Solvent systems for agrochemical formulations

Abstract

The present application discloses the agrochemical formulations with select solvent blends. The solvent blends exhibit a higher loadings of agrochemical ingredients compared to other solvent systems and / or improved physicochemical properties, demonstrating unexpected synergistic effects.

Description

[0001] SOLVENT SYSTEMS FOR AGROCHEMICAL FORMULATIONS

[0002] BACKGROUND OF THE INVENTION

[0003] Maintaining the solvent power of each individual solvent is crucial, and in some cases, solvent blends can exhibit synergistic solvation effects, surpassing expected solubility based on individual solvent contributions. Although the explanation for this desired phenomenon can be simplified by considering the combination of different chemical groups matching the solubility parameter of the mixed solvent to that of the solute, this is not trivial or fully understood.

[0004] The interaction between the solvent and plant leaves is a crucial consideration in solvent selection for formulations, indicating potential phytotoxicity or beneficial adjuvant effects as Al uptake enhancers. Solvents may be combined in blends to achieve desired properties, such as enhanced solvent performance, cost-effectiveness, improved ecotoxic profiles, and tailored physicochemical characteristics (e.g., higher flashpoint, lower viscosity, unique leaf cuticle interaction degree).

[0005] Applicants have discovered new solvent systems that have desirable solubilizing power and physicochemical characteristics that can be used in agrochemical formulations.

[0006] SUMMARY OF THE INVENTION

[0007] The present application discloses an agrochemical composition, comprising:

[0008] (1 ) an active ingredient,

[0009] (2) a solvent blend, comprising:

[0010] (a) a first solvent, which is dipropylene glycol dibenzoate, and

[0011] (b) a second solvent, wherein the first solvent has a first active ingredient solubility, wherein the second solvent has a second active ingredient solubility, wherein the solvent blend has a third active ingredient solubility that is at least equal to or more than first active ingredient solubility or second active ingredient solubility, and wherein the solubility is measured according to the procedure for determining active ingredient solubility disclosed herein.

[0012] The present application also discloses an agrochemical composition, comprising:

[0013] (1 ) an active ingredient,

[0014] (2) a solvent blend, comprising:

[0015] (a) a first solvent, which is ethylene glycol monopropyl ether, and

[0016] (b) a second solvent, wherein the first solvent has a first active ingredient solubility, wherein the second solvent has a second active ingredient solubility, wherein the solvent blend has a third active ingredient solubility that is at least equal to or more than first active ingredient solubility, and wherein the solubility is measured according to the procedure for determining active ingredient solubility disclosed herein.

[0017] DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention may be understood more readily by reference to the following detailed description of the invention and the examples provided therein. It is to be understood that this invention is not limited to the specific methods, formulations, and conditions described, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects of the invention only and is not intended to be limiting.

[0019] Definitions

[0020] In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings. Values may be expressed as “about” or “approximately” a given number. Similarly, ranges may be expressed herein as from “about” one particular value and / or to “about” or another particular value. When such a range is expressed, another aspect includes from the one particular value and / or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect.

[0021] As used herein, the terms “a,” “an,” and “the” mean one or more.

[0022] As used herein, the term “and / or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and / or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination.

[0023] As used herein, the terms “comprising,” “comprises,” and “comprise” are open-ended transition terms used to transition from a subject recited before the term to one or more elements recited after the term, where the element or elements listed after the transition term are not necessarily the only elements that make up the subject.

[0024] As used herein, the terms “having,” “has,” and “have” have the same open-ended meaning as “comprising,” “comprises,” and “comprise” provided above.

[0025] As used herein, the terms “including,” “includes,” and “include” have the same open-ended meaning as “comprising,” “comprises,” and “comprise” provided above.

[0026] Numerical Ranges

[0027] The present description uses numerical ranges to quantify certain parameters relating to the invention. It should be understood that when numerical ranges are provided, such ranges are to be construed as providing literal support for claim limitations that only recite the lower value of the range as well as claim limitations that only recite the upper value of the range. For example, a disclosed numerical range of 10 to 100 provides literal support for a claim reciting “greater than 10” (with no upper bounds) and a claim reciting “less than 100” (with no lower bounds).

[0028] The present description uses specific numerical values to quantify certain parameters relating to the invention, where the specific numerical values are not expressly part of a numerical range. It should be understood that each specific numerical value provided herein is to be construed as providing literal support for a broad, intermediate, and narrow range. The broad range associated with each specific numerical value is the numerical value plus and minus 60 percent of the numerical value, rounded to two significant digits. The intermediate range associated with each specific numerical value is the numerical value plus and minus 30 percent of the numerical value, rounded to two significant digits. The narrow range associated with each specific numerical value is the numerical value plus and minus 15 percent of the numerical value, rounded to two significant digits. For example, if the specification describes a specific temperature of 62 °F, such a description provides literal support for a broad numerical range of 25 °F to 99 °F (62 °F + / - 37 °F), an intermediate numerical range of 43 °F to 81 °F (62 °F + / - 19 °F), and a narrow numerical range of 53 °F to 71 °F (62 °F + / - 9 °F). These broad, intermediate, and narrow numerical ranges should be applied not only to the specific values, but should also be applied to differences between these specific values. Thus, if the specification describes a first pressure of 110 psia and a second pressure of 48 psia (a difference of 62 psi), the broad, intermediate, and narrow ranges for the pressure difference between these two streams would be 25 to 99 psi, 43 to 81 psi, and 53 to 71 psi, respectively.

[0029] Throughout this application, where patents or publications are referenced, the disclosures of these references in their entireties are intended to be incorporated by reference into this application, to the extent they are not inconsistent with the present invention, in order to more fully describe the state of the art to which the invention pertains. Solvent Blends Comprising Dipropylene Glycol Dibenzoate

[0030] The present application discloses, in a first aspect, an agrochemical composition, comprising: (1 ) an active ingredient, (2) a solvent blend, comprising: (a) a first solvent, which is dipropylene glycol dibenzoate, and (b) a second solvent, wherein the first solvent has a first active ingredient solubility, wherein the second solvent has a second active ingredient solubility, wherein the solvent blend has a third active ingredient solubility that is at least equal to or more than first active ingredient solubility or second active ingredient solubility, and wherein the solubility is measured according to the procedure for determining active ingredient solubility disclosed herein.

[0031] In one embodiment of this first aspect or in combination with any other embodiment of the first aspect, the first solvent is present from 5-70wt%, or from 5-60wt%, or from 5-50wt%, or from 5-40wt%, or from 5-30wt%, or from 5- 20wt%, or from 5-10wt%, or from 10-70wt%, or from 10-60wt%, or from 10- 50wt%, or from 10-40wt%, or from 10-30wt%, or from 10-20wt%, or from 20-

[0032] 70wt%, or from 20-60wt%, or from 20-50wt%, or from 20-40wt%, or from 20-

[0033] 30wt%, or from 30-70wt%, or from 30-60wt%, or from 30-50wt%, or from 30-

[0034] 40wt%, or from 40-70wt%, or from 40-60wt%, or from 40-50wt%, or from 50-

[0035] 70wt%, or from 50-60wt%, or from 60-70wt%, based on the total weight of the solvent blend.

[0036] In one embodiment of this first aspect or in combination with any other embodiment of the first aspect, the active ingredient is present at from 1 -80wt%, or from 1 -70wt%, or from 1 -60wt%, or from 1 -50wt%, or from 1 -40wt%, or from 1 -30wt%, or from 1 -20wt%, or from 1 -10wt%, or from 1 -5wt%, or from 5-80wt%, or from 5-70wt%, or from 5-60wt%, or from 5-50wt%, or from 5-40wt%, or from 5-30wt%, or from 5-20wt%, or from 5-10wt%, or from 5-5wt%, or from 10- 80wt%, or from 10-70wt%, or from 10-60wt%, or from 10-50wt%, or from 10- 40wt%, or from 10-30wt%, or from 10-20wt%, or from 20-80wt%, or from 20- 70wt%, or from 20-60wt%, or from 20-50wt%, or from 20-40wt%, or from 20-

[0037] 30wt%, or from 30-80wt%, or from 30-70wt%, or from 30-60wt%, or from 30-

[0038] 50wt%, or from 30-40wt%, or from 40-80wt%, or from 40-70wt%, or from 40-

[0039] 60wt%, or from 40-50wt%, or from 50-80wt%, or from 50-70wt%, or from 50-

[0040] 60wt%, or from 60-80wt%, or from 60-70wt%, or from 70-80wt%, based on the total weight of the agrochemical composition.

[0041] In one embodiment of this first aspect or in combination with any other embodiment of the first aspect, the active ingredient is a fungicide, an insecticide, an herbicide, an herbicide-safener, a microorganism or its derivatives, a growth regulator / bio-stimulant compound, or a combination thereof.

[0042] In one class of this embodiment, the active ingredient is a fungicide. In one class of this embodiment, the active ingredient is an insecticide. In one class of this embodiment, the active ingredient is an herbicide. In one class of this embodiment, the active ingredient is an herbicide-safener. In one class of this embodiment, the active ingredient is a microorganism or its derivative. In one class of this embodiment, the active ingredient is a growth regulator / bio- stimulant compound.

[0043] In one class of this embodiment, the active ingredient is tebuconazole, difenoconazole, metribuzin, or combinations thereof.

[0044] In one embodiment of this first aspect or in combination with any other embodiment of the first aspect, the viscosity of the solvent blend is less than 100, or less than 90, or less than 80, or less than 70, or less than 60, or less than 50 or less than 40 mPa s, wherein the viscosity is measured according to ASTM D2196-20.

[0045] In one embodiment of this first aspect or in combination with any other embodiment of the first aspect, the solvent blend exhibits a 24 hour phytotoxicity index for poinsettia of less than 80, or less than 70, or less than 60, or less than 50, or less than 40, or less than 30 as measured according to according to the procedure disclosed herein. In one embodiment of this first aspect or in combination with any other embodiment of the first aspect, the second solvent is 2,2,4-trimethyl-1 ,3- pentanediol monoisobutyrate, 2-ethylhexanol, N,N-dimethyldecanamide, diethylene glycol monobutyl ether, 2-ethylhexyl acetate, diethylene glycol monoethyl ether, 2-butoxyethyl acetate, or combinations thereof.

[0046] In one class of this embodiment, the second solvent is 2-ethylhexanol, diethylene glycol monoethyl ether, 2-Butoxyethyl acetate, or 2,2,4-trimethyl- 1 ,3-pentanediol monoisobutyrate. In one class of this embodiment, the second solvent is 2-ethylhexanol, N,N-dimethyldecanamide, diethylene glycol monobutyl ether, 2-ethylhexyl acetate, 2-butoxyethyl acetate, or2,2,4-trimethyl- 1 ,3-pentanediol monoisobutyrate. In one class of this embodiment, the second solvent is 2, 2, 4-trimethyl-1 ,3-pentanediol monoisobutyrate. In one class of this embodiment, the second solvent is 2-ethylhexanol. In one class of this embodiment, the second solvent is N,N-dimethyldecanamide. In one class of this embodiment, the second solvent is diethylene glycol monobutyl ether. In one class of this embodiment, the second solvent is 2-ethylhexyl acetate. In one class of this embodiment, the second solvent is diethylene glycol monoethyl ether. In one class of this embodiment, the second solvent is butoxyethyl acetate.

[0047] In one embodiment of this first aspect or in combination with any other embodiment of the first aspect, the solvent blend exhibits a 24 hour phytotoxicity index for poinsettia of less than 80, or less than 70, or less than 60, or less than 50, or less than 40, or less than 30 as measured according to the procedure disclosed herein.

[0048] Solvent Blends Comprising Ethylene Glycol Monopropyl Ether

[0049] The present application discloses, in a second aspect, an agrochemical composition, comprising: (1 ) an active ingredient, (2) a solvent blend, comprising: (a) a first solvent, which is ethylene glycol monopropyl ether, and (b) a second solvent, wherein the first solvent has a first active ingredient solubility, wherein the second solvent has a second active ingredient solubility, wherein the solvent blend has a third active ingredient solubility that is at least equal to or more than first active ingredient solubility, and wherein the solubility is measured according to the procedure for determining active ingredient solubility disclosed herein.

[0050] In one embodiment of this second aspect or in combination with any other embodiment of the second aspect, the first solvent is present from 5- 70wt%, or from 5-60wt%, or from 5-50wt%, or from 5-40wt%, or from 5-30wt%, or from 5-20wt%, or from 5-10wt%, or from 10-70wt%, or from 10-60wt%, or from 10-50wt%, or from 10-40wt%, or from 10-30wt%, or from 10-20wt%, or from 20-70wt%, or from 20-60wt%, or from 20-50wt%, or from 20-40wt%, or from 20-30wt%, or from 30-70wt%, or from 30-60wt%, or from 30-50wt%, or from 30-40wt%, or from 40-70wt%, or from 40-60wt%, or from 40-50wt%, or from 50-70wt%, or from 50-60wt%, or from 60-70wt%, based on the total weight of the solvent blend.

[0051] In one embodiment of this second aspect or in combination with any other embodiment of the second aspect, the active ingredient is present at from 1 -80wt%, or from 1 -70wt%, or from 1 -60wt%, or from 1 -50wt%, or from 1- 40wt%, or from 1 -30wt%, or from 1 -20wt%, or from 1 -10wt%, or from 1 -5wt%, or from 5-80wt%, or from 5-70wt%, or from 5-60wt%, or from 5-50wt%, or from 5-40wt%, or from 5-30wt%, or from 5-20wt%, or from 5-10wt%, or from 5-5wt%, or from 10-80wt%, or from 10-70wt%, or from 10-60wt%, or from 10-50wt%, or from 10-40wt%, or from 10-30wt%, or from 10-20wt%, or from 20-80wt%, or from 20-70wt%, or from 20-60wt%, or from 20-50wt%, or from 20-40wt%, or from 20-30wt%, or from 30-80wt%, or from 30-70wt%, or from 30-60wt%, or from 30-50wt%, or from 30-40wt%, or from 40-80wt%, or from 40-70wt%, or from 40-60wt%, or from 40-50wt%, or from 50-80wt%, or from 50-70wt%, or from 50-60wt%, or from 60-80wt%, or from 60-70wt%, or from 70-80wt%, based on the total weight of the agrochemical composition.

[0052] In one embodiment of this second aspect or in combination with any other embodiment of the second aspect, the active ingredient is a fungicide, an insecticide, an herbicide, an herbicide-safener, a microorganism or its derivatives, a growth regulator / bio-stimulant compound, or a combination thereof.

[0053] In one class of this embodiment, the active ingredient is a fungicide. In one class of this embodiment, the active ingredient is an insecticide. In one class of this embodiment, the active ingredient is an herbicide. In one class of this embodiment, the active ingredient is an herbicide-safener. In one class of this embodiment, the active ingredient is a microorganism or its derivative. In one class of this embodiment, the active ingredient is a growth regulator / bio- stimulant compound.

[0054] In one embodiment of this second aspect or in combination with any other embodiment of the second aspect, the active ingredient is tebuconazole, difenoconazole, metribuzin, or combinations thereof.

[0055] In one embodiment of this second aspect or in combination with any other embodiment of the second aspect, the second solvent is 2, 2,4-trim ethy I- 1 ,3-pentanediol monoisobutyrate, diethylene glycol monobutyl ether, or diethylene glycol monoethyl ether.

[0056] In one embodiment of this second aspect or in combination with any other embodiment of the second aspect, the solvent blend exhibits a flash point higher than 50 °C, or higher than 60 °C, or higher than 65 °C, or higher than 70 °C as measured according to ASTM D3941 -20.

[0057] In one embodiment of this second aspect or in combination with any other embodiment of the second aspect, the solvent blend exhibits a 24 hour phytotoxicity index for poinsettia of less than 80, or less than 70, or less than 60, or less than 50, or less than 40, or less than 30 as measured according to according to the procedure disclosed herein.

[0058] Solvent Blends Comprising Ethyl 3-Ethoxypropionate

[0059] The present application discloses, in a third aspect, an agrochemical composition, comprising: (1 ) an active ingredient, (2) a solvent blend, comprising: (a) a first solvent, which is ethyl 3-ethoxypropionate, and (b) a second solvent, wherein the first solvent has a first active ingredient solubility, wherein the second solvent has a first active ingredient solubility, wherein the agrochemical compositions has a first active ingredient solubility that is at least the same as the first active solubility of the first solvent, and wherein the agrochemical composition has a third active ingredient solubility that is at least equal to or more than first active ingredient solubility or second active ingredient solubility, and wherein the solubility is measured according to the procedure for determining active ingredient solubility disclosed.

[0060] In one embodiment of this third aspect or in combination with any other embodiment of the third aspect, the first solvent is present from 5-70wt%, or from 5-60wt%, or from 5-50wt%, or from 5-40wt%, or from 5-30wt%, or from 5- 20wt%, or from 5-10wt%, or from 10-70wt%, or from 10-60wt%, or from 10- 50wt%, or from 10-40wt%, or from 10-30wt%, or from 10-20wt%, or from 20-

[0061] 70wt%, or from 20-60wt%, or from 20-50wt%, or from 20-40wt%, or from 20-

[0062] 30wt%, or from 30-70wt%, or from 30-60wt%, or from 30-50wt%, or from 30-

[0063] 40wt%, or from 40-70wt%, or from 40-60wt%, or from 40-50wt%, or from 50-

[0064] 70wt%, or from 50-60wt%, or from 60-70wt%, based on the total weight of the solvent blend.

[0065] In one embodiment of this third aspect or in combination with any other embodiment of the third aspect, the active ingredient is present at from 1- 80wt%, or from 1 -70wt%, or from 1 -60wt%, or from 1 -50wt%, or from 1 -40wt%, or from 1 -30wt%, or from 1 -20wt%, or from 1 -10wt%, or from 1 -5wt%, or from 5-80wt%, or from 5-70wt%, or from 5-60wt%, or from 5-50wt%, or from 5-

[0066] 40wt%, or from 5-30wt%, or from 5-20wt%, or from 5-10wt%, or from 5-5wt%, or from 10-80wt%. or from 10-70wt%. or from 10-60wt%. or from 10-50wt%. or from 10-40wt%, or from 10-30wt%, or from 10-20wt%, or from 20-80wt%, or from 20-70wt%, or from 20-60wt%, or from 20-50wt%, or from 20-40wt%, or from 20-30wt%, or from 30-80wt%, or from 30-70wt%, or from 30-60wt%, or from 30-50wt%, or from 30-40wt%, or from 40-80wt%, or from 40-70wt%, or from 40-60wt%, or from 40-50wt%, or from 50-80wt%, or from 50-70wt%, or from 50-60wt%, or from 60-80wt%, or from 60-70wt%, or from 70-80wt%, based on the total weight of the agrochemical composition. In one embodiment of this third aspect or in combination with any other embodiment of the third aspect, the active ingredient is a fungicide, an insecticide, an herbicide, an herbicide-safener, a microorganism or its derivatives, a growth regulator / bio-stimulant compound, or a combination thereof.

[0067] In one class of this embodiment, the active ingredient is a fungicide. In one class of this embodiment, the active ingredient is an insecticide. In one class of this embodiment, the active ingredient is an herbicide. In one class of this embodiment, the active ingredient is an herbicide-safener. In one class of this embodiment, the active ingredient is a microorganism or its derivative. In one class of this embodiment, the active ingredient is a growth regulator / bio- stimulant compound.

[0068] In one embodiment of this third aspect or in combination with any other embodiment of the third aspect, the active ingredient is tebuconazole, difenoconazole, metribuzin, or combinations thereof.

[0069] In one embodiment of this third aspect or in combination with any other embodiment of the third aspect, the second solvent is 2,2,4-trimethyl-1 ,3- pentanediol monoisobutyrate, 2,2,4-trimethyl-1 ,3-pentanediol monoisobutyrate, diethylene glycol monoethyl ether, bis(2-ethylhexyl) terephthalate, glyceryl triacetate, or bis(2-ethylhexyl) adipate.

[0070] In one embodiment of this third aspect or in combination with any other embodiment of the third aspect, the solvent blend exhibits a flash point higher than 50 °C, or higher than 60 °C, or higher than 65 °C, or higher than 70 °C as measured according to ASTM D3941-20.

[0071] In one embodiment of this third aspect or in combination with any other embodiment of the third aspect, the solvent blend exhibits a 24 hour phytotoxicity index for poinsettia of less than 80, or less than 70, or less than 60, or less than 50, or less than 40, or less than 30 as measured according to according to the procedure disclosed herein.

[0072] EXPERIMENTAL SECTION Abbreviations n.d. is not determined; min is minute(s); °C is degree(s) Celsius; wt% is weight percent, s is second(s), h is hour(s), g is gram(s), rpm is revolutions per minute;

[0073] Procedures

[0074] Procedure for Determination of Solubility

[0075] Glass vials were prepared to contain the specified solvent and a proportion of 5-70wt% of the material to be tested for solubility. The vials were subjected to heating and agitation at 60°C for a duration of 120 min. The vials were subsequently allowed to rest at ambient temperature and were monitored for crystallization or sedimentation of the active ingredient over a period of two weeks. The maximum active ingredient solubility was determined by determining which vial had the highest proportion of the active ingredient and still exhibited a clear solution without sediment or crystallization.

[0076] Procedure for Determination of Viscosity

[0077] The viscosity was determined according to ASTM D2196-20 using a Brookfield DVII+ viscometer.

[0078] Procedure for Determination of the Flash Point

[0079] The flash point was determined according to ASTM D3941 -20 using an Anton Paar TAG 4 using a closed cup.

[0080] Procedure for Determination of Phytotoxicity Index and Phytotoxicity Classification

[0081] The degree of solvent and leaf cuticle interaction was evaluated in terms of phytotoxicity utilizing the model plant Poinsettia. The leaves of Poinsettia are sensitive to external factors and their red color facilitates the observation of harm. In summary, leaves at the same stage and size were carefully removed from Poinsettia, and the petiole was covered with tissue paper embedded in distilled water, which kept it hydrated throughout the test. Then, three 2 pL droplets of the solvent blend were applied on the surface of the red leaves, ensuring adequate spacing between each droplet. Distilled water was used as a control reference.

[0082] The phytotoxicity induced by each solvent blend, tested undiluted (i.e., not at the concentrations used in agricultural practice), was assessed through visual observation of the leaf condition over time, whereby scores were assigned for three parameters: area of spreading, wilting, and discoloration, similar to parameters described in OECD Guideline 227 (Terrestrial Plant Test: Vegetative Vigour Test). The final phytotoxicity index was computed by the sum of the scores for these parameters, as outlined in Error! Reference source not found.. A higher index implies a greater degree of interaction with the leaf cuticle. Although leaf condition was evaluated for up to 1 week, the cuticle interaction degree scale proved most effective in differentiating samples when comparing overall scores at 24 hours. Based on the cumulative phytotoxicity index, the solvents were categorized into distinct groups of cuticle interaction as described in Table 2. The phytotoxicity index for distilled water was determined to be 0 with a phytotoxicity classification of no interaction.

[0083] Table 1. Parameters used to determine phytotoxicity index.

[0084] Table 2. Overall scoring scale for phytotoxicity.

[0085] Solvents

[0086] Table 3 provides the solvents that were studied. Table 3. Solvents evaluated and properties of the solvents.

[0087] 1. Agrochemical Formulations Comprising Dipropylene Glycol Dibenzoate

[0088] Table 4 provides the dipropylene glycol dibenzoate blends.

[0089] Table 4. Solvent Blends

[0090] Table 5. Solubility data of select active ingredients and dipropylene glycol dibenzoate blends or individual solvents. Table 6. Viscosity and phytotoxicity data for compositions comprising dipropylene glycol dibenzoate blends and individual solvents. Although it might be anticipated that combining two solvents in a 1 :1 ratio would result in solubility equating to the arithmetic mean of the solubilities of the individual pure solvents, this is not invariably the case. The combination can induce surprisingly synergistic effects that enhance solubility. A solvent with strong solvency power, when combined with a weaker solvent, can maintain high solubility while altering other characteristics of the individual solvents. If this effect occurs with a lower-cost or greener solvent with weaker solvency performance, it allows the formulator to replace a more expensive or environmentally harmful solvent.

[0091] In accordance with embodiments of the present invention, it has been unexpectedly discovered that the combination of solvent S14 with solvents S1 , S3, S5, S6, and S11 results in a solvent system exhibiting solvency power that is either superior or comparable to the most effective known solvent, while simultaneously achieving a substantial reduction in viscosity or the modulation of the phytotoxicity. In particular, composition B1 demonstrates a synergistic effect, enhancing the solubility of difenoconazole, tebuconazole, metribuzin, and cloquintocet-mexyl, or maintaining comparable solvency power for the dissolution of abamectin and bifenthrin. Furthermore, composition B5 has been found to increase or maintain solvency power for azoxystrobin, prothioconazole, and tebuconazole, and composition B6 exhibits a synergistic effect enhancing the solubility of tebuconazole. Composition B7 maintains comparable solvency power for the dissolution of tebuconazole, whereas composition B4 exhibits dissolution power comparable to solvent S6 with respect to difenoconazole. Composition B2 maintains solvency power for dissolving difenoconazole and bifenthrin similar to the most potent individual solvent.

[0092] Furthermore, Solvent S14 effectively reduced the phytotoxicity of the other individual solvent without diminishing, and in some cases enhancing, the solvent power of the solvent system. This was observed with solvent S6 for difenoconazole and azoxystrobin, solvent S1 for tebuconazole, azoxystrobin, and prothioconazole, solvent S10 for prothioconazole and metribuzin, and solvent S11 for tebuconazole.

[0093] 2. Agrochemical Formulations Comprising Ethylene Glycol Monopropyl Ether

[0094] Table 7 provides the ethylene glycol monopropyl ether blends that were studied.

[0095] Table 7. Ethylene glycol monopropyl ether blends. Table 8. Solubility data for ethylene glycol monopropyl ether blends and individual solvents.

[0096] Table 9. Phytotoxicity and flash point data for ethylene glycol monopropyl ether blends and individual solvents.

[0097] Solvent S7 possesses a low flashpoint value of 49 °C, necessitating classification as a flammable liquid. The incorporation of a cosolvent may elevate the flashpoint, though this process is complex and influenced by the flashpoint values and vapor pressure of each component, as well as the liquidvapor equilibrium of the solvent blend. Additionally, the choice of cosolvent may affect the solvency power of the resultant combination.

[0098] The combination of solvent S7 with solvents S4, S5, and S10 significantly increased the flashpoint above 60 °C, thereby enhancing safety while increasing solvency power for tebuconazole and difenoconazole or preserving maximum solvency power for metribuzin and cloquintocet-mexyl. Furthermore, B8 exhibits an intermediate phytotoxicity, whereas B10 demonstrates moderate phytotoxicity, similar to S10 alone.

[0099] 3. Agrochemical Formulations Comprising Ethyl 3-Ethoxypropionate

[0100] Table 10 provides the ethyl 3-ethoxypropionate blends that were studied.

[0101] Table 10. Ethyl 3-ethoxypropionate blends.

[0102] Table 11 provides the solubility data for the ethyl 3-ethoxypropionate blends and individual solvents. Table 11. Solubility data for ethyl 3-ethoxypropionate blends and individual solvents.

[0103] Table 12 provides the phytotoxicity and flash point date for the ethyl 3- ethoxypropionate blends and individual solvents.

[0104] Table 12. Phytotoxicity and flash point data for compositions comprising ethyl

[0105] 3-ethoxypropionate blends and individual solvents.

[0106] Solvent S8 possess low flashpoint value of 58 °C, necessitating classification as a flammable liquid. The incorporation of a cosolvent may elevate the flashpoint, though this process is complex and influenced by the flashpoint values and vapor pressure of each component, as well as the liquidvapor equilibrium of the solvent blend. Additionally, the choice of cosolvent may affect the solvency power of the resultant combination.

[0107] In accordance with the present invention, the combination of solvent S8 with solvent S1 significantly enhanced solvency power for bifenthrin while maintaining similar solvency for lufenuron and tebuconazole. Additionally, the binary combination with solvent S5 increased solvency for tebuconazole, azoxystrobin, abamectin, and cloquintocet-mexyl, while maintaining similar solvency for lufenuron. The combination of solvent S8 with solvent S12 preserved similar solvency power for azoxystrobin, difenoconazole, and tebuconazole. The combination of solvent S8 with solvent S12 preserved similar solvency power for, bifenthrin, cloquintocet-mexyl difenoconazole, lufenuron, metribuzin, and tebuconazole. The combination of solvent S8 with solvent S4 preserved similar solvency power for difenoconazole and tebuconazole. The combination of solvent S8 with solvent S13 preserved similar solvency power for tebuconazole. In each of these instances, the flashpoint of the solvent system was significantly increased above 70 °C, thereby enhancing safety.

[0108] It has been unexpectedly discovered that composition B16 demonstrates stronger phytotoxicity relative to the individual solvents, whereas B11 exhibited similar phytotoxicity to S1 , and B12 an intermediate phytotoxicity.

[0109] Model Agrochemical Formulations

[0110] This section demonstrates that the solvent systems can be effectively incorporated into model agrochemical formulations.

[0111] The chemicals used in the formulation study are as follows: polyaklene oxide block copolymer (Atlas G-5002, Croda), Polyoxyethyene (5) tridecyl mono / di-phosphate (Crodafos T5A, Croda), Bis(2-ethylhexyl)terephthalate (Eastman 168, Eastman), ethyl 3-ethoxypropionate (EEP solvent, Eastman), dodecyl benzene sulfonate (Rhodacal 70B, Solvay), tristyrylphenol ethoxylate 16 EO (Surfom CE 1299, Oxiteno), castor oil ethoxylate 15 EO (Surfom R 150, Oxiteno).

[0112] Formulation 1

[0113] S4 (24.38 g) and S14 (24.38 g) were added to a beaker placed in a water bath set to 60°C. Pyraclostrobin (18.75g) was added, and the mixture was stirred at 250 rpm with an overhead stirrer until the active ingredient was fully dissolved. Castor oil ethoxylate 15 EO (1.10g) was added and the mixture was stirred at 250 rpm for 5-10 min until homogeneous. Tristyrylphenol ethoxylate 16 EO (4.65g) was added and the mixture was stirred at 250 rpm for 5-10 min until homogeneous. Dodecyl benzene sulfonate (1.75g) was added and the mixture was stirred at 250 rpm for 1 -2 h to produce a homogeneous formulation. The mixture was allowed to cool under agitation, as required. The formulation accelerated storage stability and emulsion performance were determined following standard protocols as described in CIPAC MT 39.3, CIPAC MT 46.3, and CIPAC MT 36.3.

[0114] Table 13. Composition of formulation in Formulation 1.

[0115] Table 14. Accelerated storage stability and emulsion performance of formulation from Formulation 1.

[0116] Formulation 2

[0117] S8 (22.80 g) and S12 (22.80 g) were added to a beaker placed in a water bath set to 60 °C. Difenoconazole (18.75g) was added and the mixture was stirred at 250 rpm with an overhead stirrer until the active ingredient was fully dissolved. Tristyrylphenol ethoxylate 16 EO (5.85g) was added and the mixture was stirred at 250 rpm for 5-10 min until homogeneous. Polyalkylene oxide block copolymer (1 ,8g) was then added and the mixture was stirred at 250 rpm for 5-10 min until homogeneous. Polyoxyethyene (5) tridecyl mono / di- phosphate (3.0g) was added and the mixture was stirred at 250 rpm for 1 -2 h to produce a homogeneous formulation. The mixture was allowed to cool under agitation, as required. The formulation accelerated storage stability and emulsion performance were determined following standard protocols as described in CIPAC MT 39.3, CIPAC MT 46.3, and CIPAC MT 36.3.

[0118] Table 15. Composition of formulation in Formulation 2. Table 16. Accelerated storage stability and emulsion performance of formulation from Formulation 2.

[0119] Formulation 3 S8 (41 .04 g) and S9 (4.56 g) were added to a beaker placed in a water bath set to 60°C. Bifenthrin (18.75g) was added and the mixture was stirred at 250 rpm with an overhead stirrer until the active ingredient was fully dissolved. Tristyrylphenol ethoxylate 16 EO (5.85g) was added and the mixture was stirred at 250 rpm for 5-10 min until homogeneous. Polyalkylene oxide block copolymer (1 ,80g) was added and the mixture was stirred at 250 rpm for 5-10 min until homogeneous. Polyoxyethyene (5) tridecyl mono / di-phosphate (3.0g) was added, and the mixture was stirred at 250 rpm for 1 -2 h to produce a homogeneous formulation. The mixture was allowed to cool under agitation, as required. The formulation accelerated storage stability and emulsion performance were determined following standard protocols as described in CIPAC MT 39.3, CIPAC MT 46.3, and CIPAC MT 36.3. Table 17. Composition of formulation in Formulation 3.

[0120] Table 18. Accelerated storage stability and emulsion performance of formulation from Formulation 3.

[0121] Formulation 4

[0122] S4 (24.38 g) and S14 (24.38 g) were added to a beaker placed in a water bath set to 60°C. Bifenthrin (15.0g) was added and the mixture was stirred at 250 rpm with an overhead stirrer until the active ingredient was fully dissolved. Castor oil ethoxylate 15 EO (2.25g) was added and the mixture was stirred at 250 rpm for 5-10 min until homogeneous. Tristyrylphenol ethoxylate 16 EO (6.00 g) was added, and the mixture was stirred at 250 rpm for 5-10 min until homogeneous. Dodecyl benzene sulfonate (3.0g) was added, and the mixture was stirred at 250 rpm for 1-2 h to produce a homogeneous formulation. The mixture was allowed to cool under agitation, as required. The formulation accelerated storage stability and emulsion performance were determined following standard protocols as described in CIPAC MT 39.3, CIPAC MT 46.3, and CIPAC MT 36.3.

[0123] Table 19. Composition of formulation in Formulation 4.

[0124] Table 20. Accelerated storage stability and emulsion performance of formulation from Formulation 4.

Claims

CLAIMSWhat is claimed is:

1. An agrochemical composition, comprising:(1 ) an active ingredient,(2) a solvent blend, comprising:(a) a first solvent, which is dipropylene glycol dibenzoate, and(b) a second solvent, wherein the first solvent has a first active ingredient solubility, wherein the second solvent has a second active ingredient solubility, wherein the solvent blend has a third active ingredient solubility that is at least equal to or more than first active ingredient solubility or second active ingredient solubility, and wherein the solubility is measured according to the procedure for determining active ingredient solubility disclosed herein.

2. The agrochemical composition of claim 1 , wherein the viscosity of the solvent blend is less than 100, or less than 90, or less than 80, or less than 70, or less than 60, or less than 50 or less than 40 mPa s, wherein the viscosity is measured according to ASTM D2196-20.

3. The agrochemical composition of any one of claims 1 or 2, wherein the solvent blend exhibits a 24 hour phytotoxicity index for poinsettia of less than 80, or less than 70, or less than 60, or less than 50, or less than 40, or less than 30 as measured according to according to the procedure disclosed herein.

4. The agrochemical composition of any one of claims 1 -3, wherein the second solvent is 2,2,4-trimethyl-1 ,3-pentanediol monoisobutyrate, 2-ethylhexanol, N,N-dimethyldecanamide, diethylene glycol monobutyl ether, 2-ethylhexyl acetate, diethylene glycol monoethyl ether, 2-butoxyethyl acetate, or combinations thereof.

5. The agrochemical composition of any one of claims 1 -4, wherein the active ingredient is a fungicide, an insecticide, an herbicide safener, or a combination thereof.

6. The agrochemical composition of any one of claims 1 -5, wherein the active ingredient is tebuconazole, azoxystrobin, difenoconazole, bifenthrin , lufenuron, abamectin, metribuzin, cloquintocet-mexyl, or combinations thereof.

7. An agrochemical composition, comprising:(1 ) an active ingredient,(2) a solvent blend, comprising:(a) a first solvent, which is ethylene glycol monopropyl ether, and(b) a second solvent, wherein the first solvent has a first active ingredient solubility, wherein the second solvent has a second active ingredient solubility, wherein the solvent blend has a third active ingredient solubility that is at least equal to or more than first active ingredient solubility, and wherein the solubility is measured according to the procedure for determining active ingredient solubility disclosed herein.

8. The agrochemical composition of claim 7, wherein the solvent blend exhibits a flash point higher than 50 °C, or higher than 60 °C, or higher than 65 °C, or higher than 70 °C as measured according to ASTM D3941 -20.

9. The agrochemical composition of any one of claims 7-8, wherein the solvent blend exhibits a 24 hour phytotoxicity index for poinsettia of less than 80, or less than 70, or less than 60, or less than 50, or less than 40, or less than 30 as measured according to the procedure for determining active ingredient solubility disclosed herein.

10. The agrochemical composition of any one of claims 7-9, wherein the second solvent is 2,2,4-trimethyl-1 ,3-pentanediol monoisobutyrate, diethylene glycol monobutyl ether, or diethylene glycol monoethyl ether.

11. The agrochemical composition of any one of claims 7-10, wherein the active ingredient is a fungicide, an insecticide, an herbicide safener, or a combination thereof.

12. The agrochemical composition of any one of claims 7-11 , wherein the active ingredient is tebuconazole, difenoconazole, metribuzin, or combinations thereof.

13. An agrochemical composition, comprising:(1 ) an active ingredient,(2) a solvent blend, comprising:(a) a first solvent, which is ethyl 3-ethoxypropionate, and(b) a second solvent, wherein the first solvent has a first active ingredient solubility, wherein the second solvent has a first active ingredient solubility, wherein the agrochemical compositions has a first active ingredient solubility that is at least the same as the first active solubility of the first solvent, and wherein the agrochemical composition has a third active ingredient solubility that is at least equal to or more than first active ingredient solubility or second active ingredient solubility, and wherein the solubility is measured according to the procedure for determining active ingredient solubility disclosed.

14. The agrochemical composition of claim 13, wherein the solvent blend exhibits a flash point higher than 50°C, or higher than 60°C, or higher than 65°C, or higher than 70 °C as measured according to ASTM D3941 -20.

15. The agrochemical composition of any one of claims 13-14, wherein the agrochemical composition exhibits a 24 hour phytotoxicity index for poinsettia of less than 80, or less than 70, or less than 60, or less than 50, or less than 40, or less than 30 as measured according to the procedure for determining phytotoxicity index disclosed herein.

16. The agrochemical composition of any one of claims 11 -13, wherein the second solvent is 2,2,4-trimethyl-1 ,3-pentanediol monoisobutyrate, 2,2,4- trimethyl-1 ,3-pentanediol monoisobutyrate, diethylene glycol monoethyl ether, bis(2 -ethylhexyl) terephthalate, glyceryl triacetate, or bis(2-ethylhexyl) adipate.

17. The agrochemical composition of any one of claims 1 -4, wherein the active ingredient is a fungicide, an insecticide, an herbicide safener, or a combination thereof.

18. The agrochemical composition of any one of claims 11 -14, wherein the active ingredient is tebuconazole, difenoconazole, metribuzin, or combinations thereof.

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