阅读说明：本技术 用于降低喷雾漂移的组合物和方法 (Compositions and methods for reducing spray drift ) 是由 S·夏尔马 S·哈伯特 于 2019-06-19 设计创作，主要内容包括：一种用于喷雾施用的农药水溶液浓缩物,其包含水溶性农药盐和包含蛋白质和脂肪酸的漂移降低剂。(An aqueous pesticide solution concentrate for spray application comprising a water soluble pesticide salt and a drift reduction agent comprising a protein and a fatty acid.)

1. An aqueous pesticide solution concentrate for spray application comprising a water soluble pesticide salt and a drift reduction agent comprising a protein and a fatty acid, wherein the concentration of the fatty acid is at least 5g/L of the solution concentrate.

2. The pesticide solution concentrate as set forth in claim 1 wherein the protein is present in an amount of at least 0.1g/L of the solution concentrate.

3. The aqueous pesticide solution concentrate as claimed in any one of the preceding claims wherein the weight ratio of protein to fatty acid is from 1:500 to 1: 1.

4. The aqueous pesticide solution concentrate as claimed in any one of the preceding claims, wherein the weight ratio of protein to fatty acid is from 1:100 to 1: 5.

5. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the fatty acid is present in an amount of from 5 to 300 g/L.

6. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the fatty acid is present in an amount of from 50 to 250 g/L.

7. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the protein is present in an amount of from 0.1 to 100 g/L.

8. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the protein is present in an amount of from 1 to 20 g/L.

9. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the protein is present in an amount of from 1 to 10 g/L.

10. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the water-soluble pesticide salt is selected from the group consisting of herbicides, plant growth regulators, and nematicides.

11. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the water soluble pesticide salt is an organic acid pesticide in the form of a salt selected from the group consisting of a carboxylate, a phosphonate, a sulfonate or mixtures thereof.

12. The aqueous pesticide concentrate of claim 11 wherein the water soluble pesticide salt comprises a salt counterion selected from the group consisting of an alkali metal counterion, an ammonia counterion, an amine counterion, and mixtures thereof.

13. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the water-soluble pesticide is present in an amount of at least 50g/L based on the active ion of the water-soluble pesticide.

14. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the water-soluble pesticide is present in an amount of at least 100g/L based on the active ion of the water-soluble pesticide.

15. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the water-soluble pesticide is present in an amount of at least 300g/L based on the active ion of the water-soluble pesticide.

16. The pesticidal solution concentrate as claimed in any one of the preceding claims, wherein the fatty acid is C₆-C₂₂A fatty acid or a salt thereof.

17. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the fatty acid comprises at least one C₈-C₂₂Fatty acids or salts thereof, preferably C₁₄-C₁₈A fatty acid or salt thereof, or a combination thereof.

18. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the fatty acid is ethylenically unsaturated.

19. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the fatty acid is selected from the group consisting of oleic acid, ricinoleic acid, linoleic acid, caproic acid, pelargonic acid, stearic acid, salts thereof, and mixtures thereof.

20. The aqueous pesticide solution concentrate as claimed in any one of the preceding claims, wherein the protein is selected from the group consisting of casein, albumin, lactalbumin, whey protein, soy protein isolate, pea protein, cereal protein, bovine protein, or salts or combinations thereof.

21. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the protein is sodium caseinate.

22. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the pesticide is selected from herbicides in the form of carboxylates and phosphates.

23. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the pesticide is a water soluble salt present in an amount of at least 50g/L and at most 750g/L, wherein the concentration is based on the pesticidally active ion of the salt.

24. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims, wherein the pesticide is selected from the group consisting of water-soluble salts of one or more of aromatic acid herbicides, organophosphorus herbicides, phenoxyalkanoic acid herbicides, aryloxyphenoxyalkanoic acid herbicides, picolinic acid herbicides, quinolone carboxylic acid herbicides.

25. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims wherein the pesticide comprises a water soluble salt of at least one acid herbicide selected from the group consisting of benzoic acid herbicides, phenoxyacetic acid herbicides, phenoxybutyric acid herbicides, phenoxypropionic acid herbicides, and picolinic acid herbicides.

26. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims, wherein the pesticide comprises a water soluble salt of at least one acid herbicide selected from the group consisting of 2,4-d, dicamba, 2-methyl-4-chloro, aminopyralid, clopyralid, picloram, halauxifen, flopyrauxifen, 2,4-d propionic acid, 2-methyl-4-chloropropionic acid, high 2,4-d propionic acid, 2-methyl-4-chloropropionic acid.

27. The aqueous pesticide solution concentrate as set forth in any one of the preceding claims comprising a mixture of water-soluble herbicide acid salts, wherein the herbicide acid comprises: (a) dicamba, high 2,4-d propionic acid and 2, 4-d; (b)2 methyl 4 chloro and refined 2 methyl 4 chloropropionic acid; (c) 2-methyl-4-chloro and 2, 4-d-propionic acid; (d) dicamba and purified 2-methyl-4-chloropropionic acid; (e) dicamba and high 2,4-d propionic acid; or (f)2, 4-D and high 2,4-D propionic acid; (g)2, 4-D and refined 2-methyl-4-chloropropionic acid.

28. The aqueous pesticidal solution concentrate of any one of claims 24-27 wherein the acid herbicide is present in an amount of at least 150gae/L, preferably at least 300gae/L, more preferably at least 500 gae/L.

29. The aqueous pesticide solution concentrate as claimed in any one of the preceding claims, wherein the pesticide is selected from water soluble salts of 2,4-d, dicamba and mixtures thereof, wherein the salt is selected from amine salts.

30. The aqueous pesticide solution concentrate as claimed in any one of the preceding claims, wherein the pH of a 1% sample of the solution concentrate in water is between 3.5 and 9.0, preferably between 5.5 and 8.0.

31. The aqueous pesticide solution concentrate as claimed in any one of the preceding claims, wherein the pesticide comprises at least one selected from the group consisting of plant growth regulators, nematicides and insecticides, preferably selected from the group consisting of: a nematicide selected from the group consisting of water soluble salts of 3,4, 4-trifluoro-3-butenoic acid and N- (3,4, 4-trifluoro-1-oxo-3-butenyl) glycine; a plant growth regulator selected from the group consisting of water-soluble salts of ethephon, gibberellic acid, glyphosine, maleic hydrazide, fluorobensulfuron, 1-naphthylacetic acid, and triiodobenzoic acid; and water-soluble organophosphorus insecticides such as acephate and methamidophos.

32. The aqueous pesticide solution concentrate as claimed in any one of the preceding claims wherein the generation of fine mist droplets having a diameter of less than 150 μm is reduced below the generation of fine mist droplets of a composition which does not comprise a drift reduction component when tested at an application rate for pesticide control.

33. The aqueous pesticide solution concentrate as claimed in any one of the preceding claims wherein the generation of fine mist droplets having a diameter of less than 105 μm is reduced below the generation of fine mist droplets of a composition which does not comprise a drift reduction component when tested at an application rate for pesticide control.

34. A method of pest control which comprises diluting an aqueous pesticidal concentrate as claimed in any preceding claim with water and applying the diluted concentrate to the locus of the pest to be controlled by spray application.

FIELD

The present invention relates to an aqueous pesticide concentrate for spray application having reduced spray drift, a method of making the solution concentrate, and a method of reducing spray drift using the concentrate.

Background

The potential for off-target spray drift of pesticide applications is of agricultural and social concern. Off-target movement due to spray drift has the potential to adversely affect adjacent crops and cause adverse environmental effects. In addition, spray drift may require the use of more chemicals than would otherwise be required to achieve the desired pest control in the desired area.

Spray drift is caused by airborne motion, particularly of fine droplets produced by the nozzle, and is exacerbated by evaporation of the droplets and wind shear. Droplets with a size of less than 150 microns, in particular less than 105 microns, can travel a considerable distance.

Spray drift can be controlled by adding additives to the spray tank, wherein the pesticide concentrate is diluted with water prior to spray application. High molecular weight polymers such as polysaccharide gums, polyacrylamides, polyethylene oxides, and other synthetic polymers have been used as drift control agents. Such polymers can be difficult to disperse in aqueous concentrate and can lead to nozzle clogging. They are also often incompatible with water soluble salt pesticides because they form gels with the pesticide. Esterified seed and mineral oils have also been investigated, but generally cannot be easily incorporated into solution concentrates without compromising the stability of the concentrate and/or the diluted concentrate prepared prior to spray application.

It would be useful to include a drift control agent in the pesticide concentrate such that it is present in an amount relative to the pesticide to provide a predetermined level of drift control. The use of drift control agents in concentrates presents additional problems due to the need to provide stability of the concentrate upon storage. The presence of much higher loadings of pesticide and any adjuvant, as compared to diluted concentrates used for spraying, also exacerbates the problem of incompatible components, which can lead to phase separation, precipitation, gel formation, or unacceptably high viscosities for convenient dispensing of the concentrate. Furthermore, the incorporation of drift control agents in concentrates presents a problem risk, such as phase separation or precipitation when the concentrate is diluted prior to spray application of the diluted concentrate. The problems that occur with dilution are often exacerbated by the different qualities of water used in agricultural settings.

There is a need for drift control agents that can be used in pesticide solution concentrates.

SUMMARY

We have found that the combination of protein and fatty acid in an aqueous pesticide concentrate makes it possible to provide a stable formulation in the concentrate and on dilution, and has a favourable effect on the atomisation performance of the diluted solution, thereby providing a significant drift reduction on spray application of the diluted concentrate. Accordingly, there is provided an aqueous pesticide solution concentrate for spray application comprising a water soluble pesticide salt and a drift reduction agent comprising protein and fatty acids, wherein the concentration of fatty acids is at least 5 g/L.

The aqueous pesticide concentrate can be an aqueous concentrate of a water-soluble pesticide salt (e.g., an organic pesticide in the form of a water-soluble salt). The invention is particularly suitable for controlling the drift of organic acid pesticides, such as carboxylic, phosphonic and sulphonic acid pesticides, in the form of water soluble salts selected from alkali metal, ammonium and amine salts.

The present invention further provides a method for controlling pests using the aqueous pesticide solution concentrate, comprising diluting the aqueous pesticide solution concentrate with water and applying the diluted concentrate to the locus of the pests to be controlled by spray application.

Detailed Description

The term pesticide as used herein includes insecticides, fungicides, herbicides, acaricides, nematicides, plant growth regulators and mixtures thereof, typically applied in the form of a liquid composition. Preferred pesticides for use in the concentrate of the present invention are nematicides, plant growth regulators and herbicides, especially herbicides. The pesticide is a water-soluble pesticide salt, for example a salt selected from the group consisting of herbicide acids, plant growth regulators and nematicides. More preferred pesticides are water-soluble salts of herbicidal acids, particularly auxin herbicides, such as one or more herbicides selected from the group consisting of benzoic acid herbicides, phenoxyacetic acid herbicides, phenoxybutyric acid herbicides, pyridine carboxylic acid herbicides, phenoxypropionic acid herbicides and picolinic acid herbicides.

Where the terms "comprises," "comprising," or "including" are used in this specification (including the claims), they are to be interpreted as specifying the presence of the stated features, integers, steps or components, but not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

The term "spray mixture" refers to a concentrated composition of herbicide in a liquid diluent, especially water, suitable for spray application. The spray mixture may contain adjuvants such as surfactants and spray oils which are part of the herbicide concentrate, added during the preparation of the spray mixture, or both.

The term "water-soluble pesticide" as used herein includes any pesticide that is water-soluble at the concentrations used in the concentrate. Typically, the water-soluble pesticide, e.g., a water-soluble salt of a herbicidal acid, has a solubility in pure water of at least 50g/L, e.g., 100g/L, at least 150g/L, at least 200g/L, at least 300g/L, at least 500g/L, or at least 600g/L at a temperature of 25 ℃.

The term "fatty acid" describes an aliphatic monocarboxylic acid. Various embodiments include fatty acids having an aliphatic hydrocarbon chain, known naturally occurring fatty acids are generally unbranched and contain an even number of from about 6 to about 24 carbons, from about 8 to 22 carbons, and other embodiments include fatty acids having 12 to 18 carbons in the aliphatic hydrocarbon chain. Embodiments of the present invention include naturally occurring fatty acids as well as non-naturally occurring fatty acids, which may contain an odd number of carbons. Thus, in some embodiments of the invention, the fatty acid has an odd number of carbons, such as from 7 to 23 carbons, and in other embodiments, from 11 to 19 carbons.

The aliphatic hydrocarbon chain of the fatty acids of the various embodiments may be unsaturated. The term "unsaturated" refers to a fatty acid having an aliphatic hydrocarbon chain containing at least one double bond and/or substituent. In contrast, "saturated" hydrocarbon chains do not contain any double bonds or substituents. Thus, each carbon of the hydrocarbon chain is "saturated" and has the maximum number of hydrogens.

The term "adjuvant" as used herein is a broad term and has its ordinary and customary meaning to those skilled in the art (and is not limited to a specific or customized meaning) and refers to, but is not limited to, agents that modify the action of other agents and more particularly serve to enhance the efficacy of a pesticide or modify the physical characteristics of a mixture.

The pesticide concentrate typically comprises an aqueous liquid carrier. The term liquid carrier is used to refer to an aqueous carrier that does not contain fatty acids or proteins or adjuvants such as surfactants. The liquid carrier can be water and an optional co-solvent in an amount of from about 0 to about 50 weight percent of the liquid carrier. In some embodiments, the presence of a co-solvent such as an alcohol or glycol may be used to help stabilize the concentrate composition depending on the concentration of the pesticide and its water solubility. In the case of water-soluble salts of auxin herbicides, a co-solvent may not be required, or if present, may generally be limited in amount, for example to no more than 5% by weight of the liquid carrier.

The fatty acid may be in the form of a salt, for example at least one of an alkali metal salt (particularly a lithium, potassium or sodium salt or a mixture of such salts), an ammonia salt or an amine salt. Furthermore, the fatty acids may comprise mixtures of different individual fatty acids, such as those typically found in naturally occurring fatty acids. It is also understood that various fatty acid salts may form in solution depending on the pH and counterions present in the solution.

The pesticide solution concentrate includes a water soluble pesticide salt active and a drift reducer that includes a protein and a fatty acid.

The pesticidal active is water-soluble or in a water-soluble form, and the solution concentrate is an aqueous solution concentrate, i.e. the active is present in solution. The pesticide may be present in the form of a water soluble salt, for example a salt with an alkali metal, a nitrogen base, for example a pesticide acid selected from ammonia and amines or mixtures thereof.

The concentration of the pesticide in the pesticide solution concentrate depends on the solubility and efficacy of the pesticide. Typically, the pesticide is present in an amount of at least 50g/L, such as at least 100g/L, at least 150g/L, at least 200g/L, at least 300g/L, at least 400g/L, or at least 500 g/L. Where the pesticide is in the form of a water-soluble salt of a pesticidal acid, the corresponding concentration of the salt may be expressed as grams of acid equivalent of the salt per liter of solution concentrate.

The drift reduction agent includes a protein and a fatty acid. The concentration of protein and fatty acid in the composition depends on the presence of other components and the degree of drift reduction desired in the proposed spray application of the composition, including the degree of dilution of the water used in the pesticide spray application. In one group of embodiments, the drift reduction agent comprises protein in an amount of up to 100g/L, preferably up to 30g/L, such as 0.1-30g/L, 0.5-20g/L or 1-15g/L, and fatty acid in an amount of up to 300g/L, such as 5-300g/L, 10-300g/L, 20-250g/L or 50-250 g/L. It will be appreciated that in the diluted composition formed for spraying the pesticide, the concentration of drift reducing agent is very significantly reduced compared to the concentration of the concentrate.

The preferred fatty acid is C₆-C₂₂Fatty acids or salts thereof, and may be saturated or unsaturated fatty acids. In one group of embodiments, the fatty acid is C₈-C₂₂Fatty acid or salt thereof, preferably C₁₄-C₂₀A fatty acid or salt thereof, or a combination thereof. C₆-C₂₂Examples of fatty acids or salts thereof include oleic acid, ricinoleic acid, linoleic acid, caproic acid, lauric acid, capric acid, pelargonic acid, stearic acid, salts thereof, and mixtures thereof. In one set of embodiments, the fatty acid is ethylenically unsaturated. It has been found that unsaturated C₁₆-C₂₀Fatty acids (especially C)₁₆-C₁₈Fatty acids) in combination with proteins perform well in reducing spray drift. For example, in particular embodiments, it has been found effective for the pesticide solution concentrate to contain a fatty acid selected from the group consisting of oleic acid, ricinoleic acid, linoleic acid, salts thereof, and mixtures thereof.

The pesticide solution concentrate includes a protein as part of a drift reducer. Proteins from a range of sources, such as plant and animal proteins, may be used. Examples of proteins are milk proteins (e.g. casein, sodium caseinate, calcium caseinate, lactalbumin, milk powder, whey protein), vegetable proteins (e.g. gluten, e.g. from wheat; soy extract, peanut extract, zein), animal proteins (e.g. fish, meat and egg proteins). Examples of particularly suitable proteins may be selected from casein, albumin, lactalbumin, whey protein, soy protein isolate, cereal protein or salts thereof, or combinations thereof. Sodium caseinate was found to be a convenient choice for the protein component of the drift reducing agent.

The pesticide solution concentrate may contain a range of ratios of combinations of protein and fatty acid, and the optimum ratio of protein to fatty acid for a particular solution concentrate may be readily determined. In one group of embodiments, the weight ratio of protein to fatty acid is from 1:500 to 1:1, preferably from 1:100 to 1: 5.

The pesticidally active substances present in the pesticidal solution concentrate are usually soluble in the aqueous concentrate. If desired, a co-solvent may be present to improve solubility. In one set of embodiments, the pesticide active is a water-soluble pesticide in the form of a salt of a pesticide acid with a suitable cationic counterion. Examples of such pesticides include acid groups such as carboxylic acids, phosphonic acids, sulfonic acids, and the like, and the pesticide may include a counterion, such as a counterion selected from the group consisting of alkali metals, ammonia, and amines.

Examples of alkali metal counterions include sodium, potassium and lithium.

In one embodiment, the pesticide salt is a salt of an acidic pesticide, such as an auxin herbicide, with a nitrogen base. The nitrogen base may be selected from a series of compounds, such as those of formula I:

wherein:

R¹selected from hydrogen, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkanols and C₁-C₁₀An aminoalkyl group;

R²and R³Independently selected from hydrogen, C₁-C₆Alkyl radical, C₁-C₆Alkanol, C₁-C₆Aminoalkyl and wherein R²And R³Together forming a 5-or 6-membered heterocyclic ring containing the nitrogen of formula I and optionally a further heteroatom selected from O and N as ring members and optionally C₁-C₆Alkyl substitution. Wherein R is²And R³Examples of compounds of formula I which constitute heterocycles include piperazine, morpholine and N-alkyl derivatives thereof.

Preferably at least one nitrogen base is present, including in one embodiment selected from ammonia, C₁-C₁₀Alkylamine, di- (C)₁-C₆Alkyl) amine, tri- (C)₁-C₆Alkyl) amine, C₁-C₁₀Alkanolamine, C₁-C₆Alkyl radical (C)₁-C₆Alkanols) amines and di- (C)₁-C₆Alkyl) (C₁-C₆Alkanol) amine.

In one set of embodiments, the nitrogen base comprises a nitrogen base selected from the group consisting of ammonia, C₁-C₁₀Alkylamine, di- (C)₁-C₄Alkyl) amine, tri- (C)₁-C₄Alkyl) amine, C₁-C₁₀Alkanolamine, C₁-C₄Alkyl radical (C)₁-C₄Alkanols) amines and di- (C)₁-C₄Alkyl) (C₁-C₄Alkanol) amine.

In another embodiment, the amines include cycloaliphatic amines, for example 5 and 6 membered aliphatic rings containing at least one ring nitrogen and optionally other heteroatoms such as nitrogen or oxygen and which are optionally substituted.

Specific examples of readily available nitrogen bases include those selected from the group consisting of ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, tributylamine, isobutylamine, diisobutylamine, triisobutylamine, 1-methylpropylamine (D, L), bis (1-methyl) propylamine (D, L), 1-dimethylethylamine, pentylamine, dipentylamine, tripentylamine, 2-pentylamine, 3-pentylamine, 2-methylbutylamine, 3-methylbutylamine, bis (3-methylbutyl) amine and tris (3-methylbutyl) amine, diglycolamine, isophoronediamine, and aminomethylpiperazine.

In another embodiment, the pesticide active comprises an acid group, such as a carboxylic acid, phosphonic acid, sulfonic acid, and the like, and the pesticide comprises a counterion that is a quaternary amine, such as a quaternary amine of formula II:

wherein R is¹、R²And R³As defined in formula I, R⁴As for R of formula I¹As defined. Specific examples of quaternary amines include tetra (C)₁-C₄Alkyl) amines, such as tetramethylammonium.

In a preferred group of embodiments, the water-soluble pesticide salt is present in an amount of at least 50g/L and at most 750g/L, preferably at least 150g/L and at most 750g/L, more preferably at least 300g/L, such as at least 500g/L, wherein the amount is based on the pesticidally active ion, e.g., acid equivalent (gae/L).

In one embodiment, the pesticide present in the pesticide solution concentrate is a herbicide, preferably a water-soluble herbicide such as a salt of a herbicidal acid, wherein the herbicide may for example be in the form of a salt of the carboxylic, phosphoric, phosphonic and sulfonic acid groups present in the herbicide.

The salt of the acid herbicide may be selected from one or more salts selected from aromatic acid herbicides, organophosphorus herbicides, thiadiazinones, phenoxyalkanoic acid herbicides, aryloxy-phenoxyalkanoic acid herbicides, picolinic acid herbicides, quinolone carboxylic acid herbicides, and mixtures of two or more thereof. More preferred herbicides are auxin herbicides such as aromatic acid herbicides, phenoxy alkanoic acid herbicides, picolinic acid herbicides and mixtures of two or more thereof.

The salt counterion may be, for example, an alkali metal salt such as a potassium or sodium salt, or a nitrogen salt counterion such as ammonia, or an amine such as a primary, tertiary or quaternary amine salt. Specific examples of amine counterions are the counterions of formula I above.

Specific examples of readily available nitrogen bases include, but are not limited to, those selected from the group consisting of ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, tetramethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, tributylamine, isobutylamine, diisobutylamine, triisobutylamine, 1-methylpropylamine (D, L), bis (1-methyl) propylamine (D, L), 1-dimethylethylamine, pentylamine, dipentylamine, tripentylamine, 2-pentylamine, 3-pentylamine, 2-methylbutylamine, 3-methylbutylamine, bis (3-methylbutyl) amine, tris (3-methylbutyl) amine, N-bis (3-aminopropyl) methylamine, diglycolamine, isophoronediamine and aminopiperazine, monoethanolamine, diethanolamine, triethanolamine, and others, Propanolamine, ethylamine, benzylamine, triisopropanolamine, butylisopropanolamine, N- (. beta. -aminoethyl) ethanolamine, N-methylmonoethanolamine, N-ethylmonoethanolamine, N-butylmonoethanolamine, N-methyldiethanolamine and N-butyldiethanolamine, aminomethylpropanolamine, 2-amino-2-methyl-1, 3-propanediol and 2-amino-2- (hydroxymethyl) propane-1, 3-diol.

Specific examples of preferred nitrogen bases may be selected from ammonia, methylamine, isopropylamine, dimethylamine, diethylamine, diisopropylamine, triethylamine, triisopropylamine, dimethylethanolamine and diglycolamine.

In a particular embodiment, the pesticide comprises a water-soluble salt of at least one acid herbicide selected from the group consisting of benzoic acid herbicides, imidazolinones, thiadiazinones, phenoxyacetic acid herbicides, phenoxybutyric acid herbicides, phenoxypropionic acid herbicides, picolinic acid herbicides and organophosphorus herbicides, benzoic acid herbicides, imidazolinones, thiadiazinones, phenoxyacetic acid herbicides, phenoxybutyric acid herbicides, phenoxypropionic acid herbicides, picolinic acid herbicides, in particular 2,4-D, dicamba (dicamba), aminopyralid (aminopyralid), clopyralid (clopyralid), picloram (picloram), halauxifen, flopyrauxifen, 2, 4-dichloropropric acid (dichlorprop), 2-4-chloropropionic acid (mecoprop), homo 2, 4-dipropionic acid (dichlorprop-P), 2-methyl-4-chloropropionic acid (mecoprop-P), bentazone (bentazone), imazamox (imazamox), imazapyr (imazapyr), glyphosate (glyphosate), and glufosinate (glufosinate).

Particularly suitable water-soluble herbicides include auxin herbicides including water-soluble salts of 3, 6-dichloro-2-methoxybenzoic acid (dicamba), 2,4-D, clomeprop (clomeprop), 2,4-D propionic acid, homo-2, 4-D propionic acid, 2 methyl 4 chloro (MCPA), 2 methyl 4 chlorobutyric acid (MCPB), 2 methyl 4 chloropropionic acid, chloramben (chloramben), sprouten (TBA), picloram, clopyralid, aminopyralid and mixtures of two or more thereof.

In one embodiment, the composition comprises a mixture of two or more herbicides selected from 3, 6-dichloro-2-methoxybenzoic acid (dicamba), 2,4-d, barnyard grass amine, 2,4-d propionic acid, high 2,4-d propionic acid, 2 methyl 4 chloro, 2 methyl 4 chlorobutyric acid, 2 methyl 4 chloropropionic acid, ametryn, glufosinate, picloram, clopyralid or aminopyralid. Specific examples of such mixtures include (a) dicamba, high 2,4-d propionic acid and 2, 4-d; (b)2 methyl 4 chloro and refined 2 methyl 4 chloropropionic acid; (c) dicamba and high 2,4-d propionic acid; d)2, 4-D and high 2,4-D propionic acid; e)2, 4-D and refined 2-methyl-4-chloropropionic acid.

In one set of embodiments, the pesticide solution concentrate includes a water-soluble herbicide salt of a herbicidal acid, wherein the herbicide salt is present in an amount of at least 50g/L, such as at least 100g/L, at least 150g/L, at least 200g/L, at least 300g/L, at least 500g/L, or at least 600g/L, typically at most 750g/L, based on herbicidal acid equivalents per liter of solution concentrate (gae/L).

The invention is particularly suitable for use with a pesticide solution concentrate selected from the group consisting of salts of 2,4-d, dicamba and mixtures thereof, wherein the salt is selected from amine salts. One specific example of such compositions includes the auxin herbicide composition of U.S. patent 9,179,673, the contents of which are incorporated herein by reference, which discloses an aqueous liquid herbicide composition comprising a solution of 2,4-D and/or dicamba auxin herbicide having monomethylamine and dimethylamine counterions, wherein the molar ratio of monomethylamine to dimethylamine is from 20:1 to 1:1, preferably from 20:1 to 7:3, even more preferably from 20:1 to 4:1, 1:20 to 4:6, and the concentration of the auxin herbicide is at least 500g/L based on herbicide acid equivalents.

The water-soluble pesticides include certain nematicides and plant growth regulators. Exemplary water-soluble nematicides useful in the present invention include: water-soluble salts of 3,4, 4-trifluoro-3-butenoic acid and N- (3,4, 4-trifluoro-1-oxo-3-butenyl) glycine.

Exemplary water-soluble plant growth regulators useful in the present invention include water-soluble salts of ethephon, gibberellic acid, glyphosate (glyphosate), bensulide (malaic hydrazide), fluroxypyr, 1-naphthylacetic acid, and triiodobenzoic acid.

Water-soluble insecticides can include, for example, water-soluble organophosphorus insecticides such as acephate (acephate) and methamidophos (methamidophos).

One skilled in the art will readily appreciate that these pesticides exhibit sufficient water solubility such that they dissolve when mixed with water at the marked usage rate.

The pesticide component of the composition can include a mixture of pesticides for controlling different pest types (e.g., a mixture of two or more weeds and nematodes). In one embodiment, the pesticide may comprise a mixture of herbicides, for example salts of two or more herbicide acids selected from benzoic acid herbicides, imidazolinones, phenoxyacetic acid herbicides, phenoxybutyric acid herbicides, phenoxypropionic acid herbicides, pyridine carboxylic acid herbicides, picolinic acid herbicides and organophosphorus herbicides, in particular water-soluble salts of two or more of 2,4-D, 2 methyl 4 chloro, dicamba, aminopyralid, clopyralid, picloram, halauxifen, flopyrauxifen, 2,4-D propionic acid, 2 methyl 4 chloropropionic acid, high 2,4-D propionic acid, 2 methyl 4 chloropropionic acid, imazamox, imazapyr, bentazon, glyphosate and glufosinate. Use of the combination may provide improved efficacy of administration. Specific examples of mixtures include mixtures of salts of glyphosate and one or more of benzoic acid herbicides, imidazolinones, phenoxyacetic acid herbicides, phenoxybutyric acid herbicides, phenoxypropionic acid herbicides, pyridine carboxylic acid herbicides, picolinic acid herbicides and organophosphorus herbicides, especially salts of 2,4-d, 2 m 4 chloro, dicamba, aminopyralid, clopyralid, picloram, halauxifen, flopyrauxifen, 2,4-d propionic acid, 2 m 4 chloropropionic acid, imazamox, imazapyr. In another embodiment, the mixture comprises two or more of 2,4-d, 2 m 4 chloro, dicamba, aminopyralid, clopyralid, picloram, halauxifen, flopyrauxifen, 2,4-d propionic acid, 2 m 4 chloropropionic acid, homo 2,4-d propionic acid, refined 2 m 4 chloropropionic acid, imazamox, and imazapyr.

If desired, the concentrate composition may contain a co-solvent, for example in an amount of up to 50% by weight of the aqueous liquid carrier. Thus, in some embodiments, the co-solvent is 0 to 50 weight percent, such as 0 to 35 weight percent, 0 to 30 weight percent, or 0 to 25 weight percent of the aqueous liquid carrier. In many cases, such as for certain highly water-soluble auxin salts, high loadings of herbicide acid equivalents can be achieved without the use of co-solvents, thereby making water the sole liquid carrier, although co-solvents can be used if desired. The water solubility can vary significantly depending on the identity of the salt counter-ion and/or the pesticide acid, and in some cases, the co-solvent can help achieve suitable stability of the desired pesticide loading. Thus, in some embodiments, for example for certain water-soluble salts of auxin herbicides, the co-solvent may be no greater than 5 wt% or no greater than 2 wt%, and the composition may be free of co-solvent. In other embodiments, the presence of a co-solvent may be beneficial for the stability of the composition, and the co-solvent may be present in an amount of, for example, 5 to 35 weight percent or 15 to 30 weight percent, depending on the loading and water solubility of the pesticide.

The identity of any co-solvent may be selected based on the pesticide. In some cases, alcoholic solvents or glycols were found to be useful.

If desired, the concentrate composition may comprise a surfactant, which may be selected from anionic, cationic, nonionic, amphoteric surfactants, and mixtures thereof. Typically, the surfactant component comprises no more than 15 wt% (e.g., 0 to 10 wt%) or no more than 10 wt% (e.g., 0 to 5 wt%) of the composition. In many cases, such as salts of auxin herbicides, it may be preferable to have little or no surfactant to optimize pesticide loading.

The pesticide solution concentrate includes a fatty acid. The fatty acid is present in the solution concentrate in an amount of at least 5 g/L. Typically, the fatty acid is present in an amount up to about 300 g/L. We have found that very small amounts of fatty acids, for example 0.1 wt%, are not effective in controlling spray drift, whether or not used in combination with proteins such as casein, as demonstrated below. Preferably, the fatty acid is present in an amount of from 10 to 300g/L, for example from 20 to 250g/L or most preferably from 50 to 250 g/L. The protein may be present in an amount of 0.1-100g/L, preferably 0.5-20g/L, more preferably 1-15g/L, for example 1-10 g/L.

We have found that the effectiveness and stability of drift reducers can vary with the pH of the composition, where the pH is measured as a 1% sample of an aqueous concentrate. In general, the pH is from 3.5 to 9, preferably from 5.5 to 8.0.

The pesticide solution concentrate composition forms a spray upon dilution and spray application, wherein the proportion of droplets having a diameter of less than 150 μm, in particular less than 105 μm, is reduced to below that of a composition which does not comprise a drift reducing component when tested at an application rate for pesticide control.

The present invention further provides a method for controlling pests using the aqueous pesticide solution concentrate, comprising diluting the aqueous pesticide solution concentrate with water and applying the diluted concentrate to the locus of the pests to be controlled by spray application.

The method comprises applying a spray mixture formed by diluting an aqueous herbicide solution concentrate to the locus of the weeds to be controlled. The optimum application rate of the spray mixture depends on the particular formulation, the herbicide and any adjuvants present which may affect the efficacy of the herbicide. In one set of embodiments, the method comprises applying the spray mixture at an application rate of herbicide/ha in the range of from 30 to 5000gae/ha, particularly from 40 to 2000gae/ha, for example 100-.

In one set of embodiments, the method comprises applying a spray mixture formed from a concentrate having a herbicide salt concentration of 0.01 to 20 wt%, preferably 1 to 10 wt%.

In one set of embodiments, the method comprises the step of forming a spray mixture of the herbicide by mixing the concentrate composition with a spray aid, particularly a spray oil, and a diluent, typically water. Examples of spray oils include paraffinic spray oils, vegetable derived oils such as vegetable oils, and esters of vegetable oils such as methyl and ethyl esters of vegetable oils. In one embodiment, the spray oil comprises an oil, such as a paraffin oil, a naphtha-based petroleum oil, a vegetable-based oil (in an amount of, for example, 50-98% oil), and one or more surfactants (e.g., 1-40% by weight) that function as emulsifiers and/or wetting agents. In another embodiment, the spray oil may comprise 60-85% of an emulsifiable oil, such as paraffin oil, naphtha-based petroleum, vegetable-based oil, and 15-40% of a nonionic surfactant. In one embodiment, the spray oil comprises a paraffinic oil.

Products correctly identified as "vegetable oil concentrates" typically consist of 60-85% vegetable oil (i.e., seed or fruit oil, most commonly from cotton, linseed, soybean or sunflower) and 15-40% nonionic surfactant. The adjuvant properties can be improved by replacing the vegetable oil with an ester such as the methyl or ethyl ester of a fatty acid typically derived from vegetable oils. The amount of oil-based adjuvant added to the spray mixture is typically no more than about 2.5 volume percent, more typically, the amount is from about 0.1 to about 1 volume percent. The application rate of the oil-based adjuvant added to the spray mixture is typically from about 250ml to 5L per hectare, for example from 1 to about 5L per hectare, in particular, methylated seed oil-based adjuvants are typically used at application rates of from about 1 to about 2.5L per hectare.

Spray aids comprising oils, with or without emulsifiers, in particular methylated seed oil or ethylated seed oil, are particularly compatible in the spray mixture. Accordingly, one embodiment of the present invention is directed to a mixture or method for controlling weeds that further comprises forming a spray mixture. The step of forming a spray mixture may comprise mixing the concentrate composition with water and optionally an adjuvant. In a preferred aspect, an adjuvant such as a spray oil is used, which may be a crop oil concentrate or a vegetable oil concentrate, for example an esterified seed oil such as a methylated or ethylated seed oil. The method can include adding an adjuvant to the spray mixture (in any order of addition or mixing) and contacting the crop with an amount of the spray mixture effective to control the target weed.

The ratio of the volume of the concentrate to the volume of water used to dilute the concentrate is typically from about 1:10 to about 1:5000, more typically from about 1:20 to about 1: 2000. The amount of diluted spray mixture required for effective control depends on various factors including the concentration of the concentrate, the presence and concentration of any other adjuvants, the degree of dilution in water. These conditions can be determined by calculation and simple experiment by a person skilled in the art.

In one set of embodiments, the spray oil comprises a fatty acid or fatty acid derivative, such as an ethyl or methyl ester derivative, which enhances penetration of the herbicide into the weeds. The spray oil may contain a surfactant of a non-ionic, anionic or cationic nature. In one embodiment, the spray oil comprises a nonionic surfactant, such as an alkoxylated alkyl alcohol surfactant. In a preferred embodiment, the spray oil concentration in the spray water is 200-.

In another embodiment, the method may include including the additional herbicide in the spray mixture by a process step known in the art as tank mixing. For example, in one embodiment, the method comprises forming a spray mixture from the concentrate of the present invention comprising an auxin herbicidal salt and a tank-mix of other actives or adjuvants, which may be herbicides, insecticides, fungicides, plant growth regulators, safeners, ammonium sulfate, or liquid fertilizers. The tank mix of herbicides may involve herbicides selected from other auxin herbicides such as those mentioned above and organophosphorus herbicides such as glyphosate, glufosinate and glufosinate-P.

The invention will now be described with reference to the following examples. It should be understood that the examples are provided to illustrate the invention and are in no way intended to limit the scope of the invention.

Examples

When in the examples reference is made to the concentration of the pesticidal salt form of the salt of the pesticidal acid, this is based on the concentration of the acid equivalent.

Example 1 (comparative example)

The purpose is as follows: aqueous formulations containing various oils containing 2,4-D DMA MMA salt were prepared and evaluated. Table 1: a test mixture containing 2, 4-drops of DMA MMA aqueous salt and various oils (stock 1 contains 4g/L casein and 700 g/L2, 4-drops of DMA MMA in the form of a soluble salt concentrate).

The 2, 4-drop concentration in the stock solution was 56.72 wt%. Casein was present in the stock solution in an amount of 0.324 wt%.

The procedure is as follows: a physical mixture comprising oil and 2,4-d DMA MMA stock formulation as shown in table 1 was prepared. The required amount of 2,4-d amine stock solution and oil was transferred to a 100ml volumetric flask and made up to volume with tap water. The volumetric flask was shaken to mix the contents. The physical appearance of the mixture was checked and tested for dilution performance at 5 vol% dilution in tap water.

Observation of

All mixtures (as shown in Table 1) were cloudy in appearance, indicating that the oil was insoluble in 2, 4-drops of aqueous DMA MMA. All mixtures showed phase separation upon storage. These mixtures also exhibit phase separation when added to tap water at a dilution of 5% by volume and are therefore not suitable formulations.

Further formulation trials were conducted using surfactants in an attempt to stabilize oils containing 2,4-d amine compositions.

Example 2 (comparative example)

The purpose is as follows: an aqueous formulation of 2,4-D DMA MMA salt containing surfactant and oil was prepared and evaluated.

Table 2: an assay mixture containing 2, 4-drops of DMA MMA aqueous salt, various oils and surfactants (stock solution 2 contains 4g/L casein and 700 g/L2, 4-drops in the form of a soluble concentrate of DMA MMA salt).

The procedure is as follows: a physical mixture comprising oil, surfactant and 2, 4-drop DMA MMA stock formulation as shown in table 2 was prepared. The required amount of 2,4-d amine stock solution and oil was transferred to a 200ml volumetric flask and made up to volume with tap water. The volumetric flask was shaken to mix the contents. The physical appearance and homogeneity of the mixture upon storage was checked.

Observation of

All mixtures containing aqueous 2,4-D DMA MMA, surfactant and oil were unstable and separated rapidly. The test results show that oils and lipids cannot be easily incorporated into 2,4-d aqueous amine solutions without compromising the stability of the concentrate and the dilution properties of the formulation.

Example 3 (comparative example)

Polymer testing

Compositions comprising aqueous 2,4-D DMA MMA and synthetic polyethylene oxide polymers were also tried as shown in Table 3.

Table 3: test mixtures containing 2,4-D DMA MMA aqueous salt and Polymer

Procedure

0.62g of polyethylene oxide was added to 150mL of water and gently stirred until hydrated to give a homogeneous viscous solution. Casein was added to the solution with 2, 4-drops, DMA and MMA and stirred until a homogeneous solution was obtained. Finally, the solution was made up to 1L with water.

Observation of

The mixture showed development of a precipitate upon storage and was therefore not a stable combination.

Example 4

The purpose is as follows: the miscibility of oleic acid in 2,4-D DMA MMA aqueous concentrate was evaluated.

The procedure is as follows: a stock formulation containing 700gae/L of 2,4-d in the form of dimethylamine and monomethylamine and 4g/L casein was used in this test. A physical mixture comprising fatty acid in oleic acid form (Palmac 750, with 72 wt% C18:1) and 2,4-d DMA MMA stock formulation was prepared as shown in table 4. The required amount of 2, 4-drop stock formulation was transferred to a 20ml glass vial. Magnetic fleas (Magnetic flea) were then added to the vial and the stirring was set at low speed. Then, the desired amount of oleic acid was added dropwise to each vial while stirring.

The combination was mixed for 30 minutes and the physical appearance was monitored. Visual inspection showed the solution to be clear at room temperature with no signs of turbidity, separation or precipitation. The mixture was tested for dilution performance and yielded a stable dilution.

Table 4: test mixtures containing varying amounts of 2,4-D DMA MMA aqueous salt and oleic acid. (stock 4 contained 4g/L casein and 700 g/L2, 4-D soluble concentrate in the form of DMA MMA salt).

The concentration of 2, 4-drops in the stock solution was 56.72 wt%. Casein was present in the stock solution in an amount of 0.324 wt%.

Observation and review

Mixtures 1-3 (as shown in table 4) gave clear physical mixtures with no visible solids.

All combinations were tested for dilution stability (5 vol% in Melbourne tap water with nominal 20ppm hardness). Mixtures #2 and #3 formed particularly effective emulsions upon dilution.

By adding oleic acid to a stock formulation containing 2,4-d DMA MMA, a considerable reduction in amine odour was achieved. The reduction in amine odor in mixture #1 was slight. Amine odor was significantly reduced in mixtures #2 and #3 compared to 2,4-d amine without oleic acid.

The characteristics of mixture #2 were preferred, so the physical parameters were further evaluated.

Example 5

Another formulation mixture containing 50% w/v 2, 4-drops in the form of DMA MMA salt was prepared based on mixture #2 shown in Table 4 (as shown in Table 5).

A200 mL mixture containing 500g/L of 2,4-D in DMA MMA salt form and 25% w/v oleic acid was prepared and evaluated, and the relevant spray droplet distribution was characterized.

Table 5: a physical mixture containing 50% w/v 2, 4-drops in the form of DMA MMA salt. (stock solution 5 contained 4g/L casein and 700 g/L2, 4-D in the form of a soluble concentrate of DMA MMA salt).

Composition (I)	Measurement of
		Liquid storage52, 4-Diamine (g)	180.0g
Oleic acid	50.6

200ml of the mixture shown in Table 5 was prepared by mixing stock solution 2,4-d amine and oleic acid in a glass beaker using a magnetic stirrer. After 10 minutes of mixing a clear solution was obtained. The physical parameters of the mixtures were tested as shown in table 6.

Table 6: physical parameters of a mixture comprising 50% w/v 2,4-D in DMA MMA salt form and 25.3% w/v oleic acid.

Spray droplet size analysis of the compositions of Table 5

The compositions of Table 5 were diluted in tap water to obtain a final concentration of 1.4% by volume, which corresponds to 7g/L of 2,4-d acid, representing a field application rate of 700g.a.e/ha 2,4-d under 100L/ha water. The test solution was sprayed at a pressure of 3.0 bar using a flat fan nozzle XR11002 nozzle. The resulting spray droplet distribution was analyzed using an Oxford laser imaging system equipped with Visisize software. The instrument was set up to obtain an image of the cross section of the spray pattern 30cm directly below the nozzle. The image is processed to obtain the exact size of all droplets recorded within that portion of the spray pattern to obtain a spray droplet distribution characteristic of the nozzle, pressure and fluid combination being analyzed. The cumulative volume percentage of the measured droplet distribution comprising droplets with a diameter <105 μm is defined as the driftable fraction.

The driftable fraction of the test solution was compared to the driftable fraction of water (unless otherwise stated) at the matched nozzle and pressure settings.

The driftable fraction of the compositions of table 5 diluted in water at 1.4 vol% and of the 2, 4-drop DMA MMA soluble concentrate compared to the reference diluted to the same final concentration of 2, 4-drops were measured and the results are shown in table 7.

Table 7: driftable fractions of test solutions of 2, 4-drops DMA MMA stock and mixtures prepared according to table 5 compared to water.

Observations and comments when evaluating the compositions of Table 5

The compositions of table 5 were found to have satisfactory physical and dilution properties. The emulsions tested in laboratory tap water (nominal 20ppm hardness), CIPAC Std D (342ppm hardness), CIPAC Std C (500ppm hardness), and 3WHO (1000ppm hardness) water were good in stability.

The amine odor of the compositions of table 5 was significantly reduced compared to the standard 2, 4-drop DMA MMA soluble concentrate solution versus the reference.

The measured driftable fraction of the diluted formulation was significantly less than the standard 2, 4-drop DMA MMA soluble concentrate versus the reference.

Example 6 a: further testing and observations

Based on the satisfactory initial physical properties of the compositions of table 5, 1L of batches having the same composition were prepared from each raw material.

The scaled-up 1L batch was not completely clear in appearance and had slight turbidity.

To investigate the observed formation and effect of haze, two further formulations were prepared, one containing casein (formulation #1) and one without casein (formulation #2), as shown in table 5. Formulations #1 and #2 both contained 500 g/L2, 4-D DMA MMA and 25% w/v oleic acid.

Two additional formulations containing 500g/L of 2,4-d in DMA MMA salt form, casein and varying amounts of oleic acid were prepared to evaluate the effect of fatty acid concentration on formulation appearance. (formulation #3 and formulation #4, table 8).

Formulation examples #1 to #4

Table 8: formulations #1, #3 and # 4: 2,4-D DMA MMA aqueous formulation with oleic acid and casein. Formulation # 2: 2,4-D DMA MMA aqueous formulation with oleic acid and no casein.

Preparation of formulations #1, #3 and #4 (formulations comprising casein and oleic acid)

A formulation was prepared comprising 500g of acid equivalent 2,4-d in the form of DMA and MMA salts, casein, oleic acid and water. 100g of water was added to the beaker and the required amounts of DMA (60% aqueous solution) and MMA (40% aqueous solution) were slowly added to the beaker. The contents were mixed using an overhead stirrer with low agitation. While stirring, the desired amount of casein was added to the beaker. Once the casein was dissolved, technical grade 2,4-d acid (98.0 wt%) was gradually added to the beaker. After all base and technical grade 2,4-d acid were added, the contents were mixed to obtain a clear solution. Oleic acid was then added to the beaker and mixed to obtain a clear solution. The mixture was transferred to a 1L volumetric flask and the volume was made up with nominally 20ppm hardness water. The resulting formulation was slightly cloudy with no visible solid particulates.

Note 1: formulations were also prepared in which casein was pre-dissolved in alkaline base and added to a 2, 4-drop DMA MMA oleic acid solution. The formulations prepared using pre-dissolved casein were clear and free of visible solid particulates.

Note 2: the amount of basic base used to dissolve technical grade 2,4-d acid can vary due to volatile loss during preparation. An excess of base may be required to completely neutralize the technical grade 2,4-d mass.

Preparation of formulation #2 (casein-free comparative formulation)

A formulation was prepared comprising 500g of acid equivalent of 2,4-d in the form of DMA and MMA salts, oleic acid and water. 100g of water was added to the beaker and the required amounts of DMA (60% aqueous solution) and MMA (40% aqueous solution) were slowly added to the beaker. The contents were mixed using an overhead stirrer with low agitation. While stirring, the desired amount of technical grade 2,4-d acid (98.0 wt%) was gradually added to the beaker. After all base and technical grade 2,4-d acid were added, the contents were mixed to obtain a clear solution. Oleic acid was then added to the beaker and mixed to obtain a clear solution. The mixture was transferred to a 1L volumetric flask and the volume was made up with nominally 20ppm hardness water.

Note that: the amount of basic base used to dissolve the technical grade 2,4-d acid can vary due to volatile loss during manufacture. An excess of base may be required to completely neutralize the technical grade 2,4-d mass.

Properties of formulations #1, #2 (comparative), #3 and #4

Table 9: physical parameters of formulations #1 to #4

Observation of formulations #1 to #4

Dilution tests of formulations #1 and #2 show a difference in dilution performance. Upon dilution, formulation #1 containing casein produced an opaque/milky white liquid immediately. The casein-free formulation forms a translucent, visibly clear liquid upon dilution.

The measured driftable fractions of formulations #1 and #2 (comparative) were significantly different when diluted at 1.4 vol% in water. Formulation #1 containing casein resulted in a 63% reduction in the driftable fraction, whereas comparative formulation #2 containing no casein did not significantly change the driftable fraction compared to water under the same conditions. (Table 9).

Formulations #3 and #4 were tested at a 1.4 vol% dilution ratio for the driftable fraction obtained upon atomization. Formulation #3 reduced the driftable fraction to an equal extent as formulation #1, however, the reduction in driftable fraction was not as significant for formulation #4 containing the lowest amount of oleic acid.

Conclusion (formulations #1 to #4)

Formulations #1 to #4 were prepared and evaluated for physical parameters and droplet size distribution. The results obtained show the effectiveness of casein and oleic acid as in-can drift reduction systems in 2, 4-drop DMA MMA formulations. Formulations prepared with and without casein showed significant differences in spray droplet size distribution. 2,4-D DMA MMA oleic acid aqueous formulations containing casein and oleic acid showed a significant reduction in driftable fraction. In casein-free formulations, the driftable fraction was not significantly reduced. Casein has also been found to be critical for obtaining acceptable dilution performance in hard water.

Evaluation of component interactions and impact on spray Performance

To evaluate the contribution of oleic acid and casein to the spray performance of the formulations and the magnitude of any interaction present, a factoring design of the experimental model was used. The model contained three variables, each at two levels, and all measurements were compared to those of a "blank" solution consisting of 2,4-d amine and containing no casein and oleic acid.

Constant-540 g/L2, 4-drops DMA MMA salt at a stoichiometric ratio of acid to base of 1: 1.

A variable A: amine content-level 1-10% molar excess and level 2-20% molar excess.

A variable B: casein-level 1-2 g/L, level 2-8 g/L

A variable C: oleic acid-level 1-100g/L, level 2-250 g/L

"blank" solution was 700 g/L2, 4-drop DMA MMA salt solution with a molar excess of 15%.

Each formulation was diluted with water to a concentration of 7g/L of 2, 4-drops and sprayed from a Teejet AIXR11003 nozzle at a pressure of 2.75 bar. Cumulative volume% of <105 μm was measured.

Table 10: factor design:

table 11: results

Factor design evaluation for experimental study:

the magnitude of the score for each variable and its combination indicates the level of influence. An increase in deviation from zero indicates an increased effect on the resulting driftable fraction of the diluted formulation spray droplet distribution.

Positive or negative values are associated with positive or negative effects (which correlate with an increase in the variable).

In terms of the effect of the one-component on spray drift, this design shows that higher levels of amine in the formulation have a negative effect on spray drift reduction performance. The positive effect of increasing the oleic acid concentration was equally strong.

Changing the concentration of casein showed only a weak effect.

The results also show that there is a very strong positive interaction between casein and oleic acid, which is a major contributor to the reduction of the driftable fraction of the spray solution in these formulations. A moderate negative interaction between casein and increased amine content is also evident.

The design also shows that there is no significant interaction between amine content and oleic acid concentration in terms of spray drift reduction performance, and that the interaction of all three components combined is relatively weak.

It shows that the presence of oleic acid and casein results in a significant drift reduction potential. The concentrations of oleic acid and amine have a large effect on the magnitude of this effect, but the effect of changes in casein concentration is less pronounced. However, the interaction values confirm that the presence of casein is critical to provide significant drift reduction effects in these formulations.

Further work

Since casein and oleic acid show good drift reduction in 2,4-D DMA MMA, further experiments were conducted to prepare and evaluate physical properties and spray droplet size distribution of formulations containing alternative fatty acids and proteins. Selection of globular proteins was used to evaluate short, medium and long chain fatty acids.

Example 7

Substitute material

Fatty acids included in the test

Proteins included in the assay

Sodium caseinate

Soy protein isolate

Lactalbumin (lactoalbumin)

A formulation comprising 500 g/L2, 4-D in the form of DMA MMA salt in combination with 3-4g/L protein and 180g/L fatty acid was prepared and the volume was made up with water.

The physical properties of these test formulations were evaluated, including analysis of the driftable fraction of the spray droplet distribution they produced upon atomization when diluted in water at 1.4 vol%. The test results are shown in table 12.

Table 12: compositions comprising formulations replacing fatty acids and proteins and drift reduction properties of the resulting diluted solutions

All C when formulated with 2,4-D DMA MMA and casein₆-C₁₈Fatty acids result in a reduced driftable fraction of their spray droplet distribution compared to water. These fatty acids show a behavior similar to the combination of oleic acid and casein and both impart drift reducing properties.

Similarly, the use of lactalbumin, soy protein isolate or sodium caseinate in combination with oleic acid all resulted in the drift reducing properties of the diluted solution as observed with the oleic and casein formulations.

As another example, formulations #5, #6 and #7 were prepared containing 500 g/L2, 4-D in DMA MMA salt form and various amounts of oleic acid and sodium caseinate, as detailed in Table 13.

These formulations are considered duplicates of formulations #1, #3 and #4 prepared according to table 8, but using sodium caseinate as a replacement for casein.

Table 13: formulations #5 to # 7: 2,4-D DMA MMA aqueous formulation comprising oleic acid and sodium caseinate

Formulations #5, #6 and #7 (formulations containing sodium caseinate and oleic acid)

A formulation was prepared comprising 500g of acid equivalent 2,4-d in the form of DMA and MMA salts, sodium caseinate, oleic acid and water. 100g of water was added to the beaker and the required amounts of DMA (60% aqueous solution) and MMA (40% aqueous solution) were slowly added to the beaker. The contents were mixed using an overhead stirrer with low agitation. While stirring, the desired amount of sodium caseinate was added to the beaker. Once the sodium caseinate dissolved, technical grade 2,4-d acid (98.0 wt%) was gradually added to the beaker. After all base and technical grade 2,4-d acid were added, the contents were mixed to obtain a clear solution. Oleic acid was then added to the beaker and mixed to obtain a clear solution. The mixture was transferred to a 1L volumetric flask and the volume was made up with nominally 20ppm hardness water. The resulting formulation was clear and free of visible solid particulates.

Note 1: the amount of basic base used to dissolve technical grade 2,4-d acid can vary due to volatile loss during production. An excess of base may be required to completely neutralize the technical grade 2,4-d mass.

Physical parameters of formulations #5 to #7 were evaluated, including the measured driftable scores.

Properties of formulations #5, #6 and #7

Table 14: physical parameters of formulations #5 to #7

The results show the effectiveness of sodium caseinate and oleic acid as in-can drift reduction systems in a range of concentrations in 2, 4-drop DMA MMA formulations, with the driftable fractions of all three formulations being significantly reduced. Formulations comprising sodium caseinate have also been found to have acceptable dilution properties in hard water. The performance of sodium caseinate as a co-formulation of oleic acid in the 2,4-d amine formulation was not significantly different from that of casein.

As a further example of the use of fatty acids as drift reduction additives, an aqueous formulation comprising 500 g/L2 methyl 4 chloro, high 2,4-d propionic acid, 2 methyl 4 chloropropionic acid arginine in the form of a DMA MMA salt, and a combination of 2,4-d and high 2,4-d propionic acid in the form of a DMA MMA salt, a combination of 2,4-d and 2 methyl 4 chloropropionic acid arginine (each 250g/L), and a combination of dicamba and high 2,4-d propionic acid, a combination of dicamba and 2 methyl 4 chloropropionic acid arginine (each 250g/L) was prepared with oleic acid and sodium caseinate. The formulations were diluted to 1.4 vol% in water and spray analyzed, and the results are listed in table 15.

Table 15: spray analysis results for formulations of diluted 2,4-d, 2 methyl 4 chloro (MCPA), high 2,4-d propionic acid, neat 2 methyl 4 chloropropionic acid, a combination of 2,4-d and high 2,4-d propionic acid, a combination of 2,4-d and neat 2 methyl 4 chloropropionic acid, dicamba and high 2,4-d propionic acid, dicamba and combination of neat 2 methyl 4 chloropropionic acid, the formulations containing oleic acid and sodium caseinate.

When formulated in 2 methyl 4 chloro (MCPA), high 2,4-d propionic acid, and fine 2 methyl 4 chloropropionic acid concentrates, the drift reduction system comprising oleic acid and sodium caseinate showed the same performance as when formulated into 2,4-d concentrates. Various combinations of 2,4-D, dicamba, high 2,4-D propionic acid and fine 2-methyl 4-chloropropionic acid comprising oleic acid and sodium caseinate also showed good drift reduction performance.

Abbreviations

MMA-monomethylamine salt

DMA-dimethylamine salt

The DMA MMA salts mentioned in the examples represent the acidic pesticides in the form of a salt mixture. DMA MMA typically refers to a salt comprising a molar ratio of about 4: 1.

Example 8

This example compares the effect of an amount of up to 0.1 wt.% fatty acid, reported as providing foam control in CN 1026966611, the composition of the invention comprising at least 5g/L fatty acid.

Table 16: composition disclosed in part 1-CN 102696611A based on an amount of up to 0.1 wt.% fatty acid

Positive values correspond to an increased spray drift potential, while negative values indicate a decreased spray drift potential.

Table 17: part 2-compositions of the invention comprising at least 5g/L fatty acid.

The compositions of the present invention show significant improvements in spray drift control.

Example 9: this example compares the efficacy of the compositions of the present invention with several commercially available compositions.

Table 18: 2,4-D compositions of the invention

Table 19: comparison product for sale (CC1)

Technical grade 2, 4-acid (98%)	714.29g
		MMA(40％)	47.51g (+7g excess)
DMA(60％)	190.05g (+29g excess)
		Casein acid	4.0g
Water (W)	To 1L
		Density (20 ℃ C.)	1.234
pH (1% in deionized water)	9-10

Table 20: commercial contrast (CC2)

2, 4-Dihydric acid in Choline form	668.62g/L (456g/L acid equivalent)
		Density (20 ℃ C.)	1.185
pH (1% in deionized water)	5.23

Table 21: comparison product for sale (CC3)

2, 4-Dihydric acid in Choline form	24.4％
		Glyphosate DMA salt	22.1％
Propylene glycol	6.4％
		Balance of	47.1％
Density (20 ℃ C.)	1.1676
		pH (1% in deionized water)	6.17

Table 22: standard Glyphosate product available on the market (CC4)

Glyphosate IPA salt	400.80g/L
		Glyphosate K salt	297.75g/L
Balance of	601.45g/L
		Density (20 ℃ C.)	1.2216
pH (1% in deionized water)	4.98

Table 23: description of the experiments

Greenhouse trials were treated in a track sprayer. A small field test was processed using a hand-held boom.

The formulations were compared between a number of ratios (8 greenhouse trials and 4 field trials).

Preparation of treatment to deliver equal ratios of all formulations in the trial.

Note the improved efficacy of the formulation.

2,4-D fruiting (GHT-BE)

The purpose is as follows: dose-response bioefficacy assay for 2 potted seedling species.

As a result:

the average fresh weight (7 replicates) of the 8-ratio dose-response treatment was averaged for all formulations.

The results were analyzed using factorial analysis of variance analysis.

When the data for all formulations and each formulation alone were averaged, there was a clear response to the contrast ratio.

Watch 24

Formulations containing oleic acid (15-25%) were as effective as CC1 when applied to silybum marianum seedlings.

Formulations containing oleic acid (15-25%) were more effective than CC1 and CC2 when applied to brassica napus seedlings.

Dose-response analysis:

all formulations were analyzed for average control% (7 replicates) of 8-rate dose-response treatment.

Least square method

TABLE 25

The results show that:

LD of formulations comprising oleic acid₅₀Significantly lower than CC1 and CC 2.

LD of formulations comprising oleic acid₉₀Significantly lower than CC 2.

LD of formulations comprising oleic acid₉₀Less than or equal to CC 1.

FT-BE-A-fallow-QLD

The purpose is as follows: caltrop 4-rate response efficacy test.

As a result:

the average control% (4 replicates) of the 4-ratio dose-response treatment for all formulations was averaged.

The results were analyzed using factorial analysis of variance.

When the data for all formulations and each formulation alone were averaged, there was a clear response to the contrast ratio.

Watch 26

The oleic acid containing formulation was better than CC1 on caltrops.

Formulations containing oleic acid resulted in early control levels of caltrops higher than CC 1.

FT-BE-A-fallow land-NSW

The purpose is as follows: the efficacy test was performed on 4-rate responses of 2 species.

As a result:

the average control% (4 replicates) of the 4-ratio dose-response treatment for all formulations was averaged.

The results were analyzed using factorial analysis of variance.

When the data for all formulations and each formulation alone were averaged, there was a clear response to the contrast ratio.

Watch 27

The formulations containing oleic acid were better than CC1 in the Amaranthus mitchelli and Tribulius micococcus formulations.

FT-BE CS-wheat-QLD

The purpose is as follows: the 4-ratio response to 1 species was tested for efficacy.

As a result:

the average control% (4 replicates) of the 4-ratio dose-response treatment for all formulations was averaged.

The results were analyzed using factorial analysis of variance.

When the data for all formulations and each formulation alone were averaged, there was a clear response to the contrast ratio.

Watch 28

The effect of the oleic acid containing formulation on wild radish was at least as effective as CC 1.

The effect of the formulations comprising oleic acid on wild radish was more effective than CC 2.

FT-BE CS-wheat-SA

The purpose is as follows: the 4-ratio response to 1 species was tested for efficacy.

As a result:

the average control% (4 replicates) of the average 4-ratio dose-response treatment was averaged for all formulations.

The results were analyzed using factorial analysis of variance.

When the data for all formulations and each formulation alone were averaged, there was a clear correspondence in the contrast ratio.

Watch 29

Formulations comprising oleic acid are at least as effective as CC1 and CC2 in wild radish control.

FT-BE-A-wheat-ND 1

The purpose is as follows: 4-ratio response efficacy test for 4 species.

As a result:

the average control% (4 replicates) of the 4-ratio dose-response treatment for all formulations was averaged.

The results were analyzed using factorial analysis of variance.

When the data for all formulations and each formulation alone were averaged, there was a clear response to the contrast ratio.

Watch 30

Formulations containing oleic acid were more effective than CC1 on redrawn, kochia, quinoa and quinoa when evaluated early.

FT-BE-A-wheat-ND 2

The purpose is as follows: the 4-ratio response to 1 species was tested for efficacy.

As a result:

the average control% (4 replicates) of the 4-ratio dose-response treatment for all formulations was averaged.

The results were analyzed using factorial analysis of variance.

When the data for all formulations and each formulation alone were averaged, there was a clear response to the contrast ratio.

Watch 31

In all evaluations, the formulations containing oleic acid had better effect on chenopodium album than CC1 and CC 2.

FT-BE-A-Arg-maize

The purpose is as follows: the efficacy test was performed on 4-rate responses of 2 species.

As a result:

the average control% (4 replicates) of the 4-ratio dose-response treatment for all formulations was averaged.

The results were analyzed using factorial analysis of variance.

When the data for all formulations and each formulation alone were averaged, there was a clear response to the contrast ratio.

Watch 32

CC1 was less effective on purslane early in the evaluation period compared to formulations containing oleic acid.

Tank mix-2, 4-D and glyphosate

FT-BE-B-fallow-QLD-2017

The purpose is as follows: the efficacy test was performed on 4-rate responses of 3 species.

The tank mix concentrate 2, 4-drops 269g ae/ha and glyphosate 283g ae/ha, 2, 4-drops 538g ae/ha and glyphosate 566g ae/ha, 2, 4-drops 795g ae/ha and glyphosate 845g ae/ha, 2, 4-drops 1077g ae/ha and glyphosate 1133g ae/ha are compared to the co-formulated product CC 3.

As a result:

the 4-ratio dose-response treated control% (4 replicates) of all tank-mixed formulations were averaged.

The results were analyzed using factorial analysis of variance.

When the data were averaged for all tank-mixed formulations and each tank-mixed formulation alone, there was a clear response to the contrast ratio.

There was a clear response to the ratio of each 2, 4-drop formulation.

Watch 33

There was no significant difference between the tank mixes in the control and co-formulated commercial product CC2 of any species.

There was no antagonism observed in any of the treatments for dicotyledons or monocotyledons.

FT-BE-B-fallow-SA

The purpose is as follows: the efficacy test was performed on 4-rate responses of 3 species.

The tank mix concentrate 2, 4-drops 269g ae/ha and glyphosate 283g ae/ha, 2, 4-drops 538g ae/ha and glyphosate 566g ae/ha, 2, 4-drops 795g ae/ha and glyphosate 845g ae/ha, 2, 4-drops 1077g ae/ha and glyphosate 1133g ae/ha are compared to the co-formulated product CC 3.

As a result:

the average 4-ratio dose-response treated control% (4 replicates) of all tank-mixed formulations was averaged.

The results were analyzed using factorial analysis of variance.

When the data were averaged for all tank-mixed formulations and each tank-mixed formulation alone, there was a clear response to the contrast ratio.

Watch 34

Watch 35

There was no significant difference between the tank-mix formulations in controlling 27DAA on any species.

No antagonism was observed in any treatment of any species.

FT-BE-B-Arg-maize-2017

The purpose is as follows: the efficacy test was performed on 4-rate responses of 2 species.

The tank mix concentrate 2, 4-drops 270g ae/ha and glyphosate 286g ae/ha, 2, 4-drops 540g ae/ha and glyphosate 570g ae/ha, 2, 4-drops 795g ae/ha and glyphosate 845g ae/ha, 2, 4-drops 1080g ae/ha and glyphosate 1140g ae/ha was compared to the coformulated product CC 3.

As a result:

the 4-ratio dose-response treated control% (4 replicates) of all tank-mixed formulations were averaged.

The results were analyzed using factorial analysis of variance analysis.

When the data for all tank mixes and each tank mix formulation alone were averaged, there was a clear response to the contrast ratio.

Watch 36

Watch 37

There was no significant difference between the tank mix formulations in control on any species.

Antagonism was not observed in any treatment of any species.