liquid form. Depending on the physicochemical properties of the different agricultural materials considered, formulations can be in the form of emulsifiable concentrates (EC), concentrated emulsions in water (EW), microemulsions (ME), suspoemulsions (SE), oil dispersions (OD), dispersible concentrates (DC), suspension concentrates (SC), capsule suspensions (CS), soluble liquids (SL), flowable concentrates for seed treatments (FS).

[0168] Preferably, the agrochemical formulation is here in the form of an emulsifiable concentrate (EC), concentrated emulsion in water (EW), microemulsion (ME), suspoemulsion (SE), oil dispersion (OD), dispersible concentrate (DC), capsule suspension (CS), soluble liquid (SL).

[0169] Particularly, the agrochemical formulation is in the form of an emulsifiable concentrate, an emulsion in water concentrate, a microemulsion concentrate, a suspoemulsion concentrate, an oil dispersion concentrate or a dispersible concentrate.

[0170] For instance, the agrochemical formulation is in the form of an emulsifiable concentrate (EC).

[0171] Within the context of the invention, the agrochemical formulation may be generally a concentrated agrochemical formulation and may be generally intended to be spread out over a cultivated field or a field to be cultivated, most often after dilution with water, in order to obtain a diluted formulation. Dilution is generally carried out by the farm operator, directly in a tank (“tank-mix”), for example in the tank of a device intended to spread out the formulation. This does not exclude the possibility of the farm operator adding other plant-protective products, for example fungicides, herbicides, pesticides, insecticides, fertilisers, adjuvants. Thus, the formulation may be used for preparing a formulation diluted in water of the agricultural material, by mixing at least one part by weight of concentrated formulation with at least 10 parts of water, preferably less than 10,000 parts of water. The dilution ratios and the amounts to be applied over the field generally depend on the agricultural material and on the desirable dose for treating the field, and this may be determined by the farm operator.

[0172] According to a variant of the invention, the agrochemical formulation is aqueous.

[0173] In this case, the water content of the agrochemical formulation may preferably range from 5 to 99 % by weight, more preferably from 20 to 95 % by weight, in particular from 25 to 90 % by weight, for instance from 25 to 85 % by weight, notably from 25 to 70 % by weight, relative to the total weight of the agrochemical formulation.

[0174] According to this variant, the pH preferably ranges from 1 to 11, and more particularly from 2.5 to 9.5.

[0175] The pH of the compositions can be adjusted to the desired value by means of basifying agents or acidifying agents.

[0176] According to a particular variant of the invention, the agrochemical formulation may advantageously comprise: a) from 0.01 to 90 % by weight, preferably from 5 to 60 % by weight, of at least one agricultural material, relative to the total weight of the agrochemical formulation, b) from 5 to 90 % by weight, preferably from 10 to 90 % by weight, in particular from 30 to 90 % by weight, for instance 30 to 80 % by weight, of the said composition ((i) + (ii)) as described above, as solvent, relative to the total weight of the agrochemical formulation, c) from 0.05 to 40 % by weight, preferably from 0.1 to 35 % by weight, more preferably from 0.5 to 30 % by weight, in particular from 1 to 25 % by weight, for instance from 1 to 5 % by weight, of at least one surfactant, relative to the total weight of the agrochemical formulation, d) from 5 to 90 % by weight, preferably from 10 to 80 % by weight, in particular from 25 to 70 % by weight, of water, relative to the total weight of the agrochemical formulation, in the absence or substantial absence of other organic solvents in the context of the first (A) and third (A’) embodiments of the invention. Known conventional methods for preparing agrochemical formulations or mixtures of solvents may be implemented. It is possible to undertake this by simply mixing the compounds.

[0177] Within the context of the invention, the agrochemical formulation may be used to kill or inhibit pests and / or clean and / or inhibit growth of undesired plants. The agrochemical formulation may enhance field crop production, in particular its yield.

[0178] The agrochemical formulation can be diluted and applied to at least one plant, area adjacent to a plant, soil adapted to support growth of a plant, root of a plant, foliage of a plant, and / or seed adapted to produce a plant, in a customary manner; for example by watering (drenching), drip irrigation, spraying, and / or atomizing.

[0179] The examples that follow illustrate the present invention.

[0180] Examples

[0181] In the present examples, the term solvent system is a composition and can design either a solvent alone or a blend of solvents.

[0182] The term combo of actives is used to describe an association of several (at least two) different agricultural materials.

[0183] Determination of the maximal solubility of an active or a combo of actives in a solvent system

[0184] The maximal solubility of an active or a combo of actives in a solvent system is characterised by visual observation. At a given concentration, if the mixture is limpid (with the naked eye), the active ingredient(s) is (are) considered to be soluble in the solvent system at this concentration. However, if a sedimentation of the active ingredient(s) appears, it is not soluble anymore in the solvent system and the maximal solubility is reached.

[0185] The maximal solubility is thus defined as the maximum amount of active ingredient(s) that can be dissolved in the solvent system, equal to the amount at which the mixture remains limpid (with the naked eye). Test 1 : Maximal solubility - Description of the test for actives alone (solo) in a solvent system

[0186] Each active ingredient is added little by little in different solvent systems. The solutions are magnetically stirred until complete dissolution. Then an additional amount of active ingredient is added and this operation is repeated until the last part of active ingredient added could not be dissolved anymore, taking care to stir the solution after each addition of active ingredient.

[0187] Test 2: Low temperature study - Description of the test for actives alone (solo) or combo of actives

[0188] Mixtures are prepared by solubilizing an active or combo of actives at a certain concentration in different solvent systems. Each active is individually weighted and added to the solvent system. Following observations are then carried out:

[0189] Visual observation at 25 °C - The appearance of the mixture is noted and the possible presence of crystals is investigated.

[0190] Visual observation at -5 °C - The mixture is placed for 7 days at -5 °C and the appearance of the mixture is noted as well as the possible presence of crystals (CIPAC MT39 test).

[0191] Visual observation at -5 °C with nucleation - A crystal of each active ingredient is introduced in the solution having spent 7 days at -5 °C to nucleate. The mixture is stirred and placed again for 7 additional days at -5 °C for nucleation. We note the aspect of the mixture and the presence of crystals is eventually identified (CIPAC MT39 test).

[0192] A solvent system was considered as a good system if the mixture (solo or combo of actives solvent system) formed a limpid solution (homogeneous liquid phase with the naked eye), while a solvent system is denoted as a bad system if two-phase system, presence of particles, sediments, crystals or turbid solution are obtained.

[0193] Example 1 : Solubilization of active ingredients (combo) in solvent systems

[0194] The following formulation is prepared according to the following protocol: Formulation A: 9 wt% of picoxystrobin are firstly added in the solvent system.

[0195] Then 4 wt% of cyproconazole are added to the mixture, which is magnetically stirred.

[0196] Blend I in accordance with the invention consists in 35.5 % by weight of dimethyl sulfoxide (DMSO) and 64.5 % by weight of Rhodiasolv® RPDE, relative to the total weight of the blend.

[0197] The characterization is carried out following the method described above.

[0198] RT: Room Temperature (25 °C)

[0199] This formulation highlights that the use of a solvent system according to the invention is able to solubilize challenging combo of active ingredients.

[0200] The formulation remains stable for 2 weeks at -5 °C, even with the additional step of nucleation for the last 7 days.

[0201] Example 2: Solubilization of active ingredients (combo) in solvent systems

[0202] The following formulation is prepared according to the following protocol:

[0203] Formulation B: 5.0 wt% of azoxy strobin are firstly added in the solvent system. Then 9.0 wt% of tebuconazole are added to the mixture, and finally 18.0 wt% of prochloraz are added. The solution is then magnetically stirred. Blend I in accordance with the invention consists in 35.5 % by weight of dimethyl sulfoxide (DMSO) and 64.5 % by weight of Rhodiasolv® RPDE, relative to the total weight of the blend.

[0204] The characterization is carried out following the method described above.

[0205] RT: Room Temperature (25 °C)

[0206] *(not necessary to perform the test at low temperature, as the formulation is already not limpid at 25 °C)

[0207] This formulation highlights that the use of a solvent system according to the invention is able to solubilize challenging combo of active ingredients, better than each solvent alone. A synergistic effect of the blend is showed.

[0208] The formulation remains stable for 2 weeks at -5 °C, even with the additional step of nucleation for the last 7 days.

[0209] Example 3 : Solubilization of active ingredients (combo) in solvent systems

[0210] The following formulation is prepared according to the following protocol: Formulation C: 18.9 wt% of tebuconazole are firstly added in the solvent system. Then 11.3 wt% of picoxystrobin are added to the mixture, which is magnetically stirred.

[0211] Blend I in accordance with the invention consists in 35.5 % by weight of dimethyl sulfoxide (DMSO) and 64.5 % by weight of Rhodiasolv® RPDE, relative to the total weight of the blend.

[0212] The characterization is carried out following the method described above.

[0213] RT: Room Temperature (25 °C)

[0214] *(not necessary to perform the test at low temperature, as the formulation is already not limpid at 25 °C)

[0215] This formulation highlights that the use of a solvent system according to the invention is able to solubilize challenging combo of active ingredients, better than each solvent alone. A synergistic effect of the blend is showed.

[0216] The formulation remains stable for 2 weeks at -5 °C, even with the additional step of nucleation for the last 7 days. Example 4: Solubilization of active ingredient (solo) in solvent systems

[0217] The formulation containing 250 g / L of tebuconazole in the solvent system is prepared by adding the active ingredient in the solvent system, and the mixture is magnetically stirred.

[0218] Blend I in accordance with the invention consists in 35.5 % by weight of dimethyl sulfoxide (DMSO) and 64.5 % by weight of Rhodiasolv® RPDE, relative to the total weight of the blend.

[0219] The characterization is carried out following the method described above.

[0220] RT: Room Temperature (25 °C)

[0221] *(not necessary to perform the test at low temperature, as the formulation is already not limpid at 25 °C)

[0222] This formulation highlights that the use of a solvent system according to the invention is able to solubilize challenging loading of tebuconazole, better than each solvent alone. A synergistic effect of the blend is showed.

[0223] The formulation remains stable for 2 weeks at -5 °C, even with the additional step of nucleation for the last 7 days. Example 5: Solubilization of active ingredient (solo) in a solvent system

[0224] The formulation containing 18 g / L of abamectin in the solvent system is prepared by adding the active ingredient in the solvent system, and the mixture is magnetically stirred.

[0225] Blend I in accordance with the invention consists in 35.5 % by weight of dimethyl sulfoxide (DMSO) and 64.5 % by weight of Rhodiasolv® RPDE, relative to the total weight of the blend.

[0226] The characterization is carried out following the method described above.

[0227] RT: Room Temperature (25 °C)

[0228] This formulation highlights that the use of a solvent system according to the invention is able to solubilize challenging loading of abamectin.

[0229] The formulation remains stable for 2 weeks at -5°C, even with the additional step of nucleation for the last 7 days.

[0230] Example 6: Solubilization of active ingredients (solo) in solvent systems

[0231] The maximal solubility of tebuconazole, azoxystrobin and pinoxaden are measured (at room temperature (25 °C)) in Rhodiasolv® RPDE and dimethyl sulfoxide (DMSO), as comparative use, and in blend I, as use according to the invention, according to the protocol described above. Blend I in accordance with the invention consists in 35.5 % by weight of dimethyl sulfoxide (DMSO) and 64.5 % by weight of Rhodiasolv® RPDE, relative to the total weight of the blend. Values of maximal solubility (in g / lOOg of solvent) are summarised in the table below:

[0232] *Frozen at cold temperature (0 °C) These data show that the use of a solvent system according to the invention provides very improved performances in terms of solubilizing properties compared to the use of Rhodiasolv® RPDE. And if the performances are here equal or below to the use of DMSO, DMSO cannot be used as such because it freezes at classical low temperatures, at -5 °C and even at 0 °C, which is not at all satisfactory, in particular for storage stability.

Claims

CLAIMS1. Use, as a solvent in an agrochemical formulation, of a composition comprising:(i) a sulfoxide and(ii) a mixture of dimethyl glutarate, at least one ester of succinic acid and at least one ester of adipic acid, in the absence or substantial absence of other organic solvents.

2. Use according to claim 1, wherein the said composition comprises:(i) a sulfoxide in an amount ranging from 20 to 60 %, in particular from 30 to 55 %, by weight with respect to the total weight of the composition, and(ii) a mixture, in an amount ranging from 40 to 80 %, in particular from 45 to 70 %, by weight with respect to the total weight of the composition, of dimethyl glutarate, at least one ester of succinic acid and at least one ester of adipic acid, in the absence or substantial absence of other organic solvents.

3. Use according to any one of claims 1 and 2, wherein no other organic solvent in an amount of at least 1 %, in particular greater than 0.5 %, for example greater than 0.1 %, by weight with respect to the total weight of the composition, is used.

4. Use according to any one of claims 1 to 3, wherein the said composition comprises (ii) a mixture of dimethyl glutarate, dimethyl succinate and dimethyl adipate.

5. Use according to claim 4, wherein the said mixture (ii) comprises 55 to 75 % of dimethyl glutarate, 15 to 30 % of dimethyl succinate and 8 to 20 % of dimethyl adipate, by weight with respect to the total weight of the mixture (ii).

6. Use according to any one of claims 4 and 5, wherein the said composition comprises (i) a sulfoxide in an amount ranging from 20 to 50 %, preferably rangingfrom 25 to 45 %, in particular ranging from 30 to 40 %, by weight with respect to the total weight of the composition.

7. Use, as a solvent in an agrochemical formulation, of a composition comprising:(i) a sulfoxide in an amount ranging from 30 to 60 % by weight with respect to the total weight of the composition, and(ii) a mixture of dimethyl glutarate, at least one ester of succinic acid and at least one ester of adipic acid.

8. Use according to claim 7, wherein the said composition comprises (ii) a mixture of dimethyl glutarate, dimethyl succinate and dimethyl adipate.

9. Use according to claim 8, wherein the said mixture (ii) comprises 55 to 75 % of dimethyl glutarate, 15 to 30 % of dimethyl succinate and 8 to 20 % of dimethyl adipate, by weight with respect to the total weight of the mixture (ii).

10. Use according to any one of claims 7 to 9, wherein the said composition comprises (i) a sulfoxide in an amount ranging from 30 to 50 %, preferably ranging from 30 to 45 %, in particular ranging from 30 to 40 %, by weight with respect to the total weight of the composition.

11. Use according to any one of claims 1 to 10, in the presence of at least one emulsifier.

12. Use according to any one of claims 1 to 11, wherein the said sulfoxide is dimethyl sulfoxide (DMSO).

13. Agrochemical formulation comprising: a) at least one agricultural material, b) the composition, as solvent, as defined in any one of claims 1 to 6, said formulation being free or substantially free of other organic solvents.

14. Agrochemical formulation according to claim 13, said formulation not comprising other organic solvents in an amount of at least 1 %, in particular greater than 0.5 %, for example greater than 0.1 %, by weight with respect to the total weight of the composition as solvent.

15. Agrochemical formulation comprising: a) at least one agricultural material, b) the composition, as solvent, as defined in any one of claims 7 to 10.

16. Agrochemical formulation according to any one of claims 13 to 15, wherein the said sulfoxide is dimethyl sulfoxide (DMSO).

17. Agrochemical formulation according to any one of claims 13 to 16, which further comprises at least one emulsifier.

18. Agrochemical formulation according to any one of claims 13 to 17, which further comprises water.

19. Agrochemical formulation according to any one of claims 13 to 18, in the form of an emulsifiable concentrate, an emulsion in water concentrate, a microemulsion concentrate, a suspoemulsion concentrate, an oil dispersion concentrate or a dispersible concentrate; preferably an emulsifiable concentrate.

20. Agrochemical formulation according to any one of claims 13 to 19, wherein the said composition, as solvent, represents from 9 to 99 %, preferably from 20 to 95 %, in particular from 30 to 90 %, by weight with respect to the total weight of the agrochemical formulation.

21. Use of an agricultural formulation according to any one of claims 13 to 20 to enhance field crop production.

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