Emulsifier compositions and agrochemical emulsion compositions

Abstract

Described herein are emulsifier compositions comprising an agrochemical oil; an alkoxylated alkyl alcohol emulsifier comprising a hydrophilic-lipophilic balance (HLB) value of at least about 6.0; and a fatty acid ester emulsifier or fatty acid emulsifier comprising an HLB value of less than about 6.0, agrochemical emulsion compositions comprising the emulsifier compositions, methods of making same, and methods of using same.

Description

240669WG01EMULSIFIER COMPOSITIONS AND AGROCHEMICAL EMULSION COMPOSITIONSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority from U.S. Provisional Patent Application No. 63 / 706,772, filed October 14, 2024, the disclosures of which are incorporated herein by reference.FIELD OF THE INVENTION

[0002] The present disclosure relates to emulsifier compositions, agrochemical emulsion compositions, methods of making same, and methods of using same.BACKGROUND

[0003] Emulsifiers, such as polymer emulsifiers and surfactant emulsifiers, are widely recognized for their ability to emulsify or stabilize emulsion or dispersion systems. They also offer rigidity at interfaces, thereby reducing coalescence and exhibiting less sensitivity to temperature changes.

[0004] Nonylphenol ethoxylates, such as Tergitol® NP-9 and NP-6, have conventionally been used to emulsify oils useful in agrochemical applications, such as Agnique® ME 18SD-U (distilled methyl soyate), mineral oil, or paraffinic oil. For example, a blend of Tergitol® NP- 9, Tergitol® NP-6, and Agnique® ME 18SD-U may be used as a tank-mix adjuvant to boost the performance of post-emergent herbicides.

[0005] Although nonylphenol ethoxylates are inexpensive and very effective at emulsification and solubilization, they have a negative public perception due to their bioaccumulation in aquatic species, and their effect on humans and animals as an endocrine disruptor. It is therefore desirable to avoid using nonylphenol ethoxylates in emulsifier compositions.

[0006] Accordingly, there is a need for agrochemical emulsifier compositions that provide comparable or improved performance to agrochemical emulsifier compositions including nonylphenol ethoxylates.BRIEF DESCRIPTION

[0007] In one aspect, an emulsifier composition is provided. The emulsifier composition comprises an agrochemical oil, an alkoxylated alkyl alcohol emulsifier comprising a hydrophilic-lipophilic balance (HLB) value of at least about 6.0, and a fatty acid ester emulsifier or fatty acid emulsifier comprising an HLB value of less than about 6.0.

[0008] In another aspect, a method of making an emulsifier composition is provided. The emulsifier composition comprises an agrochemical oil, an alkoxylated alkyl alcohol emulsifier240669W001 comprising a hydrophilic-lipophilic balance (HLB) value of at least about 6.0, and a fatty acid ester emulsifier or fatty acid emulsifier comprising an HLB value of less than about 6.0. The method comprises forming a mixture comprising the agrochemical oil, the alkoxylated alkyl alcohol emulsifier, and the fatty acid ester emulsifier or fatty acid emulsifier, and mixing the mixture.

[0009] In yet another aspect, a method of using an emulsifier composition is provided. The emulsifier composition comprises an agrochemical oil, an alkoxylated alkyl alcohol emulsifier comprising a hydrophilic-lipophilic balance (HLB) value of at least about 6.0, and a fatty acid ester emulsifier or fatty acid emulsifier comprising an HLB value of less than about 6.0. The method comprises using the emulsifier composition to form an agrochemical emulsion composition that is storage-stable.BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 is a photograph depicting stability during storage for a comparative composition and compositions according to the present disclosure.

[0011] Figure 2 is a photograph depicting stability during storage for a comparative composition and compositions according to the present disclosure.DETAILED DESCRIPTION

[0012] It was surprisingly discovered herein that a combination of emulsifiers with specific chemistry and specific HLB values provide emulsion compositions with comparable or improved stability relative to emulsion compositions including nonylphenol ethoxylate emulsifiers. The disclosed combinations of emulsifiers are therefore suitable replacements for nonylphenol ethoxylate emulsifiers.

[0013] Provided herein is an emulsifier composition comprising: an agrochemical oil, an alkoxylated alkyl alcohol emulsifier comprising a hydrophilic-lipophilic balance (HLB) value of at least about 6.0, and a fatty acid ester emulsifier or fatty acid emulsifier comprising an HLB value of less than about 6.0.

[0014] In some embodiments, the emulsion composition does not comprise an aryl emulsifier. In some embodiments, the emulsion composition does not comprise a nonylphenol ethoxylate. Because the disclosed combination of emulsifiers provides comparable or improved stability relative to emulsion compositions including nonylphenol ethoxylate emulsifiers, such nonylphenol ethoxylate emulsifiers are not necessary or desirable to include.

[0015] In some embodiments, the alkoxylated alkyl alcohol emulsifier is an alkyl alcohol alkoxylate that comprises an HLB value of at least about 2.0, at least about 2.5, at least about 3.0, at least about 3.5, at least about 4.0, at least about 4.5, at least about 5.0, at least about240669W0015.5, at least about 6.0, at least about 6.5, at least about 7.0, at least about 7.5, at least about 8.0, at least about 8.5, at least about 9.0, at least about 9.5, at least about 10.0, at least about10.5, at least about 11.0, at least about 11.5, at least about 12.0, at least about 12.5, at least about 13.0, at least about 13.5, at least about 14.0, or at least about 14.5. In some embodiments, the alkoxylated alkyl alcohol emulsifier is an alkyl alcohol alkoxylate that comprises an HLB value of at most about 2.5, at most about 3.0, at most about 3.5, at most about 4.0, at most about 4.5, at most about 5.0, at most about 5.5, at most about 6.0, at most about 6.5, at most about 7.0, at most about 7.5, at most about 8.0, at most about 8.5, at most about 9.0, at most about 9.5, at most about 10.0, at most about 10.5, at most about 11.0, at most about 11.5, at most about 12.0, at most about 12.5, at most about 13.0, at most about13.5, at most about 14.0, at most about 14.5, or at most about 15.0.

[0016] In some embodiments, the alkoxylated alkyl alcohol emulsifier is an alkyl alcohol ethoxylate that comprises an HLB value of at least about 6.0, at least about 6.5, at least about 7.0, at least about 7.5, at least about 8.0, at least about 8.5, at least about 9.0, at least about9.5, at least about 10.0, at least about 10.5, at least about 11.0, at least about 11.5, at least about 12.0, at least about 12.5, at least about 13.0, at least about 13.5, at least about 14.0, or at least about 14.5. In some embodiments, the alkoxylated alkyl alcohol emulsifier is an alkyl alcohol ethoxylate that comprises an HLB value of at most about 6.5, at most about 7.0, at most about 7.5, at most about 8.0, at most about 8.5, at most about 9.0, at most about 9.5, at most about 10.0, at most about 10.5, at most about 11.0, at most about 11.5, at most about 12.0, at most about 12.5, at most about 13.0, at most about 13.5, at most about 14.0, at most about 14.5, or at most about 15.0.

[0017] In some embodiments, the alkoxylated alkyl alcohol emulsifier is alkoxylated with ethoxy groups, propoxy groups, butoxy groups, or a combination thereof.

[0018] In some embodiments, the alkoxylated alkyl alcohol emulsifier is alkoxylated with a number of alkoxy groups in a range of from about 1 to about 30.

[0019] In some embodiments, the alkoxylated alkyl alcohol emulsifier is alkoxylated with at least 1 , at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 11 , at least 12, at least 13, at least 14, at least 15, at least 16, at least17, at least 18, at least 19, at least 20, at least 21 , at least 22, at least 23, at least 24, at least25, at least 26, at least 27, at least 28, or at least 29 alkoxy groups.

[0020] In some embodiments, the alkoxylated alkyl alcohol emulsifier is alkoxylated with at most 2, at most 3, at most 4, at most 5, at most 6, at most 7, at most 8, at most 9, at most 10, at most 11 , at most 12, at most 13, at most 14, at most 15, at most 16, at most 17, at most18, at most 19, at most 20, at most 21 , at most 22, at most 23, at most 24, at most 25, at most26, at most 27, at most 28, at most 29 alkoxy groups, or at most 30 alkoxy groups.240669W001

[0021] In some embodiments, the alkoxylated alkyl alcohol emulsifier is an alcohol alkoxylate that is alkoxylated with at least 4, at least 5, at least 6, at least 7, at least 8, or at least 9 alkoxy groups. In some embodiments, the alkoxylated alkyl alcohol emulsifier is an alcohol alkoxylate that is alkoxylated with at most 5, at most 6, at most 7, at most 8, at most 9, or at most 10 alkoxy groups.

[0022] In some embodiments, the alkoxylated alkyl alcohol emulsifier is an alcohol ethoxylate that is alkoxylated with at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, or at least 11 ethoxy groups. In some embodiments, the alkoxylated alkyl alcohol emulsifier is an alcohol ethoxylate that is alkoxylated with at most 4, at most 5, at most 6, at most 7, at most 8, at most 9, at most 10, at most 11 , or at most 12 ethoxy groups.

[0023] In some embodiments, the alkoxylated alkyl alcohol emulsifier comprises a degree of branching in a range of from about 2 to about 4. In some embodiments, the alkoxylated alkyl alcohol emulsifier comprises a degree of branching of 2. In some embodiments, the alkoxylated alkyl alcohol emulsifier comprises a degree of branching of 3. In some embodiments, the alkoxylated alkyl alcohol emulsifier comprises a degree of branching of 4.

[0024] Generally, alkoxylated alkyl alcohol emulsifiers comprising a degree of branching of 1 are insufficient to provide improved stability. It has been discovered herein that a degree of branching in a range of from about 2 to about 4 is critical to mirror the functionality of nonylphenol ethoxylates.

[0025] In some embodiments, the fatty acid ester emulsifier or fatty acid emulsifier comprises a HLB value of at least about 2.0, at least about 2.5, at least about 3.0, at least about 3.5, at least about 4.0, or at least about 4.5.

[0026] In some embodiments, the fatty acid ester emulsifier or fatty acid emulsifier comprises a HLB value of at most about 2.5, at most about 3.0, at most about 3.5, at most about 4.0, at most about 4.5, or at most about 5.0.

[0027] In some embodiments, the fatty acid ester emulsifier or fatty acid emulsifier comprises a saturated fatty acid. In some embodiments, the fatty acid ester emulsifier or fatty acid emulsifier comprises an unsaturated fatty acid. In some embodiments, the fatty acid ester emulsifier or fatty acid emulsifier comprises a partially unsaturated fatty acid. In some embodiments, the fatty acid ester emulsifier or fatty acid emulsifier comprises a fully unsaturated fatty acid.

[0028] In some embodiments, the fatty acid ester emulsifier or fatty acid emulsifier comprises a fatty acid component selected from the group consisting of saturated fatty acids, oleate, laurate, myristate, palmate, stearate, unsaturated fatty acids, linoleic acid, linolenic acid, oleic acid, tall oil fatty acids, and combinations thereof.

[0029] Fatty acids, and their residues, are sometimes expressed in the form x:y, where x is240669W001 the number of carbon atoms in the fatty acid or residue and y is the number of carbon- carbon double bonds. In some embodiments, the fatty acid ester emulsifier or fatty acid emulsifier comprises a fatty acid component selected from the group consisting of 12:0, 14:0, 16:0, 18:0, 18:1 , 18:2, 18:3, and combinations thereof.

[0030] In some embodiments, the fatty acid ester emulsifier or fatty acid emulsifier comprises a tall oil fatty acid. In some embodiments, the fatty acid ester emulsifier or fatty acid emulsifier comprises a tall oil fatty acid comprising palmitic acid, stearic acid, oleic acid, linoleic acid, conjugated linoleic acid, other acids (rosin), and unsaponifiable matter. In some embodiments, the fatty acid ester emulsifier or fatty acid emulsifier comprises a tall oil fatty acid comprising a majority portion of oleic acid and linoleic acid.

[0031] In some embodiments, the fatty acid ester emulsifier or fatty acid emulsifier comprises an alcohol component selected from the group consisting of carbocyclic alcohols, heterocyclic alcohols, linear alcohols, branched alcohols, and combinations thereof.

[0032] In some embodiments, the fatty acid ester emulsifier or fatty acid emulsifier comprises an alcohol component selected from the group consisting of glycerol, sorbitan, glucose, sorbitol, and combinations thereof.

[0033] In some embodiments, the methylated seed oil is a methylated oil selected from the group consisting of soybean oils, corn oils, sunflower oils, canola oils, cottonseed oils, coconut oils, palm oils, and combinations thereof.

[0034] In some embodiments, the methylated seed oil is a paraffinic oil or mineral oil.

[0035] In some embodiments, the alkoxylated alkyl alcohol emulsifier and the fatty acid ester emulsifier or fatty acid emulsifier are present in a ratio in a range of from about 1.1 :1 to about 3:1.

[0036] In some embodiments, the alkoxylated alkyl alcohol emulsifier and the fatty acid ester emulsifier or fatty acid emulsifier are present in a ratio of at least 1.0:1 , at least 1.1 :1 , at least 1.2:1 , at least 1.3:1 , at least 1.4:1 , at least 1.5: 1 , or at least 1.6:1.

[0037] In some embodiments, the alkoxylated alkyl alcohol emulsifier and the fatty acid ester emulsifier or fatty acid emulsifier are present in a ratio of at most 1.1 :1 , at most 1.2:1 , at most 1.3:1 , at most 1.4:1 , at most 1.5:1 , at most 1.6:1 , or at most 1.7:1.

[0038] In some embodiments, the emulsifier composition comprises the agrochemical oil in an amount in a range of from about 75 wt% to about 90 wt%, the alkoxylated alkyl alcohol emulsifier in an amount in a range of from about 7.0 wt% to about 10.0 wt%, and the fatty acid ester emulsifier or fatty acid emulsifier in an amount in a range of from about 5.0 wt% to about 8.0 wt%.

[0039] In some embodiments, the agrochemical oil is present in an amount in a range of from about 75 wt% to about 90 wt%.240669W001

[0040] In some embodiments, the agrochemical oil is present in an amount of at least 75 wt%, at least 76 wt%, at least 77 wt%, at least 78 wt%, at least 79 wt%, at least 80 wt%, at least 81 wt%, at least 82 wt%, at least 83 wt%, or at least 84 wt%.

[0041] In some embodiments, the agrochemical oil is present in an amount of at most 76 wt%, at most 77 wt%, at most 78 wt%, at most 79 wt%, at most 80 wt%, at most 81 wt%, at most 82 wt%, at most 83 wt%, at most 84 wt%, or at most 85 wt%.

[0042] In some embodiments, the alkoxylated alkyl alcohol emulsifier is present in an amount of at least 7.0 wt%, at least 7.1 wt%, at least 7.2 wt%, at least 7.3 wt%, at least 7.4 wt%, at least 7.5 wt%, at least 7.6 wt%, at least 7.7 wt%, at least 7.8 wt%, at least 7.9 wt%, at least 8.0 wt%, at least 8.1 wt%, at least 8.2 wt%, at least 8.3 wt%, at least 8.4 wt%, at least 8.5 wt%, at least 8.6 wt%, at least 8.7 wt%, at least 8.8 wt%, at least 8.9 wt%, at least 9.0 wt%, at least 9.1 wt%, at least 9.2 wt%, at least 9.3 wt%, at least 9.4 wt%, at least 9.5 wt%, at least 9.6 wt%, at least 9.7 wt%, at least 9.8 wt%, at least 9.9 wt%, at least 10.0 wt%, at least 10.1 wt%, at least 10.2 wt%, at least 10.3 wt%, at least 10.4 wt%, at least 10.5 wt%, at least 10.6 wt%, at least 10.7 wt%, at least 10.8 wt%, at least 10.9 wt%, at least 11.0 wt%, at least 11.1 wt%, at least 11.2 wt%, at least 11.3 wt%, at least 11.4 wt%, at least 11.5 wt%, at least 11.6 wt%, at least 11.7 wt%, at least 11.8 wt%, at least 11.9 wt%, at least 12.0 wt%, at least 12.1 wt%, at least 12.2 wt%, at least 12.3 wt%, or at least 12.4 wt%.

[0043] In some embodiments, the alkoxylated alkyl alcohol emulsifier is present in an amount of at most 7.1 wt%, at most 7.2 wt%, at most 7.3 wt%, at most 7.4 wt%, at most 7.5 wt%, at most 7.6 wt%, at most 7.7 wt%, at most 7.8 wt%, at most 7.9 wt%, at most 8.0 wt%, at most 8.1 wt%, at most 8.2 wt%, at most 8.3 wt%, at most 8.4 wt%, at most 8.5 wt%, at most 8.6 wt%, at most 8.7 wt%, at most 8.8 wt%, at most 8.9 wt%, at most 9.0 wt%, at most 9.1 wt%, at most 9.2 wt%, at most 9.3 wt%, at most 9.4 wt%, at most 9.5 wt%, at most 9.6 wt%, at most 9.7 wt%, at most 9.8 wt%, at most 9.9 wt%, at most 10.0 wt%, at most 10.1 wt%, at most10.2 wt%, at most 10.3 wt%, at most 10.4 wt%, at most 10.5 wt%, at most 10.6 wt%, at most10.7 wt%, at most 10.8 wt%, at most 10.9 wt%, at most 11.0 wt%, at most 11.1 wt%, at most11.2 wt%, at most 11.3 wt%, at most 11.4 wt%, at most 11.5 wt%, at most 11.6 wt%, at most11.7 wt%, at most 11.8 wt%, at most 11.9 wt%, at most 12.0 wt%, at most 12.1 wt%, at most12.2 wt%, at most 12.3 wt%, at most 12.4 wt%, or at most 12.5 wt%.

[0044] In some embodiments, the fatty acid ester emulsifier or fatty acid emulsifier is present in an amount of at least 2.5 wt%, at least 2.6 wt%, at least 2.7 wt%, at least 2.8 wt%, at least 2.9 wt%, at least 3.0 wt%, at least 3.1 wt%, at least 3.2 wt%, at least 3.3 wt%, at least

[0045] 3.4 wt%, at least 3.5 wt%, at least 3.6 wt%, at least 3.7 wt%, at least 3.8 wt%, at least 3.9 wt%, at least 4.0 wt%, at least 4.1 wt%, at least 4.2 wt%, at least 4.3 wt%, at least 4.4 wt%, at least 4.5 wt%, at least 4.6 wt%, at least 4.7 wt%, at least 4.8 wt%, at least 4.9240669WG01 wt%, at least 5.0 wt%, at least 5.1 wt%, at least 5.2 wt%, at least 5.3 wt%, at least 5.4 wt%, at least 5.5 wt%, at least 5.6 wt%, at least 5.7 wt%, at least 5.8 wt%, at least 5.9 wt%, at least 6.0 wt%, at least 6.1 wt%, at least 6.2 wt%, at least 6.3 wt%, at least 6.4 wt%, at least 6.5 wt%, at least 6.6 wt%, at least 6.7 wt%, at least 6.8 wt%, at least 6.9 wt%, at least 7.0 wt%, at least 7.1 wt%, at least 7.2 wt%, at least 7.3 wt%, at least 7.4 wt%, at least 7.5 wt%, at least 7.6 wt%, at least 7.7 wt%, at least 7.8 wt%, or at least 7.9 wt%.

[0046] In some embodiments, the fatty acid ester emulsifier or fatty acid emulsifier is present in an amount of at most 2.6 wt%, at most 2.7 wt%, at most 2.8 wt%, at most 2.9 wt%, at most 3.0 wt%, at most 3.1 wt%, at most 3.2 wt%, at most 3.3 wt%, at most 3.4 wt%, at most 3.5 wt%, at most 3.6 wt%, at most 3.7 wt%, at most 3.8 wt%, at most 3.9 wt%, at most 4.0 wt%, at most 4.1 wt%, at most 4.2 wt%, at most 4.3 wt%, at most 4.4 wt%, at most 4.5 wt%, at most 4.6 wt%, at most 4.7 wt%, at most 4.8 wt%, at most 4.9 wt%, at most 5.0 wt%, at most5.1 wt%, at most 5.2 wt%, at most 5.3 wt%, at most 5.4 wt%, at most 5.5 wt%, at most 5.6 wt%, at most 5.7 wt%, at most 5.8 wt%, at most 5.9 wt%, at most 6.0 wt%, at most 6.1 wt%, at most 6.2 wt%, at most 6.3 wt%, at most 6.4 wt%, at most 6.5 wt%, at most 6.6 wt%, at most 6.7 wt%, at most 6.8 wt%, at most 6.9 wt%, at most 7.0 wt%, at most 7.1 wt%, at most7.2 wt%, at most 7.3 wt%, at most 7.4 wt%, at most 7.5 wt%, at most 7.6 wt%, at most 7.7 wt%, at most 7.8 wt%, or at most 7.9 wt%, or at most 8.0 wt%.

[0047] In some embodiments, the emulsifier composition further comprises an organic solvent. In some embodiments, the emulsifier composition further comprises an organic solvent selected from the group consisting of propylene glycol, ethylene glycol, and combinations thereof.

[0048] Provided herein is an agrochemical emulsion composition comprising the emulsifier composition, water, and an agrochemical active ingredient that is not water soluble.

[0049] Generally, the agrochemical active ingredient that is not water soluble may be any suitable agrochemical active ingredient known in the art that is not water soluble and facilitates the agrochemical emulsion composition.

[0050] In some embodiments, the agrochemical active ingredient has a water solubility less than 200 mg / L. In some embodiments, the agrochemical active ingredient has a water solubility less than 10 mg / L.

[0051] Generally, the agrochemical active ingredient may be any suitable agrochemical active ingredient known in the art that facilitates the compositions according to the present disclosure.

[0052] The agrochemical active ingredient may be any substance, whether a chemical or biological agent, used to control pests, such as insecticides, herbicides, fungicides, acaricides, rodenticides, nematicides, and miticides.

[0053] Suitable insecticides may be selected from the group consisting of neonicotinoids,240669W001 bisamides, benzoylureas and carbamates.

[0054] In some embodiments, the insecticide is selected from the group of fenoxycarb, piperonyl butoxide, imidacloprid, thiacloprid, acetamiprid, aldicarb, aldicarb sulfoxide, aldicarb sulfone, pirimicarb, chlorantraniliprole, terbufos, quinalphos, dyfonate, phosmet, carbaryl, etoxazole, thiamethoxam, flonicamid, etofenprox, phorate, profenofos, parathion, methylparathion, acephate, disulfoton, fenthion, fenvalerate, fipronil, baygon, methomyl, pymetrozine, oxamyl, tau-fluvalinate, cypermethrin, cyfluthrin, bifenthrin, tetramethrin, prallethrin (mix of isomers), permethrin (mix of isomers), resmethrin (mix of isomers), pyrethrin (mix of isomers), spinetoram(J), abamectin (mix of isomers), fenobucarb (BPMC), methiocarb, isoprocarb (MIPC), spirotetramat, Spinosad, trichlorfon, fenamiphos sulfoxide, fenamiphos sulfone, 3-hydroxycarbofuran, aldrin, DDE (p-p'), DDD (o-p), DDD (p-p'), DDE (o-p), DDT (o- p'), dieldrin, endrin, endrin aldehyde, endrin ketone, isodrin, chlordecone, mirex(Dodecachlorooctahydro-1 H-1 ,3,4-(epimethanetriyl)cyclobuta[cd]pentalene), and combinations thereof.

[0055] Suitable herbicides may be selected from the group of triazines and other photosystem 2 inhibitors, 2,6-dinitroanilines, ACCase inhibitors, PPO inhibitors, synthetic auxins, sulfonyl ureas, bipyrillium herbicides, chloroacetanilides, triazolopyrimidines, pyrazoles, herbicidal safeners, and combinations thereof.

[0056] In some embodiments, the herbicide is selected from the group of paclobutrazol, diuron, linuron, isoproturon, alachlor, pendimethalin, chlorpropham, fenoprop, bentazone, metolachlor, propazine, bromacil, 2,4-DB, fenoxaprop, fluometuron, molinate, cyanazine, simazine, atrazine, atrazine desethyl, metribuzin, and combinations thereof.

[0057] Suitable fungicides may be selected from the group of pyrimidines, anilinopyrimidines, triazoles and other sterol demethylation inhibitors, triazolopyrimidines, MAP kinase inhibitors, strobilurins, adenosine deaminase inhibitors, pyrazoles, carboxamides, and combinations thereof.

[0058] In some embodiments, the fungicide is selected from the group of bitertanol, boscalid, bromuconazole, cyproconazole, diclobutrazole, diniconazole, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, myclobutanil, penconazole, propiconazole, prothioconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole,2-aminobutane, 8-hydroxyquinoline sulphate, 2- phenylphenol (OPP), aldi-morph, ampropylfos, anilazine, azoxystrobin, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, blasticidin-S, bupirimate, buthiobate, calcium polysulphide, captafol, captan, carbendazim, carboxin, carpropamid, quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cyazofamid, cymoxanil, cyprodinil, cyprofuram, dichlorophen, diclocymet, diclofluanid, diclomezin, dicloran, diethofencarb, diflumetorim,240669W001 dimethirimol, dimethomorph, dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine, drazoxolon, edifenphos, enestroburin, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenarimol, fenfuram, fenhexamid, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluoromide, fluoxastrobin, flusulfamide, flutolanil, folpet, fosetyl- aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox, guazatine, hexachlorobenzene, imazalil, iminoctadine, iprobenfos (IBP), iprodione, iprovalicarb, isoprothiolane, kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copperoxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture, mancopper, mancozeb, maneb, mepanipyrim, kresoxim-methyl, mepronil, metalaxyl, methasulfocarb, methfuroxam, metiram, metominostrobin, metrafenone, metsulfovax, myclobutanil, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxycarboxin, pefurazoate, pencycuron, phosdiphen, picoxystrobin, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propineb, pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quinoxyfen, quintozene (PCNB), silthiofam, spiroxamine, sulphur and sulphur preparations, tecloftalam, tecnazene, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triazoxide, trichlamide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, validamycin, vinclozolin, zineb, ziram, zoxamide, and combinations thereof.

[0059] Suitable acaricides may be selected from the group of tebufenpyrad, aldicard, azinphosmethyl, carbophenothion, dimethoate, dicrotophos, triazophos, malathion, phosalone, methidathion, hexythiazox, propargite, spirodiclofen, methamidophos, monocrotophos, phenthoate, pirimiphosmethyl, epn, dichlorvos, ethion, fenitrothion, diazinon, chlorpyriphos, oxydemeton methyl, pyridaben, fenpropathrin, bifenazate, spiromesifen, fenpyroximate (mix of isomers), acequinocyl, carbofuran, and combinations thereof.

[0060] One suitable rodenticide is coumaphos.

[0061] One suitable nematicide is ethoprophos.

[0062] One suitable miticide is clofentezine.

[0063] In some embodiments, the agrochemical active ingredient is selected from the group of Imidacloprid, Difenoconazole, Broflanilide, Pyroxsulam, Cloquintocet-mexyl, Pyraclostrobin, Azoxystrobin, Cyflumetofen, Mesotrione, Fenpicoxamid, Metalaxyl, S- Metolachlor, Flonicamid, cypermethrin, Bifenthrin, Pyrethrin II, Azoxystrobin, Fenbuconazole, Cyproconazole, Tebuconazole, Prothioconazole, Trifloxystrobin, and combinations thereof.

[0064] In some embodiments, the agrochemical emulsion composition is in the form of a tank mix. In these embodiments, the emulsifier composition according to the present240669W001 disclosure is combined with a composition comprising water and an agrochemical active ingredient that is not water soluble. These compositions may be combined in a tank, or outside a tank and then provided to a tank, before application of the agrochemical emulsion composition.

[0065] Generally, the agrochemical active ingredient may be present in the agrochemical emulsion composition in any suitable amount known in the art that facilitates the compositions according to the present disclosure. In some embodiments, the amount of the agrochemical active ingredient in the agrochemical emulsion composition depends on the intended application rate. In some embodiments, the agrochemical active ingredient is present in the agrochemical emulsion composition in an amount sufficient to be applied at a rate in a range of from 10 g / ha to 20 kg / ha. In some embodiments, the agrochemical active ingredient is present in the agrochemical emulsion composition in an amount sufficient to be applied at a rate in a range of from 10 g / ha to 4 kg / ha. In some embodiments, the agrochemical active ingredient is present in the agrochemical emulsion composition in an amount sufficient to be applied at a rate in a range of from 20 g / ha to 1 .2 kg / ha.

[0066] In some embodiments, the agrochemical active ingredient is present in the agrochemical emulsion composition in an amount in a range of from about 0.1 wt% to about 20 wt%.

[0067] In some embodiments, the emulsifier composition is present in the agrochemical emulsion composition in an amount in a range of from about 0.5 v / v to about 2.5 v / v. In some embodiments, the emulsifier composition is present in the agrochemical emulsion composition in an amount less than 2.5 v / v. In some embodiments, the emulsifier composition is present in the agrochemical emulsion composition in an amount less than 1.5 v / v.

[0068] Provided herein is a method of making an agrochemical emulsion composition. The method comprises forming a mixture comprising the emulsifier composition, water, and an agrochemical active ingredient that is not water soluble, and mixing the mixture.

[0069] Provided herein is a method of making an emulsifier composition. The emulsifier composition comprises an agrochemical oil, an alkoxylated alkyl alcohol emulsifier comprising a hydrophilic-lipophilic balance (HLB) value of at least about 6.0, and a fatty acid ester emulsifier or fatty acid emulsifier comprising an HLB value of less than about 6.0. The method comprises forming a mixture comprising the agrochemical oil, the alkoxylated alkyl alcohol emulsifier, and the fatty acid ester emulsifier or fatty acid emulsifier; and mixing the mixture.

[0070] In some embodiments, the method further comprises adding an organic solvent to the mixture before mixing the mixture. In some embodiments, the organic solvent is selected from the group consisting of propylene glycol, ethylene glycol, and combinations thereof.

[0071] Provided herein is a use of an emulsifier composition to form an agrochemical240669W001 emulsion composition that is storage-stable.

[0072] Provided herein is a method of using an emulsifier composition. The emulsifier composition comprises an agrochemical oil, an alkoxylated alkyl alcohol emulsifier comprising a hydrophilic-lipophilic balance (HLB) value of at least about 6.0, and a fatty acid ester emulsifier or fatty acid emulsifier comprising an HLB value of less than about 6.0. The method comprises using the emulsifier composition to form an agrochemical emulsion composition that is storage-stable.

[0073] In some embodiments, the agrochemical emulsion comprises the emulsifier composition, water, and an agrochemical active ingredient that is not water soluble.

[0074] In some embodiments, the agrochemical emulsion is storage-stable for at least one week, at least one month, or at least one year under ambient conditions. In some embodiments, the agrochemical emulsion is storage-stable for at least one week, at least one month, or at least one year at 0 °C. In some embodiments, the agrochemical emulsion is storage-stable for at least one week, at least one month, or at least one year at 20 °C. In some embodiments, the agrochemical emulsion is storage-stable for at least one week, at least one month, or at least one year at 50 °C. In these embodiments, it is understood that the term “storage-stable” means that the agrochemical emulsion remains emulsified during storage and does not exhibit precipitation, flocculation, haze, or oil.EXAMPLES

[0075] The present technology will be further described in the following examples, which should be viewed as being illustrative and should not be construed to narrow the scope of the present disclosure or limit the scope to any particular embodiments.Example 1. Compositions.

[0076] A comparative composition (CE1) and compositions according to the present disclosure (IE1 , IE2, and IE3) were prepared according to the below table.

[0077] Agnique® ME 18SD-U is a distilled methyl soyate. Tergitol® NP-6 is a hydrophobic nonylphenol ethoxylate. Tergitol® NP-9 is a hydrophilic nonylphenol ethoxylate. Lutensol® TDA 6 is a six mole ethylene oxide adduct of tridecyl alcohol, which has a degree of branching of 3-4 and an HLB of 11. Mazol® 300 K is a hydrophobic blend of glycerol monooleate and propylene glycol, which has a degree of branching of <1.5 and an HLB of 3.8.240669W001Table 1a. Compositions.Example 2. Stability.

[0078] Stability was tested in accordance with the below tables. Each stability test was conducted with 5 wt% composition in 95 wt% water.240669W001Table 1. Volume of cream (mL) during storage for 34 ppm water hardness.240669W001Table 2. Volume of cream (mL) during storage for 342 ppm water hardness.240669W001Table 3. Volume of cream (mL) during storage for 1000 ppm water hardness.

[0079] These tables demonstrate that the compositions according to the present disclosure exhibit comparable or improved volume of creaming to comparative compositions including nonylphenol ethoxylates. Overall, compared to CE1 , the compositions according to the present disclosure yielded improved emulsification of Agnique ME 18S-LI in both soft and hard water for up to three hours after the initial preparation of the blend and after being stored for 30 days at 0 °C, room temperature, and 50 °C.

[0080] Particular conclusions include the following:

[0081] The freshly prepared IE2 and IE3 gave better emulsion performance when compared to freshly prepared CE1. The freshly prepared IE1 and CE1 showed equal emulsion performance.

[0082] After aging at 0 °C for 30 days, IE1 , IE2, and IE3 gave better emulsion performance240669W001 when compared to CE1.

[0083] After aging at room temperature for 30 days, only IE3 gave better emulsion performance when compared to CE1. IE1 and IE2 showed equal emulsion performance when compared to CE1.

[0084] After aging at 50 °C for 30 days, only IE3 gave better emulsion performance when compared to CE1. IE2 and IE3 showed equal emulsion performance when compared to CE1.

[0085] Overall, IE3 was the only blend that outperformed the freshly prepared and aged CE1.Example 3. Compositions.

[0086] A comparative composition (CE2) and compositions according to the present disclosure (IE4, IE5, IE6, IE7, and IE8) were prepared according to the below table.

[0087] Agnique® ME 18SD-LI is a distilled methyl soyate. Lutensol® TO 6 is a six mole ethylene oxide adduct of iso-tridecyl alcohol, which has a degree of branching of 2-3 and an HLB of 11. S-MAZ® 80 K is a hydrophobic sorbitan monooleate, which has a degree of branching of <1.5 and an HLB of 5.Table 4. Compositions.Example 4. Stability.

[0088] The stability of the comparative compositions and compositions according to the present disclosure are shown in Figures 1-2. Figure 1 shows stability for CE2, IE4, IE5, IE6, and IE7 after 24 hours at room temperature in reverse osmosis (RO) water. Figure 2 shows stability for CE2, IE4, IE5, IE6, IE7, and IE8 after 1 week at room temperature and room oxygen. As can be seen, increased amounts of S-MAZ® 80 K resulted in separation, i.e., there is reduced emulsion stability. However, compositions including 0 wt%, 10 wt% and 20 wt% S-MAZ® 80 K are stable after 1 week. Without being bound to any particular theory, it is believed that the increased hydrophobicity from increased amounts of S-MAZ® 80 K results in separation.Example 5. Component amounts.240669W001

[0089] Compositions were prepared according to the below table with various amounts of Lutensol® TDA 6 and Mazol® 300 K to demonstrate the importance of their relative amounts. Each of the compositions included 83.25 wt% Agnique® ME 18SD-LI and 1.75 wt% propylene glycol. Each of the compositions was introduced to water with a hardness of 342 ppm in an amount of 95% water and 5% composition.Table 5. Volume of cream (mL) for varying amounts of Lutensol® TDA 6 and Mazol® 300K.

[0090] It was observed that the emulsion stability was highly dependent on the relative amounts of Lutensol® TDA 6 and Mazol® 300 K.Example 6. Alkoxylation.

[0091] Compositions were prepared according to the below table with alkoxylated alkyl alcohol emulsifier having different degrees of alkoxylation to demonstrate the importance of alkoxylation and HLB.

[0092] Lutensol® TDA 3 is a three mole ethylene oxide adduct of tridecyl alcohol, which has an HLB of 8. Lutensol® TDA 9 is a nine mole ethylene oxide adduct of tridecyl alcohol, which has an HLB of 13.240669W001Table 6. Compositions.Example 7. Stability.

[0093] Stability was tested in accordance with the below table. Each stability test was conducted with 5 wt% composition in 95 wt% water.Table 7. Volume of cream (mL) after 2 hours for 342 ppm water hardness.Example 8. Compositions.

[0094] A comparative composition (CE7) and compositions according to the present disclosure (IE9-IE15) were prepared according to the below table.

[0095] MaxPure® Crop 100 is a paraffinic base oil (hydrotreated distillate, heavy paraffin, C20-C50) useful for agrochemical compositions. TOFA Altapyne® L-5 is a tall oil fatty acid that contains up to 5% rosin. TOFA Altapyne® L-5 does not have an HLB and is made up of linear fatty acids with up to 5% branching present from the rosin.240669W001Table 8. Compositions.Example 9. Stability.

[0096] Stability was tested in accordance with the below tables. Each stability test was conducted with 5 wt% composition in 95 wt% water.Table 9. Volume of cream (mL) during storage for 342 ppm water hardness after fresh240669W001 preparation at room temperature.

[0097] This table demonstrates that the compositions according to the present disclosure exhibit comparable or improved volume of creaming to comparative compositions including nonylphenol ethoxylates.

[0098] It was further observed that the addition of small amounts of water (a few drops) and >1 wt% propylene glycol could be used to remove any haze present in the compositions according to the present disclosure.Example 10. Compositions.

[0099] Compositions according to the present disclosure (IE16-IE18) were prepared according to the below table.Table 10. Compositions.Example 11. Stability.

[0100] Stability was tested in accordance with the below tables. Each stability test was conducted with 5 wt% composition in 95 wt% water.240669W001Table 11. Volume of cream (mL) during storage for 34 ppm water hardness.Table 12. Volume of cream (mL) during storage for 342 ppm water hardness.Table 13. Volume of cream (mL) during storage for 1000 ppm water hardness.240669W001

[0101] These tables demonstrates that the compositions according to the present disclosure did not exhibit any significant volume of creaming after a variety of storage conditions.Summary

[0102] It was observed that the compositions including Lutensol TDA 3 exhibited unsuitable emulsification shortly after formation. It was also observed that the compositions including Lutensol TDA 9 exhibited suitable emulsification shortly after formation. Therefore, it was determined that a relatively high degree of branching and specific amount of alkoxylation (e.g., ethoxylation) is required in order to replace a nonylphenol ethoxylate component that is hydrophobic and hydrophilic.

[0103] It was surprisingly discovered herein that compositions and methods in accordance with the present disclosure provide emulsion compositions with comparable or improved stability to emulsion compositions including nonylphenol ethoxylate emulsifiers. It was determined that a relatively high degree of branching and specific amount of alkoxylation (e.g., ethoxylation) is required in order to replace a nonylphenol ethoxylate component that is hydrophobic and hydrophilic. The disclosed compositions are therefore suitable replacements.

[0104] While embodiments of the present disclosure have been described, it should be understood that the present disclosure is not so limited and modifications may be made without departing from the present disclosure. The scope of the present disclosure is defined by the appended claims, and all devices, processes, and methods that come within the meaning of the claims, either literally or by equivalence, are intended to be embraced therein.

[0105] Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about”, is not limited to the precise value specified. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Range limitations may be combined and / or interchanged, and such ranges are identified and include all the sub-ranges stated herein unless context or language indicates otherwise. Other than in the operating examples or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions and the like, used in the specification and the claims, are to be understood as modified in all instances by the term “about”.

[0106] “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, or that the subsequently identified material may or may not be present, and that the description includes instances where the event or circumstance240669W001 occurs or where the material is present, and instances where the event or circumstance does not occur or the material is not present.

[0107] As used herein, the terms “comprises”, “comprising”, “includes”, “including”, “has”, “having”, or any other variation thereof, are intended to cover a non- exclusive inclusion. For example, a process, method, article or apparatus that comprises a list of elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0108] As used herein, the term “consisting of” excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0109] Where an invention or a portion thereof is defined with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the term “consisting of.”

[0110] Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0111] Also, the indefinite articles “a” and “an” preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore “a” or “an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.

[0112] As used herein, the term “wt%” refers to a percent by weight of the recited component relative to a total weight of the recited composition.

[0113] As used herein, the term “degree of branching” refers to the number of distinct side chains branching from a molecular backbone.

[0114] As used herein, the term “agrochemical oil” refers to an oil that is useful in agrochemical applications and functions a retention, wetting, spreading, and update agent.

[0115] As used herein, the term “fatty acid ester” refers to a compound that is formed from the combination of a fatty acid component and an alcohol component.

[0116] As used herein, the term “alkyl alcohol” refers to a compound that includes an alcohol group bonded to an alkyl group.

[0117] As used herein, the term “carbocyclic” refers to a cyclic hydrocarbon group and240669W001 does not include aryl groups.

[0118] As used herein, the term “heterocyclic” refers to a cyclic hydrocarbon group having at least one heteroatom and does not include aryl groups.

Claims

240669W001CLAIMSWHAT IS CLAIMED IS:

1. An emulsifier composition comprising: an agrochemical oil; an alkoxylated alkyl alcohol emulsifier comprising a hydrophilic-lipophilic balance (HLB) value of at least about 6.0; and a fatty acid ester emulsifier or fatty acid emulsifier comprising an HLB value of less than about 6.0.

2. The emulsifier composition of claim 1, wherein the emulsion composition does not comprise an aryl emulsifier.

3. The emulsifier composition of claim 1, wherein the emulsion composition does not comprise a nonylphenol ethoxylate.

4. The emulsifier composition of claim 1 , wherein the alkoxylated alkyl alcohol emulsifier is alkoxylated with ethoxy groups, propoxy groups, butoxy groups, or a combination thereof.

5. The emulsifier composition of claim 1 , wherein the alkoxylated alkyl alcohol emulsifier is alkoxylated with a number of alkoxy groups in a range of from about 1 to about 30.

6. The emulsifier composition of claim 1 , wherein the alkoxylated alkyl alcohol emulsifier comprises a degree of branching in a range of from about 2 to about 4.

7. The emulsifier composition of claim 1, wherein the fatty acid ester emulsifier or fatty acid emulsifier comprises an unsaturated fatty acid.

8. The emulsifier composition of claim 1, wherein the fatty acid ester emulsifier or fatty acid emulsifier comprises a fatty acid component selected from the group consisting of saturated fatty acids, oleate, laurate, myristate, palmate, stearate, unsaturated fatty acids, linoleic acid, linolenic acid, oleic acid, tall oil fatty acids, and combinations thereof.

9. The emulsifier composition of claim 1, wherein the fatty acid ester emulsifier or fatty acid emulsifier comprises an alcohol component selected from the group consisting of carbocyclic alcohols, heterocyclic alcohols, linear alcohols, branched alcohols, and combinations thereof.

10. The emulsifier composition of claim 1, wherein the agrochemical oil is selected from240669W001 the group consisting of methylated seed oils, methylated soybean oil, methylated corn oil, methylated sunflower oil, methylated canola oil, methylated cottonseed oil, methylated coconut oil, methylated palm oil, paraffinic oils, mineral oils, and combinations thereof.

11. The emulsifier composition of claim 1 , wherein the alkoxylated alkyl alcohol emulsifier and the fatty acid ester emulsifier or fatty acid emulsifier are present in a ratio in a range of from about 1.1 :1 to about 3: 1.

12. The emulsifier composition of claim 1, comprising: the agrochemical oil in an amount in a range of from about 75 wt% to about 90 wt%; the alkoxylated alkyl alcohol emulsifier in an amount in a range of from about 7.0 wt% to about 10.0 wt%; and the fatty acid ester emulsifier or fatty acid emulsifier in an amount in a range of from about 5.0 wt% to about 8.0 wt%.

13. The emulsifier composition of claim 1, further comprising an organic solvent selected from the group consisting of propylene glycol, ethylene glycol, and combinations thereof.

14. An agrochemical emulsion composition comprising: the emulsifier composition of claim 1; water; and an agrochemical active ingredient that is not water soluble.

15. A method of making an agrochemical emulsion composition, comprising: forming a mixture comprising the emulsifier composition of claim 1 , water, and an agrochemical active ingredient that is not water soluble; and mixing the mixture.

16. A method of making an emulsifier composition comprising an agrochemical oil; an alkoxylated alkyl alcohol emulsifier comprising a hydrophilic-lipophilic balance (HLB) value of at least about 6.0; and a fatty acid ester emulsifier or fatty acid emulsifier comprising an HLB value of less than about 6.0, the method comprising: forming a mixture comprising the agrochemical oil, the alkoxylated alkyl alcohol emulsifier, and the fatty acid ester emulsifier or fatty acid emulsifier; and mixing the mixture.

17. The method of claim 15, further comprising adding an organic solvent to the mixture before mixing the mixture.

18. A method of using an emulsifier composition comprising an agrochemical oil; an240669W001 alkoxylated alkyl alcohol emulsifier comprising a hydrophilic-lipophilic balance (HLB) value of at least about 6.0; and a fatty acid ester emulsifier or fatty acid emulsifier comprising an HLB value of less than about 6.0, the method comprising: using the emulsifier composition to form an agrochemical emulsion composition that is storage-stable.

19. The method of claim 15, wherein the agrochemical emulsion comprises the emulsifier composition, water, and an agrochemical active ingredient that is not water soluble.

20. The method of claim 15, wherein the agrochemical emulsion is storage-stable for at least one week under ambient conditions.

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