Agricultural fluid deposition aid

Abstract

A deposition aid is provided comprising a low molecular weight, low viscosity polysiloxane in combination with crop oil concentrate or esterified seed oil concentrate. Combinations containing said modified silicone can improve leaf spreading and / or adhesion. Adding about 5% to about 20% of the modified silicone can provide a disproportionate increase in spreading and / or adhesion.

Description

Technical Field

[0001] This invention generally relates to additives that improve the deposition properties of certain fluids, and more particularly to formulations and methods for improving the deposition properties of fluids sprayed onto plant surfaces for agricultural purposes. The compositions according to the invention are particularly useful for agrochemicals, and more particularly for herbicides, insecticides, fungicides, biological agents, and growth regulators. Background Technology

[0002] Many chemical formulations benefit from the inclusion of surfactants. For example, the presence of certain surfactants in a chemical formulation can effectively reduce its surface tension. This improves the formulation's ability to adhere to the surface it is applied to and its ability to spread over a larger area of ​​surface with the same amount of formulation. Therefore, in agriculture, the addition of appropriate surfactants can promote improved adhesion of the formulation to the plants it is applied to and can help the same amount of agricultural chemical formulation cover a larger area of ​​plants.

[0003] Emulsifiable petroleum oils (crop oil concentrates or COCs) and emulsifiable methylated seed oils (MSOs) have long been used as agricultural spray adjuvants to enhance the performance of systemic pesticides and other agrochemicals. Crop oil concentrates and methylated seed oil concentrates typically contain surfactant packages designed to aid emulsification and deposition properties. These oils are typically used to enhance the application and penetration of agrochemicals into plants, fungi, and insects. In addition to oil emulsification, surfactants can improve spray deposition properties and thereby enhance droplet adhesion to leaf surfaces by reducing the surface tension of dispersions or emulsions. As used herein, the term surfactant will encompass emulsifiers, dispersants, and spreaders that affect the surface tension of the compositions to which they are incorporated.

[0004] However, there is a desire to further improve the spreading, adhesion, and other properties of agricultural chemicals, including COC and MSO. Therefore, it is desirable for adjuvant compositions to improve the adhesion and spreading properties of agricultural pesticides beyond what can be achieved using existing technologies. Summary of the Invention

[0005] In general, according to the present invention, spreading and depositing aids are provided. These aids may comprise polysiloxanes such as polydimethylsiloxane, oils, and surfactants. Preferably, low-molecular-weight, low-viscosity polysiloxanes are preferred, for example, those having a molecular weight of less than about 5000 g / mol, preferably less than about 4000 g / mol, and more preferably less than about 2000 g / mol (as used herein, the molecular weight of silicone oils will refer to the number-average molecular weight of these oils). Preferred polysiloxanes have a kinematic viscosity (ASTM D 445) of less than about 100 centistokes (cSt) at 25 degrees Celsius, preferably less than about 50 cSt at 25 degrees Celsius, and more preferably less than about 20 cSt at 25 degrees Celsius. Agricultural compositions according to the present invention may comprise bioactive materials in combination with spreading and depositing aids discussed herein, comprising a polysiloxane component, optionally an oil component, and a surfactant. Agricultural compositions according to the present invention may comprise crop oil concentrate (COC) or methylated seed oil concentrate (MSO). These may contain 20% or less, preferably 10% or less, of polysiloxanes. In these compositions, polysiloxanes significantly improve the adhesion and / or spreading of sprayed agricultural composition droplets on vegetation compared to conventional compositions containing COC and MSO. The carbon-to-siloxane ratio in these polysiloxanes should be sufficient to make them soluble or dispersible in oil base stock.

[0006] The organosilicon-based agricultural composition for agricultural use according to the invention may comprise a combination of: (a) an optional oil component, (b) a surfactant, and (c) about 1% to 95% of a polysiloxane having a molecular weight of less than about 5,000 g / mol, preferably less than about 4,000 g / mol, and a viscosity at 25°C of less than about 100 cSt, preferably less than about 50 cSt, wherein the polysiloxane is soluble or dispersible in the oil component (when present).

[0007] The compositions according to the invention can improve the spreading or adhesive properties of agricultural formulations (when compared with the same formulation except that the polysiloxane or organically modified polysiloxane is absent).

[0008] The oils of this invention can be petroleum, alkane oils, mineral oils, vegetable oils, and / or esterified vegetable oils (e.g., methylated seed oil, soybean methyl ester, methylated rapeseed oil, methylated cottonseed oil, methylated palm oil, methylated corn oil), comprising methyl, ethyl, propyl, and isopropyl esters of C8 to C18 fatty acids from natural sources or artificially prepared (e.g., isopropyl myristate, methyl oleate, ethyl oleate, and methyl palmitate). The surfactants, dispersants, and / or spreading agents of the deposition aids of this invention may include at least one ethoxylated or alkoxylated surfactant derived from primary or secondary alcohols. This includes surfactants selected from: polyoxyethylene, polyoxypropylene, polyoxybutene, and mixed polyoxyethylene alkoxylates of fatty alcohols. Surfactants may also include trisiloxane alkoxylates, alkynyl glycol alkoxylates, and block or random polyoxyethylene / polyoxypropylene copolymers.

[0009] Optionally, the composition may also contain a solvent selected from d-limonene, glyceryl triacetate, isopropyl myristate, esterified seed oil, or other suitable solvents. Attached Figure Description

[0010] To gain a fuller understanding of the invention, please refer to the following description in conjunction with the accompanying drawings, in which:

[0011] Figure 1 A diagram illustrating an example of the equilibrium surface tension of a mineral oil / silicone oil mixture;

[0012] Figure 2 A diagram illustrating an example of the equilibrium surface tension of a mixture of OSIL-1 and MO-1;

[0013] Figure 3 A diagram illustrating an example of the equilibrium surface tension of a soybean oil methyl ester / silicone oil mixture;

[0014] Figure 4 A figure illustrating an example of the effect of adding PDMS on the dynamic surface tension (DST) of COC;

[0015] Figure 5 A graph showing the spreading diameter of the 0.5% dispersion in two examples;

[0016] Figure 6 A graph showing the emulsion stability in two examples;

[0017] Figure 7 A figure illustrating an example of the effect of low MW PDMS on the foam volume of MSO adjuvants containing silicone superspreader;

[0018] Figure 8 A diagram illustrating an example of the equilibrium surface tension of an alkyl silicone / MO-1 blend;

[0019] Figure 9 A diagram illustrating the adhesion of droplets between the various formulations on a poinsettia leaf; and

[0020] Figure 10 A figure illustrating an example of the effect of PDM on the dynamic surface tension of COC. Detailed Implementation

[0021] In the specification and claims herein, the following terms and expressions shall be understood as indicated.

[0022] The singular forms “a,” “an,” and “the” include the plural, and references to a particular value include at least that particular value, unless the context clearly specifies otherwise.

[0023] Except as provided in the working embodiments or otherwise indicated, all quantities in the specification and claims that represent the amount of material, reaction conditions, duration of time, quantitative properties of the material, etc., shall be understood to be modified by the term "about" in all cases.

[0024] All methods described herein may be performed in any suitable order unless otherwise indicated herein or otherwise clearly contrary to the context. Any and all instances or exemplary language (such as “for example”) provided herein are intended only to better illustrate the invention and do not constitute a limitation on the scope of the invention, unless otherwise asserted.

[0025] The language used in this specification should not be construed as indicating that any element not claimed is necessary for the implementation of this invention.

[0026] The terms “comprising,” “including,” “containing,” “characterized by,” and their grammatical equivalents are inclusive or open-ended terms that do not exclude additional unmentioned elements or method steps, but will also be understood to include the more restrictive terms “consisting of” and “substantially consisting of.”

[0027] It will be understood that any numerical range referred to herein includes all subranges within that range and any combination of the different endpoints of such ranges or subranges.

[0028] As used herein, integer values ​​of stoichiometric subscripts refer to molecular species, and non-integer values ​​of stoichiometric subscripts refer to mixtures of molecular species expressed as average molecular weight, average number, or mole fraction.

[0029] It will be further understood that any compound, material, or substance that is explicitly or implicitly disclosed in the specification and / or described in the claims as belonging to a group of compounds, materials, or substances that are structurally, compositionally, and / or functionally related includes individual representatives of that group and all combinations thereof.

[0030] As used herein, the terms "agricultural chemicals" or "agricultural products" should be understood to mean all bioactive compounds suitable for agricultural use, including biological agents such as their extracts, fractions, and byproducts, and living organisms including microorganisms, such as pesticides, herbicides, fungicides, insecticides, nematicides, larvicides, miticides, ovicides, plant growth regulators, seed treatment agents, etc. "Agricultural composition" refers to a composition applied to plants, weeds, gardens, grasslands, trees, pastures, or used for other agricultural applications. Agricultural compositions may be provided in concentrated or diluted form. Agricultural compositions may or may not contain agricultural chemicals (agricultural products).

[0031] As used herein, the term "adjuvant" includes optional components that impart functionally useful properties to a composition, such as dispersion, wetting, spreading, etc., and / or enhance the functionally useful properties that the composition already possesses to a certain extent, including any composition, material, or substance that enhances the potency of any agrochemical or active material to which it is incorporated.

[0032] The term "bioactive substance" refers to an agricultural chemical or material that has biological activity, either positive or negative, on living organisms (plants, animals, bacteria, or protozoa), including but not limited to pest control agents such as herbicides, fungicides, insecticides, acaricides, and molluscicides; plant or animal nutrients; defoliants; and plant or animal growth regulators.

[0033] The term "hydrocarbon group" or "hydrocarbon group" means any hydrocarbon that has had one or more hydrogen atoms removed, and includes alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, aralkyl and arenyl groups, and includes hydrocarbon groups containing at least one heteroatom.

[0034] The term "alkyl" refers to any monovalent, saturated, straight-chain, branched, or cyclic hydrocarbon group; the term "alkenyl" refers to any monovalent, straight-chain, branched, or cyclic hydrocarbon group containing one or more carbon-carbon double bonds, wherein the linkage site of the group may be at a carbon-carbon double bond or other positions thereof; and the term "alkynyl" refers to any monovalent, straight-chain, branched, or cyclic hydrocarbon group containing one or more carbon-carbon triple bonds and optionally one or more carbon-carbon double bonds, wherein the linkage site of the group may be at a carbon-carbon triple bond, a carbon-carbon double bond, or other positions thereof. Examples of alkyl groups include methyl, ethyl, propyl, and isobutyl. Examples of alkenyl groups include vinyl, propynyl, allyl, methylallyl, ethylidene norbornene, ethylidene norbornenealkyl, ethylidene norbornene, and ethylidene norborneneyl. Examples of alkynyl groups include ethynyl, propynyl, and methylethynyl.

[0035] As used herein, the term "superspreader" refers to adjuvant surfactants that possess "superspreading" or "superwetting" properties. Superspreading / superwetting is the ability of a drop of superspreader surfactant solution to spread to a diameter greater than that of a drop of distilled water on a hydrophobic surface, and also greater than the diameter of a solution of water and a non-superspreader surfactant on that hydrophobic surface.

[0036] The term "tank-mix" refers to the combination of at least one agricultural chemical with a spray medium such as water or oil at the point of use (application). The term "in-can" refers to a formulation or concentrate containing at least one agricultural chemical component. "In-can" formulations may then be diluted to their application concentration at the point of use (typically in tank-mixes), or may be used undiluted.

[0037] Crop oil concentrate (COC) and methylated seed oil (MSO) are agricultural adjuvants based on petroleum and seed oil bases, respectively. COC and MSO typically contain a surfactant packet comprising 5-40% of the product composition. COC and MSO are sold undiluted and then diluted with water by the end user before spraying. The surfactant packet disperses or emulsifies the oil phase in water and helps the sprayed emulsion or dispersion deposit (adhere) and spread onto the target surface. COC and MSO enhance the penetration of systemic pesticides and other agrochemicals into the plants, fungi, and insects to which they are applied.

[0038] It has been determined that the addition of low molecular weight polysiloxanes (e.g., silicone oils) according to the invention can further reduce the surface tension of petroleum and seed oil base oils used to manufacture COCs and MSOs. The benefits imparted to COCs and MSOs by the addition of the polysiloxanes, and to the resulting agricultural compositions containing these COCs and MSOs (e.g., improved droplet adhesion, spreading, and / or emulsion stability), can surprisingly exceed those benefits expected from agricultural formulations alone (i.e., without the polysiloxanes).

[0039] Surprisingly, it was determined that the spray droplets containing the aforementioned polysiloxane exhibited improved adhesion to plant (e.g., leaf) surfaces, even without a corresponding reduction in the dynamic surface tension of the formulations. Furthermore, the high spreading capacity and improved emulsion stability described herein are also quite remarkable.

[0040] The spreading and depositing aid according to the invention can be formed by combining the following components: (a) 5% to 95%, preferably 50% to 90%, of an optional oil component; (b) 1% to 50%, preferably 5% to 20%, of an emulsifier, surfactant, dispersant, or superspreader component; and (c) about 1% to 95%, preferably 2% to 20%, and more preferably 5% to 15%, of a polysiloxane having a low molecular weight. The preferred polysiloxane has a molecular weight of about 5000 g / mol or less, preferably about 4000 g / mol or less, more preferably 2000 g / mol or less. The polysiloxane should have a viscosity at 25°C below about 50 cSt, preferably below about 20 cSt. The polysiloxane should be soluble or dispersible in the oil component (when present). The preferred agricultural composition according to the invention spreads or adheres to the leaf surface at least 10%, preferably more than 20%, and more preferably at least 50% better than the same formulation in the absence of the polysiloxane.

[0041] The oil component may be mineral oil, alkane crop oil, vegetable oil, or esterified seed oil, and the polysiloxane is polydimethylsiloxane or an organo-modified polysiloxane. Preferred oil components include: mineral oil, alkane oil, seed oil, soybean oil, corn oil, rapeseed oil, sunflower oil, palm oil, cottonseed oil, methylated seed oil, methylated soybean oil, methylated rapeseed oil, methylated cottonseed oil, methylated corn seed oil, partially methylated seed oil, partially methylated soybean oil, methyl octanoate, methyl laurate, methyl myristate, methyl palmitate, methyl oleate, and methyl stearate.

[0042] The compositions of the present invention may optionally be combined with one or more other adjuvant components known for their introduction into aqueous agricultural sprays. Among a variety of optional adjuvants are surfactants (both silicone and non-silicone types) and defoaming additives, as well as additives such as adhesives, thickeners, dyes, etc.

[0043] Suitable emulsifiers and surfactants include nonionic, anionic, cationic, and amphoteric surfactants. Non-limiting examples of suitable nonionic surfactants include alcohol ethoxylates, alkyl polyglycosides, alkylene oxide copolymers of ethylene oxide with propylene oxide and butane oxide, alkyl polyglycerols, alkynyl glycol alkoxylates, etc. Non-limiting examples of suitable anionic surfactants include alkyl sulfate salts (e.g., sodium lauryl sulfate, sodium lauryl ethoxylate, and 2-ethylhexyl sulfate), alkylbenzene sulfonates (e.g., sodium dodecylbenzene sulfonate), and C8-C6 compounds with alkylene oxides. 18 Phosphate mono-, di-, and tri-ester salts, alkyl sarcosine salts such as sodium lauryl sarcosine, etc. Non-limiting examples of suitable cationic surfactants include C8-C... 18 Alkoxylated fatty amines and imidazolines. Non-limiting examples of suitable zwitterionic surfactants include C8-C... 18 Aminopropyl betaine, such as, but not limited to, lauryl betaine, myristyl betaine, lauramidopropyl betaine, daidzeinopropyl betaine, lauramidopropyl betaine, oleyl betaine, lecithin, etc. Agricultural compositions may preferably include fatty alcohol alkoxylated surfactants, such as polyoxyethylene, polyoxypropylene, polyoxybutene, and mixed polyoxyethylene alkoxylated surfactants of fatty alcohols. Non-interfering superspreading surfactants with short-chain hydrophobic groups described in U.S. Patent No. 5,558,806, the entire contents of which are incorporated herein by reference, are also available.

[0044] Specific qualified examples include isodecanol ethoxylates (Oxiteno's Alkosynt ID 30, Solvay's Rhodasurf DA 530, Ethox's Ethal DA-4), isotracetyl alcohol ethoxylates (Clariant's Genapol X 050, Genapol X 060, Genapol X 080, Oxiteno's Alkosint IT 60, Alkosint IT 120), tridecyl alcohol ethoxylates (BASF's Lutensol TDA 6, Lutensol TDA 9, Lutensol TDA 10), Guerbet alcohol alkoxylates (BASF's Lutenxol XL 50, Lutensol XP 50, Lutensol XL 60, Lutensol XP 60, Lutensol XL 80, Lutensol XP 80), and secondary alcohol ethoxylates (Dow Chemical's Tergitol). 15-S-3, Tergitol 15-S-5, Tergitol 15-S-7, Tergitol 15-S-9), polyethylene glycol trimethyl nonyl ether (Dow Chemical's Tergitol TMN 3, Tergitol TMN 6, Tergitol TMN 10), alkyl alkynyl diols (Air Products' Surfynols), pyrrilodone-based surfactants (e.g., Ashland's Surfadone LP 100), 2-ethylhexyl sulfate, ethylenediamine alkoxylates (BASF's Tetronics), ethylene oxide / propylene oxide copolymers (BASF's Pluronics), gemini surfactants (Rhodia / Solvay), and diphenyl ether gemini surfactants (Dow Chemical's DOWFAX).

[0045] Preferred solvents include isopropyl myristate, d-limonene, citrus terpene oil, or triacetin.

[0046] Preferred superspreaders include siloxane polyoxyethylene copolymers. Non-limiting examples include polyoxyethylene, polyoxypropylene, polyoxybutene, and mixed polyoxyethylene alkoxylates of trisiloxane, tetrasiloxane, and pentasiloxane.

[0047] The polysiloxanes according to the invention may have the following general formulas (I), (II), or (III). The viscosity of the polysiloxane should be low, and can be up to about 50 cSt. The most preferred polysiloxanes are low-viscosity polysiloxanes having, for example, a viscosity up to 20 cSt and / or an average MW up to 2000 g / mol. Of the three formulas, general formula (I) is most preferred, especially general formula (I) with a viscosity equal to or below about 20 cSt:

[0048] M 1 D x D 1 y M 2 (I)

[0049] in:

[0050] M 1 =R 1 R 2 R 3 SiO 1 / 2

[0051] M 2 =R 4 R 5 R 6 SiO 1 / 2

[0052] D = R 7 R 8 SiO 2 / 2

[0053] D 1 =R 9 R 10 SiO 2 / 2

[0054] R 1 and R 4 Independently selected from hydroxyl (OH), R 8 OR 8 ;

[0055] R 2 R 3 R 5 and R 6 Independently selected from monovalent alkyl hydrocarbon groups of 1-18 carbon atoms and aryl or alkylaryl hydrocarbon groups of 6-14 carbon atoms;

[0056] R 7 Selected from hydroxyl (OH), OR 8 Monovalent hydrocarbon groups with 1-4 carbon atoms, -OSi(R 8 )3 or -(OSiR 8 R 8 ) fOSi(R 8 2 oz, where Z is H or R 8 And the subscript f is 0-8;

[0057] R 8 It is a monovalent hydrocarbon group with 1-4 carbon atoms;

[0058] R 9 and R 10 Independently selected from monovalent hydrocarbon groups of 1-18 carbon atoms and aryl or alkylaryl hydrocarbon groups of 6-14 carbon atoms; and

[0059] The subscripts x and y are independently 0-50, provided that x+y is approximately 1-50.

[0060] The preferred structure of formula (I) is one in which Y = 0 and all R groups are methyl groups, and the viscosity is 50 cSt or less at 25 degrees Celsius, preferably 20 cSt or less. Other preferred examples of formula I include those where x + y is 5-50; or where y = 0 and x is 3-50; or where R 1 R 4 and R 7 Independently selected from hydroxyl (OH) or methyl; or wherein R 2 R 3 R 5 R 6 and R 8 It is methyl; wherein R 1 -R 8 It is a methyl group; or where y = 0, x = 3-50, and R 1 -R 8 It is methyl; or where y = 0 and x is about 5-25 and R 1 -R 8 It is methyl; or R is one of the following: 10 It is a monovalent alkyl hydrocarbon group with 1-18 carbon atoms or an aryl or alkylaryl hydrocarbon group with 6-14 carbon atoms and R 1 To R 9 It is methyl; or R is one of the following: 1 and R 4 It is a monovalent alkyl hydrocarbon group with 1-18 carbon atoms or an aryl or alkylaryl hydrocarbon group with 6-14 carbon atoms, and R 2 R 3 and R 5 To R 10 It is methyl; or R is one of the following: 10 It is a monovalent alkyl hydrocarbon group with 1-18 carbon atoms or an aryl or alkylaryl hydrocarbon group with 6-14 carbon atoms; or R 1 To R 9 It is a methyl group. In the preferred example of formula (I), R1 It is OH and R 4 and R 7 Methyl; R 1 and R 4 It is OH and R 7 Methyl; R 1 R 4 and R 7 Each is OH; or R 1 R 4 and R 7 Each is a methyl group.

[0061] The polysiloxane according to the present invention can also be defined by structure (II).

[0062] TS 1 R 11 TS 2 (II)

[0063] in,

[0064] TS 1 and TS 2 Independently for R 12 R 13 R 14 Si-O-Si a (R A )-O-SiR 15 R 16 R 17

[0065] in

[0066] Si a It is a monovalent group and R 11 With Si a connect

[0067] R 11 Selected from divalent hydrocarbon groups with 4-18 carbons,

[0068] R A R 12 R 13 R 14 R 15 R 16 and R 17 Independently selected from monovalent hydrocarbon groups of 1-4 carbons.

[0069] Preferred examples of Formula II include the following: where R 11 It is a divalent hydrocarbon group containing 4-18 carbons, wherein R A and R 12 To R 17 It is a methyl (-CH3) group.

[0070] The polysiloxane according to the present invention can also be defined by structure (III).

[0071] R 19 -[Si(CH3)2O 1 / 2 -(D 2 )zO 1 / 2 Si(CH3)2–R 18 ] w -R 20 (III)

[0072] in

[0073] R 19 =H-, CH3- or HR 18 -

[0074] R 20 =H- or -Si(CH3)2O 1 / 2 -(D 2 )zO 1 / 2 Si(CH3)2H or

[0075] -Si(CH3)2O 1 / 2 -(D 2 ) z -O 1 / 2 Si(CH3)2CH3,

[0076] R 18 Divalent hydrocarbon groups selected from 4 to 18 carbons

[0077] D 2 =R 21 R 22 SiO 2 / 2 ,

[0078] R 21 and R 22 Independently selected from monovalent hydrocarbon groups of 1-4 carbons,

[0079] z = 2 - 20, and

[0080] w = 1-20 (w = 1 or 2 is preferred).

[0081] Preferred examples of Formula III include the following: where w = 1-10 and where R 21 and R 22 It is a methyl (-CH3) group.

[0082] The agricultural composition may preferably include a solvent selected from d-limonene, triacetin, isopropyl myristate, and esterified seed oil.

[0083] The method according to the invention relates to improving the spreading and / or adhesive properties of agricultural compositions comprising mineral oil, alkane crop oil, esterified seed oil, or vegetable oil (including COC and MSO), comprising adding to the agricultural composition an effective amount of a selected polysiloxane or organo-modified polysiloxane having an average molecular weight of less than about 5000 g / mol, preferably less than about 4000 g / mol, and more preferably less than about 2000 g / mol. Preferred polysiloxanes have a kinematic viscosity (ASTM D 445) of less than about 100 centistokes (cSt) at 25°C, preferably less than about 50 cSt at 25°C, and more preferably less than about 20 cSt at 25°C. Preferred polysiloxanes have the general formula I, II, or III shown above. The method can effectively result in the composition exhibiting improved adhesion and / or spreading (compared to the same composition but without the polysiloxane or organo-modified polysiloxane). Increases in spreading and / or adhesion of 10%, 20%, and even more than 50% are possible.

[0084] The deposition aid according to the invention can be provided as an agricultural composition in which the individual components or combinations thereof are blended on-site. For example, it can be provided as an isolated polysiloxane or in combination with other materials such as mineral oil, vegetable oil, esterified seed oil, surfactants and agrochemicals to form a barrel blend, which can then be applied as needed.

[0085] The optimal amount of polysiloxane spreading and depositing aids for a specific spray composition and spraying operation can be readily determined using conventional experimental testing procedures known in the art. For many spray compositions, the compositions of the present invention can be introduced in amounts ranging from 0.01-5 wt%, and preferably 0.05-1 wt%, which generally yields good spreading and adhesion results. Therefore, the present invention comprises MSO and / or COC containing polysiloxanes as described herein, preferably at a concentration of 1-20% in the MSO or COC. This MSO or COC can then be diluted with water by the end user for agricultural purposes to prepare an emulsion or spray solution. The MSO or COC will typically comprise 0.1-2% of the final emulsion or spray solution.

[0086] In addition to the compositions of the present invention, agricultural sprays may also include one or more known and conventional active ingredients or agrochemicals of agricultural compositions, such as pesticides, fertilizers and micronutrients.

[0087] Pesticide sprays include at least one pesticide. Optionally, pesticide sprays may include excipients, surfactants, solvents, foam control agents, sedimentation aids, biological agents, micronutrients, fertilizers, etc. The term "pesticide" means any compound used to destroy pests, such as rodenticides, insecticides, acaricides, miticides, fungicides, herbicides, etc. Illustrative examples of usable pesticides include, but are not limited to, growth regulators, photosynthesis inhibitors, pigment inhibitors, mitotic disruptors, lipid biosynthesis inhibitors, cell wall inhibitors, and cell membrane disruptors. The amount of pesticide used in the spray composition will vary depending on the specific type of pesticide.

[0088] Specific examples of herbicidal and plant growth regulator compounds that can be introduced into spray compositions include, but are not limited to: phenoxyacetic acid, phenoxypropionic acid, phenoxybutyric acid, benzoic acid, triazine and mesazine, substituted urea, uracil, bentazon, betaine, betaine, betaine, pyrazosulfuron, chlorpyrifos, isoxaflutole, fluroxypyr, fluroxypyr, dinitroaniline, isoxaflutole, ammonium sulfadiazine, pendimethalin, amfluroxypyr, fluroxypyr, glyphosate, sulfonylurea, imidazolinone, clethodim, quizalofop-p-ethyl, oxazol, quizalofop-p-ethyl, flupyridine, quizalofop-p-ethyl, dichlorvos, isoxaflutole, bipyridon compounds, etc. Common and Chemical Names of Herbicides Approved by the Weed Science Society of America, Weed Science, 58:511-18 (2010) is incorporated herein by reference.

[0089] Specific examples of fungicidal compositions include, but are not limited to, pyraclostrobin, clotrimazole, dodecyl morpholine, dimethomorph; flusilazole, tebuconazole, cyclophosphamide, flutriafol, furazolidone, propiconazole, tebuconazole, etc.; imazalil, thiophanate-methyl, benomyl, carbendazim, chlorothalonil, chlorpyrifos, azoxystrobin, fluopyram, pyraclostrobin, dimethomorph, prochloraz, sulfadiazine, oxadixyl, captan, mancozeb, mancozeb, doxycycline, styraxazol, metalaxyl, etc.

[0090] Specific examples of insecticides, larvicides, acaricides, and ovicides that can be introduced into aqueous spray compositions include, but are not limited to, Bacillus thuringiensis (or Bt), spinosad, abamectin, doramectin, fibronectin, pyrethroids, carbaryl, chlorpyrifos, methomyl, amectin, boric acid, trichlorfon, novoflurane, triflusulfone, triflusulfone, difluorobenzofuran, imidacloprid, imidacloprid, imidacloprid, metronidazole, ethyl glutathione, methyl glutathione, oxazolidinone, chlorpyrifos, chlorfenapyr, lambda-cyhalothrin, permethrin, bifenthrin, cypermethrin, etc.

[0091] Fertilizers and micronutrients include, but are not limited to, zinc sulfate, ferrous sulfate, ammonium sulfate, urea, urea ammonium nitrogen, ammonium thiosulfate, potassium sulfate, monoammonium phosphate, urea phosphate, calcium nitrate, boric acid, potassium and sodium salts of boric acid, phosphoric acid, magnesium hydroxide, manganese carbonate, calcium polysulfide, copper sulfate, manganese sulfate, ferric sulfate, calcium sulfate, sodium molybdate, calcium chloride, etc.

[0092] Buffers, preservatives, and other standard agricultural excipients known in the art may also be included in the spray composition.

[0093] Agricultural spray compositions can be prepared by combining one or more of the above spray components with the composition of the present invention (as a barrel mix or as a "canned" formulation) in any combination and / or sequence by means known in the art (e.g., mixing in water).

[0094] This invention also includes agricultural compositions of the invention, which are applied to and used to treat crop plants, garden and ornamental plants, trees, and pastures. For example, they can also be used in forestry applications and on golf courses. Crop plants include, for example, vegetable crops such as broccoli, cabbage, kale, spinach, onions, and peppers; legumes such as lentils, peas, and soybeans; cereal crops such as wheat, corn, barley, rye, rice, and oats; flowering crops such as roses, tulips, daisies, daffodils, gerberas, sunflowers, orchids, jasmine, and carnations; and root and tuber crops such as potatoes, beets, radishes, parsnip, turnips, and carrots. Crop plants may further include fruits such as citrus fruits, apples, tomatoes, grapes, watermelons, pears, raspberries, blueberries, plums, peaches, bananas, pineapples, strawberries, plantain, kiwifruit, and mangoes; and nut trees such as almonds, chestnuts, hazelnuts, pecans, macadamia nuts, walnuts, pine nuts, pistachios, and walnuts. It can also be applied to agricultural compositions and used to treat pastures such as clover, alfalfa and grass, and crop plants such as squash, tubers, zucchini, pumpkin, as well as coconut, palm and cocoa trees.

[0095] The agricultural compositions of the present invention can be combined with herbicides and applied to control weeds, such as those listed below: *Anoda cristata*, *Momordica charantia*, barley (*Hordeum vulgare*), barnyard grass (*Echinochloa crus-galli*), *Bassia hyssopifolia*, shepherd's purse (*Cardamine spp.*), bluegrass (*Poa bulbosa*), bromegrass (*Bromus tectorum*), bromegrass (*Bromus japonicas*), golden chrysanthemum (*Ranunculus spp.*), *Alopecurus carolinianus*, geranium carolinianum, castor bean (*Ricinus communis*), chamomile (*Anthemis cotula*), ryegrass-like bromegrass (*Bromus secalinus*), *Anthriscus cerefolium*, and *Cerastium*. *Vulgatum*, *Xanthium strumarium*, *Coreopsis tinctoria*, *Zea mays*, *Digitaria spp.*, *Krigia virginica*, *Glyceria spp.*, *Eclipta prostrata*, *Pyrrhopappus carolinianus*, *Camelina Microcarpa*, *Amsinckia spp.*, *Thlaspi arvense*, *Erigeron annuus*, *Conyza bonariensis*, *Erigeron strigosus*, *Richardia scabra*, *Setaria spp.*), Cylindrical Goat's Sheepgrass, Eleusine indica, Senecio vulgaris, Lamium amplexicaule, Conyza Canadensis, Rottboellia cochinchinensis, Sorghum halepense, Echinochloacolona, ​​Polygonum spp., Kochia scoparia, Chenopodium album, Taeniatherum caput-medusae, Ipomoea spp.Mustard, Chorispora tenella, Mustard, Garlic Mustard (Sisymbrium altissimum), Mustard, Xinjiang White Mustard (Sinapis arvensis), Oats, Wild Oats (Avena fatua), Millet, Wild Millet (Panicum dichotomiflorum), Pigweed, Amaranthus retroflexus, Pigweed, Green Spinach (Amaranthus hybridus), Wild Lettuce (Lactuca serriola), Tribulus terrestris, Portulaca oleracea, Ragweed (Ambrosia artemisiifolia), Three-lobed Ragweed (Ambrosia trifida), London Water Garlic Mustard (Sisymbrium irio), Russian Spiny Sand Sprout (Salsola tragus), Cereal Rye (Secale cereal), Italian Ryegrass (Lolium perenne), Field Tribulus (Cenchrus) spinifex, Sesbania herbacea, Sorghum bicolor, Capsella bursa-pastoris, Sennaobtusifolia, Urochloa platyphylla, Pennsylvania Polygonum pensylvanicum, Sonchus oleraceus, Bidens bipinnata, Veronica arvensis, Veronica peregrina, Leptochloaspp., Chamaesyce spp., Chamaesyce humistrata, Chamaesyce maculate, Holostemma umbellatum, Eragrostis cilianensis, Helianthus (Annuus), pinnate-leaved lepidium (Descurainia pinnata), spiny tea grass / yellow flower sage (Sida spinosa), Texas millet (Panicum spp.)), Abutilon theophrasti, Lepidium virginicum, Triticumaestivum, Panicum capillare, Eriochloa villosa, Barbareavulgaris.

[0096] Additional plants for receiving the agricultural composition according to the invention include perennial plants such as alfalfa, anise / fennel, Kentucky bluegrass, clover, dandelion, ivy, milkweed, hemlock, thistle, and grass. Trees include alder, patchouli, beaches, poplar, cherry, elderberry, elm, hickory, honeysuckle, kudzu, maple, oak, pine, spruce, sumac, ferns, Virginia creeper, and poplar.

[0097] Example

[0098] Preferred aspects and properties of the invention will be described with reference to the following embodiments, which are presented for illustrative purposes only and should not be construed as limiting. Furthermore, unless otherwise stated, as used in these embodiments, R... 1 -R 10 Each can be considered as a methyl group.

[0099] Product Description

[0100] Table 1-4 describes the products used in the examples below.

[0101] Table 1: Organo-based modified polysiloxanes

[0102]

[0103] * - Not measured; a. DMS-S12, b. DMS-S15 and c. DMS-S21 – from Gelset

[0104] Table 2: Organic Surfactants

[0105]

[0106] Table 3: Adjuvants containing organosilicon

[0107]

[0108] Table 4: Sources and Types of Crop Oils

[0109]

[0110] Spreading measurement

[0111] The spreading ability of various compositions and formulations is evaluated by depositing a drop (10 μL) of the emulsion (or other material) to be evaluated onto a clean, flat polystyrene dish. The diameter of the resulting droplet is then measured after 30 seconds. Each solution is tested 2-4 times and the average diameter is calculated. Alternatively, spreading ability is also evaluated by depositing a drop (10 μL) of the sample to be evaluated onto a leaf surface. The area of ​​the resulting droplet is then measured after 3 minutes, unless otherwise specified. Each sample is tested 2-4 times and the average spreading area is calculated.

[0112] The effect of PDMS oil on surface tension when blended with base oils

[0113] Low surface tension is beneficial for agricultural pesticide applications because it is associated with better droplet adhesion and spreading. The effect of polydimethylsiloxane (PDMS) oil on surface tension when blended with different base oils was evaluated, and the results show… Figure 1 , 2 Figures 3 and 4 are on a logarithmic scale, making the straight lines effectively represent nonlinear results. Therefore, the results demonstrate that even a small amount of silicone oil addition leads to a disproportionately large decrease in the equilibrium surface tension.

[0114] like Figure 1 As can be seen, the surface tension of oil MO-1 was reduced from 30 mN / m to 26 mN / m (a reduction of more than 10%) by adding only 1% OSIL-2 (a 10 cSt polydimethylsiloxane (PDMS) oil, identified as Element 14 10A, with an equilibrium surface tension slightly below 20). The addition of only 10% OSIL-2 silicone oil reduced the surface tension of the blend to 23 mN / m, a reduction of more than half the difference between the surface tensions (30 and 20). As used herein, all percentages are calculated on a weight basis. Similarly, as... Figure 2 As shown, adding 10% (wt) OSIL-1 (a 5cSt PDMS oil) to MO-1 reduced the equilibrium surface tension of the product from 29.1 mN / m to 24.3 mN / m. Adding 10% (wt) OSIL-3 (a 20cSt PDMS oil) to MO-3 resulted in a decrease in the surface tension of the product from 30 mN / m to 22.8 mN / m.

[0115] Figure 3 The results show that the addition of low molecular weight silicone oil OSIL-2 to esterified seed oil MS-1 also resulted in a significant decrease in surface tension with a relatively small amount of silicone oil. The addition of 1% OSIL-1 reduced the surface tension of soybean oil methyl ester from about 30 mN / m to about 26 mN / m and 10% reduced it to about 23 mN / m.

[0116] Product oil concentrates (COCs) were formulated to evaluate the effects of low molecular weight, low viscosity PDMS oils according to the present invention on their leaf spreading and dynamic surface tension. The surfactant mixture SURF-1 as defined in Table 5 was used in each formulation. A commercially available nonionic surfactant was added to two of the samples. 15-S-5 is used to increase the HLB value of the surfactant package. 15-S-3 and 15-S-5 are 3 and 5 moles of ethoxylates of the C11-C15 secondary alcohol mixture, respectively. TMN-3 is a 3-molar ethoxylated derivative of trimethylnonyl alcohol. The results are summarized in Table 6.

[0117] Table 5: Basic Raw Materials for Surfactant Formulations (SURF-1)

[0118]

[0119] The data in Table 6 show that the addition of the PDMS oil (OSIL-2) according to the invention to crop oil concentrate (COC) formulations surprisingly resulted in a significant, and sometimes very substantial, increase in spreading on the leaves of both poinsettia and philodendron. This is surprising because the spreading of COC or MSO dispersions is typically driven by the surface tension of the aqueous phase of the spray droplets (rather than the equilibrium surface tension of the dispersed oil phase). Figure 4 The dynamic surface tension (DST) curves of the sprayed aqueous solutions of SIL-1 to SIL-5 shown are all substantially the same and significantly lower than those of the COC-1 dispersion. Therefore, we expect SIL-1 to SIL-5 to produce similar spreading areas on plant leaves, and expect all five to spread significantly more than the COC-1 dispersion. As expected, the COC-1 dispersion is the least effective spreader. However, surprisingly, formulations containing the polysiloxane OSIL-2 spread significantly better than their silicone-free counterparts.

[0120] The benchmark crop oil concentrate SIL-3 was prepared by co-blending 11.25% of the SURF-1 surfactant package into MO-1. In SIL-1, 10% OSIL-2 was added, replacing the same amount of MO-1. As shown in Table 6, SIL-1 containing OSIL-2 spread almost twice as much on poinsettia as the SIL-3 benchmark and increased by 12.5% ​​on philodendron leaves.

[0121] A second baseline COC formulation, SIL-5, was formulated. SIL-5 contained a SURF-1 surfactant package plus a small amount of surfactant NIS-2 to increase the HLB (hydrophilic-lipophilic balance) of the total surfactant package. The COC formulation SIL-2 was prepared by adding polysiloxane OSIL-2 to this formulation. SIL-4 is a similar formulation containing SURF-1, NIS-2, and OSIL-2. As shown in Table 6, compared to SIL-5 (the baseline without polysiloxane oil), the polysiloxane-containing formulations SIL-2 and SIL-4 exhibited 7.6 to 8 times greater spreading on poinsettia leaves and 1.7 to 3.6 times greater spreading on philodendron leaves.

[0122] Table 6: Effects of silicone oil on leaf cover

[0123]

[0124] Agri-Dex, from Helena Chemical Co., is a commercial benchmark crop oil concentrate.

[0125] In summary, compared to a 1% COC-1 solution (a commercially available crop oil concentrate), the experimental COC formulations SIL-1 to SIL-5 all exhibited significantly improved spreading. Furthermore, a surprisingly significant improvement in spreading properties was observed for formulations containing polysiloxanes, while the dynamic surface tension curves for SIL-1 to SIL-5 were essentially the same. This indicates that the improved spreading is not only a result of decreased surface tension but also an unexpected consequence of the silicone oil of this invention (especially when combined with the surfactant NIS-2). Therefore, the addition of OSIL-2 did not significantly affect the DST (dynamic surface tension) of the 1% solutions of these experimental COCs, but the spreading unexpectedly increased (see Table 6).

[0126] Tables 7 and 8 below show the effects of different combinations of PDMS oils and different surfactants according to the invention on leaf spreading in the experimental COC formulations. As shown in these tables, the addition of the silicone oil according to the invention resulted in significant spreading improvements in all surfactant cases when tested on philodendron, bamboo, broccoli, and poinsettia leaves. COC formulations SIL-21 and SIL-22 demonstrated that when using different base oils (in this case...) 80(MO-2) instead When preparing COC with 796(MO-1), the improvement seen with the addition of OSIL-2 was also observed.

[0127] The greatest increase in leaf spreading was observed when the silicone oil was combined with surfactants NIS-2 (SIL-7 and SIL-8), NIS-1 (SIL 16), NIS-4 (SIL-10), and NIS-6 (SIL-18). As can be seen when comparing SIL-7 and SIL-8, the 50 cSt PDMS oil (OSIL-4, Element 14 PDMS 50) used in formulation SIL-8 appears to be at least as effective as (if not better than) OSIL-2. However, the higher the viscosity of the silicone oil, the more difficult it is to dissolve and / or emulsify in crop oil concentrate formulations.

[0128] Table 7: Effects of surfactants and PDMS on COC spreading (1% dispersion)

[0129]

[0130] Table 8: Effects of surfactants and PDMS on COC spreading (1% dispersion)

[0131]

[0132] 1 No alkyl silicone added

[0133] The data in Table 9 show that SIL-23 (a COC formulation containing OSIL-1) increased the spread on bamboo, philodendron and poinsettia leaves by about 3 times compared to SIL-6 (a non-silicone oil baseline).

[0134] Table 9: Effects of OSIL-1 and OSIL-2 on COC spreading

[0135]

[0136] 1 No alkyl silicone added

[0137] Table 10 summarizes the results of spreading examples using 0.5% solutions of SIL-6 and SIL-7 (COC prepared from MO-1, MO-1 being an alkane oil from Calumet Specialty Chemicals Orchex 796) and SIL-24 and SIL-25 (MSO prepared from MS-1, MS-1 being a soybean oil methyl ester from Chemical Associates, ADivision of Univar USA, Inc. CA3050). For both base oils, the addition of the silicone oil (OSIL-2) according to the invention significantly improved the leaf spreading properties of the products.

[0138] Table 10: Spreading of 0.5% COC spray solution

[0139]

[0140] *10 is opaque / milky white and very stable; 1 is almost clear and separates rapidly.

[0141] *Considering the low concentration, the dispersibility of the 0.5% emulsion is quite good.

[0142] Except for (Agri-Dex), which is tested at 1.0%.

[0143] Table 11 summarizes the results of spreading examples using a 1.0% solution of formulations containing OSIL-3 (a 20 cSt polydimethylsiloxane (PDMS) oil) and NIS-2 in two different mineral oils (MO-1 and MO-3). SIL-6 and SIL-7 were used as benchmarks for formulation SIL-26. All three products were based on MO-1. Formulation SIL-27 was used as a benchmark for SIL 28. Both of these products were based on MO-3. For both base oils, the addition of the silicone oil according to the invention significantly improved the leaf spreading properties of the products compared to the same mineral oil containing only the nonionic surfactant NIS-2.

[0144] Table 11: Effects of OSIL-1 and OSIL-3 on COC spreading

[0145]

[0146] 1 No alkyl silicone added

[0147] Adhesion tests conducted with a 0.5% aqueous solution of Sil-6 and SIL-7 demonstrated a significant improvement in the adhesion of the formulation according to the invention to leaves. Solution droplets were generated using a syringe pump and a Nisco Encapsulation Unit (Var J1) J1 with a nozzle having an inner diameter of 0.41 mm. Data in Table 12 show that the addition of PDMS oil OSIL-2 to the COC formulation (SIL-6) increased the number of droplets adhering to the grass leaf surface by approximately three times, from 16.3% (SIL-6) to 45.9% (SIL-7). Figure 10 As can be seen, the two COC formulations exhibit essentially the same dynamic surface tension. Therefore, the enhanced adhesion observed here is unexpected, given the understanding that droplet adhesion increases with decreasing dynamic surface tension (DST).

[0148] Table 12: Adhesion of droplets on barnyard grass (Echinochloa crus-galli)

[0149]

[0150] Water droplet size ≈ 950μm

[0151] COC droplet size ≈ 700 μm

[0152] The droplet fell a distance of 49.5 cm.

[0153] Droplet impact velocity ≈ 2.5-3 m / s

[0154] Similar droplet adhesion studies were conducted using methylated seed oil (MSO) formulations with and without OSIL-2 (SIL-24 and SIL-25, respectively). Droplets with a diameter of approximately 400 μm were generated at a height of 53 cm above the cabbage leaf surface. The leaves were fixed at an incline of 22.5°. The percentage of impacted droplets that adhered to the cabbage leaf surface was then measured. As in the case of petroleum (mineral oil)-based COC in Table 12, the addition of silicone oil to MSO unexpectedly and significantly improved droplet adhesion to the cabbage leaf surface. The results are summarized in Table 13 below.

[0155] Table 13: Adhesion of adjuvant solution on the adaxial leaf surface of cabbage

[0156]

[0157] The difference in the average adhesion was statistically significant, with a 95% confidence level (P < 0.05, LSD test).

[0158] Referring to Table 14 below, Silwet 641 (OSS-1) is a surfactant mixture based on a superspreader (trisiloxane alkoxylate), an organosilicon, and several nonionic surfactants. It is typically added to MSO base oils at concentrations ranging from 10-20%. Sample SIL-29 in Table 14 is a blend of 20 wt% OSS-1 and 80 wt% MS-1. Sample SIL-30 is a blend containing 20 wt% OSS-1, 70 wt% MS-1, and 10 wt% OSIL-2. Silwet 641 is often referred to as a superspreader and has consistently been considered to provide the best available spreading properties. Table 14 and... Figure 5 and 6 The data demonstrates that the addition of the silicone oil according to the invention reduces the equilibrium surface tension, improves the emulsion stability of the added MSO concentrate, and surprisingly increases the spreading diameter of the product. Note that... Figure 6 In this context, TSI measures emulsion separation, with a lower TSI corresponding to improved emulsion stability.

[0159] Table 14: Blends of PDMS, nonionic & silicone surfactants in MSO

[0160]

[0161] A similar study was conducted by adding silicone oil to the MSO adjuvant formulation and evaluating the spray coverage of the product. Instead of measuring the spreading diameter on the hydrophobic surface, twelve sprays were performed using a 0.5% spray solution of samples SIL-31 and SIL-32. The solution was sprayed using an 8002E flat fan nozzle at a pressure of 20 psig. These spraying conditions correspond to a field spray volume of 100 L / ha. For each spray, the coverage achieved on a square piece of water-sensitive paper was measured. The average spray coverage for each product was then calculated. The results are summarized in Table 15. The data show that increased spray coverage was achieved by adding the low molecular weight silicone oil (polysiloxane) according to the invention to the MSO formulation, wherein SIL-32 (with OSIL-2) provides better coverage than SIL-31 without PDMS oil.

[0162] Table 15: Spray Coverage of Surfactant Blends in MSO Adjuvants

[0163]

[0164] Following the methodology previously described by Gaskin et al. (Stevens, PJ, Kimberley, MO, Murphy, DS, & Policello, GA; Adhesion of spray droplets to foliage: the role of dynamic surface tension and advantages of organosilicone surfactants), Pesticide Science, Vol. 38, 1993, pp. 237-245; Forster, WA, Mercer, GN and Schou, WC, Process-driven models for spray droplet shatter, adhesion or bounce, Baur P, Bonnet M, editors. Proceedings 9th International Symposium on Adjuvants and Agrochemicals. ISAA 978-90-815702-1-3; 2010), the effect of the composition of the present invention on droplet adhesion of the spray solution was tested on barnyard grass (Echinochloa crus-galli), which is difficult to wet. Droplets with a diameter of approximately 400 μm were impacted from a height of 53 cm onto a leaf fixed at a 22.5-degree angle to the horizontal plane. Droplet adhesion was compared with the dynamic surface tension of the corresponding formulation.

[0165] The composition of samples SIL-33 to SIL-36 is shown in Table 16.

[0166] Table 16: Examples of Preparation of Agricultural Deposition Aids

[0167]

[0168] AgroSpred 820 is an MSO concentrate made from 20 wt% Silwet 641 and 80% MS-1.

[0169] The adaxial leaf surface of barnyard grass is extremely difficult to wet. Therefore, it is a good target for comparative droplet adhesion studies. Table 17 presents droplet adhesion as a percentage of impacted droplets remaining on the leaf surface. As can be seen in Table 17, the compositions of the present invention produce a surprisingly large increase in droplet adhesion relative to the commercial benchmark AgroSpred 820 (20 wt% Silwet 641, 80 wt% MSO) and relative to the SIL-34 benchmark without PDMS oil. This unexpected improvement is associated with the use of 10 cSt PDMS oil OSIL-2. Given the small to insignificant differences in DST observed at typical impact times (50 to 250 ms), this level of improvement (droplet adhesion increasing by more than twofold) is a surprising and unexpected result.

[0170] Table 17: Adhesion of adjuvant treatment on barnyard grass (BYDG) leaves

[0171]

[0172] The effect of low MW PDMS oil on the foam volume of MSO concentrate was also tested. Figure 7 The foam volume is shown as determined by a spaghetti test. In this test, nitrogen gas was bubbled in a spray solution at 1.0 L / min for 1 minute using a metallic frit. Foam volumes were measured at the initial point (the point where bubbling stopped), and at 1, 2, 5, and 10 minutes. As can be seen, the low MW PDMS oil reduced the foam level to below that achievable using a high-performance defoamer (e.g., SAG-1572, available from MomentivePerformance Materials). This result is unexpected, as the presence of trisiloxane alkoxylates typically renders commercial defoamers ineffective at typical usage rates, a result associated with the low equilibrium surface tension created by the silicone superspreader.

[0173] As described above, the addition of low concentrations (1-20%) of the low molecular weight, low viscosity polydimethylsiloxane (silicone oil) according to the invention to COC and MSO significantly reduces the surface tension of petroleum and seed oil base oils. The presence of silicone oil also enhances the adhesion of sprayed COC and MSO droplets to the leaf surface. Moreover, the addition of these low molecular weight silicone oils to crop oil concentrates and MSO unexpectedly results in significantly improved spreading on a variety of leaf surfaces, while also improving emulsion stability and reducing foam volume.

[0174] Note that the limiting factor may be the poor solubility of PDMS oil in crop oil bases. The following results describe the investigation of the effects of various alkyl silicone oils on the properties of COC and MSO. All the alkyl silicone oils evaluated here exhibited good solubility in both mineral oils and methylated seed oils and significantly reduced the equilibrium surface tension of the resulting COC and MSO. Furthermore, all alkyl silicone oils improved the spreading of COC and MSO on plant leaves. The alkyl-modified silicones tested are described below.

[0175] Alkyl-modified silicone. The alkyl group is C8 or C12.

[0176]

[0177] n = 0 or 4

[0178] OSIL-5 (n=0) and OSIL-6 (n=4)

[0179]

[0180] n = 0 or 4

[0181] OSIL-7 (n=1) and OSIL-8 (n=5)

[0182]

[0183] First, the solubility of alkyl silicone oils in typical mineral oils and methylated seed oils was determined. Then, the effect of alkyl silicones on the equilibrium surface tension of blends with crop-based oilseeds was measured. Finally, the spreading properties of simple COC and MSO formulations containing alkyl-modified silicone oils were determined.

[0184] OSIL-5, OSIL-6, OSIL-7, and OSIL-8 all exhibited good solubility in MO-1. The equilibrium surface tension of these net (unadulterated, neat) alkyl silicone oils was then measured. They had surface tensions of 22–23 mN / m (see Table 18), significantly lower than that of net MO-1 (29.9 mN / m).

[0185] The effect of alkyl silicone concentration on the equilibrium surface tension of MO-1 was determined. Adding 10% OSIL-5 to MO-1 resulted in a significant reduction in surface tension, from 29.9 mN / m to approximately 26 mN / m. For OSIL-6 through OSIL-8, adding 10% alkyl silicone to MO-1 reduced the surface tension to below 24 mN / m. This is similar to the reduction in surface tension achieved when adding OSIL-2 to MO-1. It was observed that while the compositions of the present invention are capable of reducing the equilibrium surface tension of unadulterated oil blends, such a reduction is not always observed for aqueous dispersions of their respective oil-based formulations. Furthermore, no significant difference was observed in the dynamic surface tension (DST) of spray solutions containing COC or MSO with and without the compositions of the present invention. Those skilled in the art would expect that droplet adhesion in those formulations would be comparable, as droplet adhesion is generally associated with dynamic surface tension; however, the introduction of the compositions of the present invention resulted in increased droplet adhesion, although the DST was not significantly reduced. This observation is unexpected and surprising. The solubility of alkyl silicones in MSO and the data from EST measurements are summarized in Table 18. The surface tension versus alkyl silicone concentration curves are shown in... Figure 8 middle.

[0186] Table 18: Solubility and equilibrium surface tension of alkyl silicones in MSO

[0187]

[0188] Crop oil concentrates (COCs) based on MO-1 and 10% of the nonionic surfactant NIS-2 were formulated to determine the effect of alkyl silicones according to the invention on spreading. As a baseline, a 10:90 blend of surfactants in oil was used. The spreading of the COC formulations and 1% dispersions of these products is shown in Table 19. All COC formulations containing alkyl silicone oils spread significantly better on philodendron and bamboo leaves than the NIS-2 / MO-1 control (SIL-41).

[0189] Table 19: Effect of alkyl silicones on the spreading of NIS-2 / MO-1 blends (1% dispersion)

[0190]

[0191] A similar set of data was generated to examine how the four alkyl silicones behaved in MS-1. Table 20 shows the solubility and equilibrium surface tension of the alkyl silicones blended with MS-1. All four products exhibited good solubility in soybean methyl ester base oil. The effect of different concentrations of alkyl silicones OSIL-6 and OSIL-7 on the equilibrium surface tension of MS-1 was determined, and both alkyl silicones at a 10% concentration reduced the surface tension of CA-1 by more than 5 mN / m.

[0192] Table 20: Solubility and equilibrium surface tension of alkyl silicones in MS-1

[0193]

[0194] 1 MS-1 without alkyl silicone oil

[0195] Methylated seed oil concentrates (MSOs) based on MS-1 were prepared. They contained 10 wt% NIS-2, 10 wt% alkyl silicone, and 80 wt% MS-1. As a baseline, a 10:90 blend of surfactant NIS-2 in seed oil MS-1 was used. The spreading of the MSO formulations and dispersions of 1% of these products are shown in Table 21. Both MSO formulations containing alkyl silicone showed significantly better spreading than the SIL-44 baseline after 15 and 120 minutes of spreading (except for the SIL-42 dispersion, which was comparable to the control after 2 hours on philodendron).

[0196] Table 21: Effect of alkyl silicones on the spreading of NIS-2 / MS-1 blends (1% dispersion)

[0197]

[0198] Table 22 shows the effects of OSIL-9 and OSIL-10 on the equilibrium surface tension of MO-1. Both alkyl silicones significantly reduced the surface tension of the oil at relatively low concentrations.

[0199] Table 22: Equilibrium surface tension of MO-1 blends with alkyl silicones

[0200]

[0201] Samples of crop oil concentrates containing OSIL-9 and OSIL-10 were prepared. A 10:90 blend of NIS-2 in MO-1 was also used as a baseline. The spreading of 1% dispersions of these products was determined on polystyrene boards, philodendron leaves, and bamboo leaves. The results are summarized in Table 23. The composition SIL-45 of the present invention produced very excellent spreading compared to the baseline sample SIL-47. SIL-46, also a composition of the present invention, exhibited significantly better spreading on leaf surfaces than the SIL-47 baseline.

[0202] Table 23: Effect of alkyl silicones on the spreading of NIS-2 / MO-1 blends (1% dispersion)

[0203]

[0204] 1 No alkyl silicone added

[0205] OSIL-9 and OSIL-10 were also evaluated in MS-1. Both products showed good solubility in the seed oil. The effect of different concentrations of these two alkyl silicones on the equilibrium surface tension of soybean oil methyl esters was determined and is shown in Table 24.

[0206] Table 24: Equilibrium surface tension of blends of MS-1 and alkyl silicones

[0207]

[0208] MSO concentrates were formulated using 10 wt% NIS-2, 10 wt% OSIL-10, and 80 wt% MS-1. As a control, a 10:90 blend of NIS-2 surfactant in seed oil MS-1 was used. The spreading of the formulations and 1% dispersions of these products is shown in Table 24. The alkyl silicone-containing formulation SIL-48 produced very good spreading on all tested surfaces and was significantly superior to the control formulation SIL-49.

[0209] Table 25: Effect of alkyl silicones on the spreading of NIS-2 / MS-1 blends (1% dispersion)

[0210]

[0211] 1 No alkyl silicone added

[0212] Figure 9 The images show some droplet adhesion tests conducted on poinsettia leaves using the compositions of the present invention. Results are expressed as the average percentage of hit droplets remaining on the leaf surface. As can be seen, the compositions of the present invention deliver significantly higher droplet deposition rates than the baseline COC formulation.

[0213] The following examples include alkyl silicones in MSO formulations containing organosilicon superspreaders. The evaluated MSO samples consisted of 70 wt% MS-1, 20 wt% OSS-1, and 10 wt% of the alkyl-modified silicone oils described above. These MSO compositions are described in Table 26. Table 26 also shows the effect of alkyl silicones on the foam volume of seed oil concentrates containing organosilicon superspreaders. As can be seen, the compositions of the present invention deliver lower foam volumes when combined with organosilicon superspreaders in seed oil concentrates.

[0214] Table 26: Effect of alkyl silicones on foam volume of methylated seed oil concentrate containing organosilicon superspreader (foaming test)

[0215]

[0216] Example A. Solubility of silanols in low HLB ethoxylated alcohols and crop oils

[0217] The silanol components of the present invention (wherein R) are shown in Table 27 below. 1 and R 4 Illustrative examples of the solubility of OH in various nonionic surfactants. Blends comprising silanols (from Formula 1 and Table 1) and alcohol ethoxylates (from NIS in Table 2) can be prepared by physically combining the two components in a 50 mL container at a 1:1 ratio and mixing with a magnetic stir bar until homogeneous (approximately 10 minutes at ambient temperature). The initial appearance of the mixture and its phase stability after 24 hours are visually observed.

[0218] Table 27 demonstrates that when the silanol component has a viscosity below 45 cSt (i.e., OSIL-12), NIS with an HLB of 9.0 or lower provides a clear (appearance) and stable (no phase separation) mixture. Furthermore, when blended with NIS components with an HLB of 9.0 or lower, compositions containing silanol components with viscosities between 45 and 85 cSt (OSIL-13) give a clear initial appearance. However, except for blends containing OSIL-13 and NIS-9 which remain stable after 24 hours, all blends show signs of separation after 24 hours. Additionally, blends consisting of OSIL-14 (viscosity between 90 and 120 cSt) and the NIS component all give a cloudy appearance and separate after 24 hours. This indicates that the HLB of the NIS and the viscosity of the silanol component of the present invention play a role in the solubility of the mixture. Furthermore, since the Si-OH content increases as viscosity decreases, it provides polar groups that associate with alkylene oxide groups on the NIS, thus the viscosity of the silanol component can indirectly contribute to solubility.

[0219] Table 27. Solubility of silanols in alkoxylated alcohols (50:50 w / w blend) as a function of silanol viscosity and surfactant HLB (initial appearance and phase stability after 24 hours)

[0220]

[0221] Example B. Solubility in agricultural oils

[0222] Furthermore, the silanol components of this invention exhibit 50% solubility in methylated seed oils when the viscosity is ≤85 cSt (OSIL-12 and OSIL-13), and are insoluble when the viscosity is greater than 90 cSt (OSIL-14). However, none of the silanol components are 50% soluble in alkane mineral oils (MO-1) (Table 28).

[0223] Table 28. Solubility of silanols in crop oils

[0224]

[0225] a.MO-1: Orchex 796; Alkane mineral oil, Calumet

[0226] b.MS-1: CA 3040; methylated soybean oil, Chemical Associates

[0227] Example C. Spreading properties of silanol / surfactant blends

[0228] The spreading performance of the silanol component of this invention in a 1:1 mixture with various NIS components was evaluated as follows: 10 μL of a 0.25% aqueous dispersion was applied as a droplet onto a polystyrene Petri dish (low-energy surface), and the spreading diameter was measured after 1 minute. Table 29 below demonstrates that adding the silanol component of this invention to the NIS component (1:1) increased the spreading by 14% to 28%. Although the total NIS delivered in the 0.25% dispersion was only 0.125%, the improved spreading indicates that the silanol component of this invention promotes the spreading of aqueous dispersions containing NIS.

[0229] Table 29. Spreading of silanol / surfactant blend (50:50 w / w) on polystyrene surface. 10 μL droplet, 1 minute, T = 23 °C, RH = 38%, 0.25% mixture.

[0230] standalone NIS 7.0 OSIL-12 / TMN-3 8.0 OSIL-12 / 15-S-3 8.0 OSIL-12 / 15-S-5 9.0 OSIL-12 / ID-30 8.0 OSIL-12 / XP-30 8.0 S12 / XL-50 8.0 OSIL-13 / XP-30 8.0

[0231] Example D. Effect of oil formulation on the performance of topramizone on barnyard grass

[0232] The effect of adjuvants on the performance of benzoxazine 30% OD formulation (herbicide) was determined on barnyard grass (Echinachloa crus-galli). Barnyard grass (BYDG) was grown in an environmental chamber at 20–25 °C. Plants were treated with a spray solution containing 0.33% of the herbicide alone, or with 0.2% or 0.4% adjuvant (see Table 30). Treatments were applied at a spray volume equivalent of 450 L / ha, and weed control was assessed at 4, 7, 13, and 15 DAT (days after treatment) compared to an untreated check. Weed control was determined by visual observation in grades from 0 to 100%, compared to the untreated check.

[0233] Table 30 demonstrates that the compositions of the present invention can be used as agricultural oils, thereby replacing vegetable oils with organosilicon oils (OSIL-11 in this embodiment). All treatments containing adjuvants improved the performance of the herbicide formulations. However, the strongest response was provided by treatments 6 and 11 containing the adjuvant compositions of the present invention.

[0234] Table 30. Herbicide / adjuvant response in controlling barnyard grass (Echinochloa crus-galli)

[0235]

[0236] a. The herbicide is benzoxazine with an OD of 30% applied at 0.033%.

[0237] b. 90 / 10 or 50 / 50 indicates the w / w ratio of each component.

[0238] c.OSS-1 is a silicone-based oil emulsifier / surfactant package (see Table 3).

[0239] d. NIS-11 is a nonionic surfactant (see Table 2); DAT = number of days after treatment.

[0240] Example E. Spray test against citrus psoriatic mites (Panonychus citri)

[0241] Spraying trials were conducted on citrus trees (oranges) to determine the effect of the composition of the present invention (OSIL-11 / NIS-11) on controlling the citrus phanonychus citri compared to a crop oil formulation—crop oil A (a mixture of mineral oil (90%) and trisiloxane alkoxylates with 10% nonionic surfactant). Furthermore, a comparison was made between (OSIL-11 / NIS-11) + Movento insecticide and Movento alone. Note that the active ingredient in Movento (Bayer Crop Science) is spirotetramat (22.4% SC). Therefore, citrus trees were treated with an aqueous dispersion of 0.5% crop oil A (treatment A) or 1:1 blends of OSIL 11 / NIS-11 at 0.2%, 0.1%, and 0.067% (treatments 1-3). In addition, treatment was performed using the insecticide Movento (0.025%) blended with 0.067% OSIL-1 / NIS-11 (treatment 4) or Movento alone (treatment 5). Treatment 6 was an untreated examination.

[0242] Spray treatments were applied at 2 L / tree in a randomized block design, with each treatment repeated three (3) times. Table 31 below demonstrates that all treatments containing crop oil A or the OSIL-11 / NIS-11 blend gave significant improvements over Movento insecticide alone at 1, 3, and 7 DAT (days after treatment). However, treatments containing the lowest dose of OSIL-11 / NIS-11 (0.067%, treatments 3 and 4) alone or in combination with Movento showed no difference from Movento alone at 14 DAT.

[0243] Furthermore, treatments 1-3 yielded similar results to crop oil A, but at concentrations less than half (i.e., treatment 2 was 1 / 5).

[0244] Table 31. Effects of the compositions of the present invention on the control of *Pseudomonas stomatitis*

[0245]

[0246] *Subscripts sharing the same letter showed no significant difference.

[0247] Example F. Effect of polysiloxane on surface tension

[0248] The effect of polysiloxanes (silanols) on the surface tension of soybean methyl ester (MSO) was evaluated using a Kruss surface tension meter with a platinum blade as a sensor via the Wilhelmy Plate method. Mixtures of MSO and different ratios of the silanol components of this invention (OSIL-12 and OSIL-13) were prepared by combining and mixing the two components in a beaker until homogeneous.

[0249] Table 32 below demonstrates that even at 1% inclusion of OSIL-12 or OSIL-13, the surface tension of MSO is significantly reduced. Surface tension decreases with a corresponding increase in the silanol component. Achieving low surface tension in the oil phase can be important for spray droplet adhesion, as discussed above in paragraph 00124, "The Effect of PDMS Oil on Surface Tension When Blended with Base Oils." Figure 2 In the middle; and paragraph 00124 and Figure 9 As demonstrated in [the document]. As explained above in paragraph 00124, Figure 9 The images show some droplet adhesion tests conducted on poinsettia leaves using the compositions of the present invention. Results are expressed as the average percentage of impacted droplets remaining on the leaf surface. As can be seen, the compositions of the present invention provide a significantly higher droplet deposition rate than the baseline COC formulation.

[0250] Table 32. Effect of polysiloxane silanol components on the surface tension of MSO

[0251]

[0252] Although the invention has been described with reference to specific embodiments, those skilled in the art will understand that various changes can be made and elements thereof can be substituted with equivalents without departing from the scope of the invention. It is intended that the invention be not limited to the specific embodiments disclosed, but rather encompasses all embodiments falling within the scope of the appended claims.

Claims

1. An organosilicon-based agricultural composition comprising: (a) an optional oil component, (b) a surfactant, and (c) a polysiloxane having an average molecular weight of 4,000 g / mol or less and a viscosity of 50 cSt or less at 25°C. When the optional oil component is present, the polysiloxane is soluble or dispersible in the oil component and has the general formula (I): M 1 D x D 1 y M 2 (I) in: M 1 =R 1 R 2 R 3 SiO 1 / 2 M 2 =R 4 R 5 R 6 SiO 1 / 2 D=R 7 R 8 SiO 2 / 2 D 1 =R 9 R 10 SiO 2 / 2 R 1 R 2 R 4 R 5 R 7 and R 8 It is methyl; R 3 and R 6 Independently selected from monovalent alkyl hydrocarbon groups of 1-18 carbon atoms and aryl or alkylaryl hydrocarbon groups of 6-14 carbon atoms; R 9 and R 10 Independently selected from monovalent hydrocarbon groups of 1-18 carbon atoms and aryl or alkylaryl hydrocarbon groups of 6-14 carbon atoms; and The subscript y=0 and x is 5-25.

2. The agricultural composition of claim 1, wherein 5% to 95% of the composition comprises the oil component, 1% to 50% of the composition comprises the surfactant, and 1% to 95% of the composition comprises the polysiloxane component.

3. The agricultural composition of claim 1, wherein, Compared to the same composition in the absence of the polysiloxane, the composition will result in at least a 50% improvement in leaf spreading or a 50% improvement in leaf deposition.

4. The agricultural composition of claim 1, wherein the oil component is mineral oil, alkane crop oil, vegetable oil or esterified seed oil, and the polysiloxane is polydimethylsiloxane or an organo-modified polysiloxane.

5. The agricultural composition of claim 1, wherein the polysiloxane has a viscosity of 20 cSt or lower at 25°C.

6. The agricultural composition of claim 5, wherein the polysiloxane has a molecular weight of 2,000 g / mol or lower.

7. The agricultural composition of claim 1, wherein the optional oil component (a) is present.

8. The agricultural composition of claim 1, wherein... The composition comprises 0% to 95% of the oil component (a); 1% to 50% of the composition comprises the surfactant (b); and 1% to 95% of the composition comprises the polysiloxane component (c).

9. The agricultural composition of claim 1, comprising a C4 to C18 alcohol alkoxylate surfactant.

10. The agricultural composition of claim 1, wherein the composition comprises a solvent selected from d-limonene, triacetin, isopropyl myristate, and esterified seed oil.

11. The agricultural composition of claim 1, wherein it comprises an oil carrier selected from petroleum, mineral oil, alkane mineral oil, vegetable oil, esterified vegetable oil, and esterified seed oil.

12. A method for improving the spreading or adhesive properties of an agricultural composition containing (a) an oil component and (b) a surfactant, comprising adding to the formulation a polysiloxane or an organo-modified polysiloxane of formula (I) having a molecular weight of less than 4,000 g / mol as defined in any one of claims 1 to 11, wherein the amount added effectively results in the combination exhibiting a 10% improvement in adhesion or spreading compared to the same formulation except for the absence of said polysiloxane or organo-modified polysiloxane.

13. The method of claim 12, wherein the polysiloxane or organo-modified polysiloxane has a viscosity of not more than 50 cSt at 25 degrees Celsius.

14. An agricultural chemical composition comprising a bioactive component and the agricultural composition as claimed in claim 1.

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