Agricultural fluid adhesion aid

Abstract

A deposition aid is provided that includes a low molecular weight, low viscosity polysiloxane in combination with a crop oil concentrate or an esterified seed oil concentrate. The combination, including the modified silicone, can improve leaf spreading and / or adhesion. Addition of about 5% to about 20% of the modified silicone can result in a greater than proportional increase in spreading and / or adhesion.

Description

[Technical Field]

[0001] The present invention relates in general to additives that can improve the adhesion properties of specific fluids, and more particularly to formulations and methods for improving the adhesion properties of fluids sprayed onto plant surfaces for agricultural purposes. The compositions according to the present invention are particularly useful for pesticides, more specifically herbicides, insecticides, fungicides, biological agents and growth regulators. [Background technology]

[0002] Many chemical formulations benefit from the inclusion of surfactants. For example, the inclusion of certain surfactants in a chemical formulation can effectively lower its surface tension. This improves the formulation's ability to adhere to the surface to which it is applied, and the ability of the same amount of formulation to spread over a wider area of ​​the surface. Therefore, in agriculture, adding the right surfactant can improve the adhesion of the formulation to the plant to which it is applied, and help the same amount of pesticide formulation cover a wider area of ​​the plant.

[0003] Emulsified petroleum (crop oil concentrate or COC) and emulsified methylated seed oil (MSO) have long been used as agricultural spray adjuvants to enhance the performance of systemic insecticides and other pesticides. Crop oil concentrates and methylated seed oil concentrates generally contain surfactant packages designed to aid in emulsification and adhesion properties. These oils are typically used to facilitate the application and penetration of pesticides to plants, fungi, and insects. In addition to emulsifying oils, surfactants can improve spray adhesion properties by reducing the surface tension of the dispersion or emulsion, thereby enhancing the adhesion of droplets to leaf surfaces. As used herein, the term surfactant includes emulsifiers, dispersants, and spreaders that affect the surface tension of the composition to which they are added.

[0004] However, it is desirable to further improve the spreading, adhesion, and other properties of pesticides containing COC and MSO. Therefore, an adjuvant composition is desirable that can improve the adhesion and spreading properties of agricultural pesticides beyond what can be achieved using prior art. [Overview of the project]

[0005] Generally speaking, the present invention provides spreading and adhesion aids. The aids may include polysiloxanes such as polydimethylsiloxane, oils, and surfactants. Low viscosity polysiloxanes having low molecular weight are preferred, for example, those having a molecular weight of less than about 5,000 g / mol, preferably less than about 4,000 g / mol, and more preferably less than about 2,000 g / mol (as used herein, the molecular weight of silicone oil refers to the number average molecular weight of these oils). Preferred polysiloxanes have a kinematic viscosity 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 (ASTM D445). The agricultural compositions according to the present invention may include bioactive materials in combination with the spreading and adhesion aids described herein, comprising a polysiloxane component, an optional oil component, and a surfactant. The agricultural compositions according to the present invention may include crop oil concentrate (COC) or methylated seed oil concentrate (MSO). These compositions may contain 20% or less, preferably 10% or less, of polysiloxane. In these compositions, the polysiloxane significantly improves the adhesion and / or spreading of droplets of the sprayed agricultural composition to vegetation compared to conventional COC and MSO-containing compositions. The carbon-to-siloxane ratio in these polysiloxanes should be sufficient to make them soluble or dispersible in an oil-based stock.

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

[0007] The compositions according to the present invention can increase the spreading or adhesion properties of agricultural formulations compared to the same formulations that do not contain polysiloxane or organically modified polysiloxane.

[0008] The oils of the present invention may be petroleum, paraffinic oils, mineral oils, vegetable oils and / or esterified vegetable oils (e.g., methylated seed oil, methylated soybean oil, methylated rapeseed oil, methylated cottonseed oil, methylated palm oil, methylated corn oil) containing methyl, ethyl, propyl and isopropyl esters of naturally derived or synthetically prepared C8 to C18 fatty acids (e.g., isopropyl myristate, methyl oleate, ethyl oleate, and methyl palmitate). The surfactants, dispersants and / or spreaders of the adhesion aids of the present invention may include at least one surfactant derived from the ethoxylation or alkoxylation of primary or secondary alcohols. This includes surfactants selected from polyoxyethylene, polyoxypropylene, polyoxybutylene, and mixed polyalkylene oxide alkoxylates of fatty alcohols. Surfactants may also include trisiloxane alkoxylates, alkyne diol alkoxylates, and block or random polyoxyethylene / polyoxypropylene copolymers.

[0009] Optionally, the composition may also include a solvent selected from d-limonene, triacetin, isopropyl myristate, esterified seed oil, or other suitable solvents. [Brief explanation of the drawing]

[0010] For a more complete understanding of the present invention, please refer to the following description in relation to the accompanying drawings.

[0011] [Figure 1] Figure 1 is a graph showing an example of the equilibrium surface tension of a mineral oil / silicone oil mixture.

[0012] [Figure 2] Figure 2 is a graph showing an example of the equilibrium surface tension of an OSIL-1 mixture in MO-1.

[0013] [Figure 3] Figure 3 is a graph showing an example of the equilibrium surface tension of a soybean methyl / silicone oil mixture.

[0014] [Figure 4] Figure 4 is a graph showing an example of the effect of PDMS addition on the dynamic surface tension (DST) of COC.

[0015] [Figure 5] Figure 5 is a graph showing the diffusion diameter of 0.5% dispersions in two examples.

[0016] [Figure 6] Figure 6 is a graph showing the emulsion stability in two examples.

[0017] [Figure 7] Figure 7 is a graph showing an example of the effect of low MWPDMS on the foam volume of an MSO adjuvant containing an organosilicone superspreader.

[0018] [Figure 8] Figure 8 is a graph showing an example of the equilibrium surface tension of alkyl silicone / MO-1 formulations.

[0019] [Figure 9] Figure 9 is a graph showing examples of droplet adhesion to poinsettia leaves among the example formulations.

[0020] [Figure 10] Figure 10 is a graph showing an example of the effect of PDM on the dynamic surface tension of COC. [Modes for carrying out the invention]

[0021] In this specification and in the claims, the following terms and expressions should be understood as they are shown.

[0022] The singular forms "a," "an," and "the" include the plural forms, and references to specific numbers include at least that specific value unless the context explicitly indicates otherwise.

[0023] Unless otherwise indicated in the examples or other instructions, all figures relating to quantities of materials, reaction conditions, durations, quantified properties of materials, etc., described in the specification and claims should be understood in all cases as being modified by the term “approximately”.

[0024] All methods described herein may be performed in any suitable order unless otherwise indicated herein or unless the context clearly contradicts it. Any use of any examples or illustrative words (e.g., "etc.") provided herein is intended solely to better illustrate the invention and, unless otherwise claimed, does not limit the scope of the invention.

[0025] The wording in the specification should not be interpreted as indicating that elements not claimed are essential for carrying out the invention.

[0026] The terms “comprising,” “including,” “containing,” “characterized by,” and their grammatical equivalents are understood to be inclusive or unrestricted terms that do not exclude additional unlisted elements or method steps, but include the more restrictive terms “consisting of” and “consisting essentially of.”

[0027] Any numerical range described herein is understood to include all subranges within that range, and any combination of various endpoints of such ranges or subranges.

[0028] Where used herein, integer values ​​of stoichiometric subscripts refer to molecular species, and non-integer values ​​of stoichiometric subscripts refer to mixtures of molecular species on a molecular weight average basis, a number average basis, or a mole fraction basis.

[0029] Furthermore, any compound, material, or substance disclosed explicitly or implicitly 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 will be understood to include individual representatives of the group and all combinations thereof.

[0030] As used herein, the terms “pesticides” or “agricultural chemicals” should be understood to refer to all physiologically active compounds, their extracts, fractions, and by-products, including biological materials, microorganisms, and other organisms, suitable for agricultural uses such as pesticides, herbicides, fungicides, insecticides, nematicides, larval repellents, acaricides, ovicidal agents, plant growth regulators, and seed treatment agents. “Agricultural composition” refers to a composition applied to plants, weeds, landscapes, grasses, trees, pastures, or other agricultural uses. Agricultural compositions may be provided in concentrated or diluted forms. Agricultural compositions may or may not contain pesticides (agricultural chemicals).

[0031] As used herein, the term “adjuvant” includes any selected component that enhances any functionally useful properties already possessed to some extent by any composition, material or substance, which imparts functionally useful properties to a composition, such as dispersion, wetting, spreading, etc., and / or enhances the effectiveness of the pesticide or active substance to which it is added.

[0032] The term "biological activity" refers to agricultural chemicals or materials that have a positive or negative effect on living organisms (plants, animals, bacteria, or protozoa), including but not limited to herbicides, fungicides, insecticides, acaricides, mollusk repellents, and other pesticides; plant or animal nutrients; defoliants; and plant or animal growth regulators.

[0033] The terms "hydrocarbon group" or "hydrocarbon radical" mean any hydrocarbon from which one or more hydrogen atoms have been removed, including alkyl, alkenyl, alkynyl, cyclic alkyl, cyclic alkenyl, cyclic alkynyl, aryl, aralkyl, and allenyl groups, and include hydrocarbon groups containing at least one heteroatom.

[0034] The term "alkyl" means any monovalent saturated linear, branched, or cyclic hydrocarbon group; the term "alkenyl" means any monovalent linear, branched, or cyclic hydrocarbon group containing one or more carbon-carbon double bonds, where the bond site of the group may be either a carbon-carbon double bond or any other location therein; and the term "alkynyl" means any monovalent linear, branched, or cyclic hydrocarbon group containing one or more carbon-carbon triple bonds, and optionally one or more carbon-carbon double bonds, where the bond site of the group is a carbon-carbon triple bond, a carbon-carbon double bond, or any other location therein. Examples of alkyl groups include methyl, ethyl, propyl, and isobutyl. Examples of alkenyl groups include vinyl, propenyl, allyl, methallyl, ethylidenylnorbornane, ethylidenenorbornyl, ethylidenylnorbornene, and ethylidenenorbornenyl. Examples of alkynyl groups include acetylenyl, propargyl, and methylacetylenyl.

[0035] As used herein, the term “superspreader” refers to an adjuvant surfactant having “superspreading” or “superspreading” properties. Superspreading / superspreading is the ability of a droplet of a superspreader surfactant solution to spread to a diameter larger than that of a distilled water droplet on a hydrophobic surface, and to a diameter larger than that of a solution of a non-superspreading surfactant on a hydrophobic surface.

[0036] The term "tank mix" refers to a combination of at least one pesticide and a spray medium such as water or oil at the time of use (application). The term "canned" refers to a formulation or concentrate containing at least one pesticide component. A "canned" formulation can be diluted to its application concentration, typically in a tank mix, or used without dilution at the time of use.

[0037] Crop oil concentrates (COCs) and methylated seed oils (MSOs) are classes of agricultural adjuvants based on petroleum and seed oil base stocks, respectively. COCs and MSOs typically contain a surfactant package, which accounts for 5 to 40% of the product's composition. COCs and MSOs are sold in concentrate form and are diluted with water before the end user sprays them. The surfactant package works to disperse or emulsify the oil phase in water, helping the sprayed emulsion or dispersion adhere and spread to the target surface. COCs and MSOs facilitate the penetration of systemic insecticides and other pesticides into the plants, fungi, and insects to which they are applied.

[0038] The addition of low molecular weight polysiloxanes (e.g., silicone oils) according to the present invention has been found to further reduce the surface tension of petroleum and seed oil base stocks used to produce COC and MSO. The benefits borne by COC and MSO (e.g., improved droplet adhesion, spreading (diffusion), and / or emulsion stability), and the resulting agricultural compositions containing these COC and MSO with the addition of polysiloxanes, can surprisingly exceed what would be expected from agricultural formulations alone, i.e., those without polysiloxanes.

[0039] Surprisingly, spray droplets of formulations containing polysiloxane were found to exhibit improved adhesion to plant (e.g., leaf) surfaces, even without a corresponding decrease in the dynamic surface tension of each formulation. Furthermore, the high spreading ability of the emulsions described herein, along with improved emulsion stability, was quite remarkable.

[0040] The spreading and adhesion aids according to the present invention can be formed by combining (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%, more preferably 5% to 15%, of a low molecular weight polysiloxane. The preferred polysiloxane has a molecular weight of about 5000 g / mol or less, preferably about 4000 g / mol or less, and more preferably 2000 g / mol or less. The polysiloxane should have a viscosity of less than about 50 cSt, preferably less than about 20 cSt, at 25°C. The polysiloxane, if present, must be soluble or dispersible in the oil component. The preferred agricultural composition according to the present invention can spread or adhere to the leaf surface at least 10% better, preferably 20% better, and more preferably at least 50% better than the same formulation without polysiloxane.

[0041] The oil components are mineral oil, paraffinic crop oil, vegetable oil, or esterified seed oil, and the polysiloxane is polydimethylsiloxane or organically modified polysiloxane. Preferred oil components include mineral oil, paraffinic oil, seed oil, soybean oil, corn oil, canola 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 caprylate, methyl laurate, methyl myristate, methyl palmitate, methyl oleate, and methyl stearate.

[0042] The compositions of the present invention can optionally be combined with one or more other adjuvant components known to be incorporated into aqueous agricultural sprays. Among the many types of optional adjuvants are surfactants of both organosilicon and non-organosilicon types, defoaming additives, and additives such as stickers, thickeners, and dyes.

[0043] Acceptable emulsifiers and surfactants include nonionic, anionic, cationic, and zwitterionic surfactants. Non-limiting examples of suitable nonionic surfactants include alcohol ethoxylates, alkyl polyglycosides, alkylene oxide copolymers with ethylene oxide and propylene oxide, butylene oxide, alkyl polyglycerols, and acetylenediol alkoxylates. Non-limiting examples of suitable anionic surfactants include alkyl sulfates (e.g., sodium lauryl sulfate, sodium lauryl ethoxysulfate, and 2-ethylhexyl sulfate), alkylbenzene sulfonates (e.g., sodium dodecylbenzenesulfonate), and C8-C 18 This includes phosphates, monoesters, diesters and triesters made from alkylene oxides, and alkyl sarcosinates such as sodium lauryl sarcosinate. A non-limiting example of a suitable cationic surfactant is C8-C 18 This includes alkoxylated aliphatic amines and imidazolines. A non-limiting example of a suitable zwitterionic surfactant is C8-C 18 Examples of amidopropyl betaines include, but are not limited to, lauryl betaine, myristyl betaine, lauramidopropyl betaine, soyamidopropyl betaine, laurylamide betaine, oleyl betaine, and lecithin. Agricultural compositions may preferably contain fatty alcohol alkoxylate surfactants, such as polyalkylene oxide alkoxylates of polyoxyethylene, polyoxypropylene, polyoxybutylene, and fatty alcohols. Surfactants having short-chain hydrophobic substances that do not interfere with superspreading are described in full in U.S. Patent No. 4,111,110, which is incorporated herein by reference, and are also useful.

[0044] Specific examples of acceptable alcohols include isodecyl alcohol ethoxylates (Alkosynt ID 30, Oxiteno, Rhodasurf DA 530, Solvay, Ethal DA-4, Ethox), isotridecyl alcohol ethoxylates (Genapol X 050, Genapol X 060, Genapol X 080, Clariant, Alkosint IT 60, Alkosint IT 120, Oxiteno), tridecyl alcohol ethoxylates (Lutensol TDA 6, Lutensol TDA 9, Lutensol TDA 10, BASF), and Guerbet alcohol alkoxylates (Lutenxol XL 50, Lutensol XP 50, Lutensol XL 60, Lutensol XP 60, Lutensol XL 80, Lutensol XP 80). These include BASF, secondary alcohol ethoxylates (Tergitol 15-S-3, Tergitol 15-S-5, Tergitol 15-S-7, Tergitol 15-S-9, Dow Chemical), polyethylene glycol trimethyl nonyl ethers (Tergitol TMN3, Tergitol TMN6, Tergitol TMN10, Dow Chemical), alkyl acetylenediols (Surfynols, Air Products), pyrilodone-based surfactants (e.g., Surfadone LP 100, Ashland), 2-ethylhexyl sulfate, ethylenediamine alkoxylates (Tetronics, BASF), ethylene oxide / propylene oxide copolymers (Pluronics, BASF), gemini-type surfactants (Rhodia / Solvay), and diphenyl ether gemini-type surfactants (DOWFAX, Dow Chemical).

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

[0046] Preferred super spreaders include siloxane polyalkylene oxide copolymers. Non-limiting examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, and mixed polyalkylene oxide alkoxylates of trisiloxane, tetrasiloxane, and pentasiloxane.

[0047] The polysiloxane according to the present invention can have the following general formula (I), (II), or (III). The viscosity of the polysiloxane must be low and can be up to about 50 cSt. The most preferred polysiloxane is a low-viscosity polysiloxane having a viscosity of, for example, up to 20 cSt and / or an average MW of up to 2000 g / mol. Among the three formulas, the most preferred is general formula (I), especially having a viscosity of about 20 cSt or less, M 1 D x D 1 y M 2 (I) where 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 [[ID=�4]]SiO 2 / 2 R 1 and R 4 are independently selected from hydroxyl (OH), R 8 , or OR 8 ; R 2 、R 3 、R 5 and R 6These are independently selected from monovalent alkyl hydrocarbon radicals with 1 to 18 carbon atoms and aryl or alkaryl hydrocarbon radicals with 6 to 14 carbon atoms; R 7 hydroxyl (OH), OR 8 -OSi(R) 8 )3, or -(OSiR 8 R 8 ) f OSi(R 8 ) Selected from 2 oz, where Z is H or R 8 And the subscript f is from 0 to 8; R 8 It is a monovalent hydrocarbon radical consisting of 1 to 4 carbon atoms; R 9 and R 10 These are independently selected from monovalent hydrocarbon radicals with 1 to 18 carbon atoms and aryl or alkaryl hydrocarbon radicals with 6 to 14 carbon atoms; and The subscripts x and y are independently between 0 and 50, provided that x + y is approximately between 1 and 50.

[0048] A preferred structure of formula (I) is one in which Y=0, all R groups are methyl, and the viscosity is 50 cSt or less at 25°C, preferably 20 cSt or less at 25°C. Other preferred examples of formula I include those in which x+y is from 5 to 50; or those in which y=0 and x is from 3 to 50; or R 1 , R 4 and R 7 However, one independently selected from hydroxyl (OH) or methyl; or R 2 , R 3 , R 5 , R 6 and R 8 Those in which are methyl; R 1 From R 8 Those where is methyl; or y=0, x=3 to 50, and R 1 From R 8 Those where is methyl; or where y=0, x is approximately 5 to 25, and R 1from R 8 where R is methyl; or R 10 is a monovalent alkyl hydrocarbon radical of 1 to 18 carbons, or an aryl or alkaryl hydrocarbon radical of 6 to 14 carbon atoms, and R 1 from R 9 is methyl; or R 1 and R 4 are monovalent alkyl hydrocarbon radicals of 1 to 18 carbons, or aryl or alkaryl hydrocarbon groups of 6 to 14 carbon atoms, R 2 , R 3 and R 5 from R 10 is methyl; or R 10 is a monovalent alkyl hydrocarbon radical of 1 to 18 carbons, or an aryl or alkaryl hydrocarbon radical of 6 to 14 carbon atoms; or R 1 [[ID=2...]]from R 9 is methyl, are included. In a preferred example of formula (I), R 1 is OH, R 4 and R 7 are methyl; R 1 and R 4 are OH, R 7 is methyl; R 1 , R 4 and R 7 are each OH; or R 1 , R 4 and R 7 are each methyl.

[0049] The polysiloxane according to the present invention can also be defined by structure (II), TS 1 R 11 TS 2 (II) where [[ID=6...]]TS 1 and TS 2 are, independently, R 12 R 13 R 14 Si - O - Si a (R A)-O-SiR 15 R 16 R 17 wherein where Si a is a monovalent radical, and R 11 is bonded to Si a ; R 11 is selected from divalent hydrocarbon radicals having 4 to 18 carbon atoms, R A , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are independently selected from monovalent hydrocarbon radicals having 1 to 4 carbon atoms.

[0050] Preferred examples of formula II include those wherein R 11 is a divalent hydrocarbon radical containing 4 to 18 carbon atoms, and examples wherein R A and R 12 ]>to R 17 are methyl (-CH3) groups.

[0051] The polysiloxane according to the present invention can also be defined by structure (III), R 19 -[Si(CH3)2O 1 / 2 -(D 2 )z-O 1 / 2 Si(CH3)2-R 18 w -R 20 (III)<00OO343>where R 19 =H-, CH3-, or HR 18 - R 20 =H-, or -Si(CH3)2O 1 / 2 -(D 2 )z-O 1 / 2 Si(CH3)2H, or -Si(CH3)2O 1 / 2 -(D 2 ) z -O 1 / 2 Si(CH3)2CH3,​​​18 These are selected from 4 to 18 carbon-divalent hydrocarbon radicals. D 2 =R 21 R 22 SiO 2 / 2 , R 21 and R 22 These are independently selected from monovalent hydrocarbon radicals with 1 to 4 carbon atoms. z=2 to 20, and w=1 to 20 (w=1 or 2 is preferred).

[0052] A preferred example of Equation III is when w = 1 - 10, and R 21 and R 22 Examples include those where the group is a methyl (-CH3) group.

[0053] The agricultural composition may preferably contain a solvent selected from d-limonene, triacetin, isopropyl myristate, and esterified seed oils.

[0054] The present invention relates to improving the spreading and / or adhesion properties of an agricultural composition comprising mineral oil, paraffinic crop oil, esterified seed oil, or vegetable oil, including COC and MSO, and comprises adding an effective amount of a selected polysiloxane or organo-modified polysiloxane having an average molecular weight of less than about 5,000 g / mol, preferably less than about 4,000 g / mol, and more preferably less than about 2,000 g / mol, to the agricultural composition. The preferred polysiloxane has a kinematic viscosity 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 (ASTM D445). The preferred polysiloxane has general formula I, II, or III as defined above. This method may be effective in producing a composition that exhibits improved adhesion and / or spreading compared to the same composition in the absence of the polysiloxane or organo-modified polysiloxane. Improved spreading and / or bonding is possible, with increases of 10%, 20%, and even more than 50%.

[0055] The adhesion aids according to the present invention can be provided as agricultural compositions, either mixed in-situ from individual components or as combinations thereof. For example, they may be provided as isolated polysiloxanes, or in combination with other materials such as mineral oil, vegetable oil, esterified seed oil, surfactants, and pesticides to form a tank mix that can then be applied as needed.

[0056] The optimal amount of polysiloxane spreading and adhesion aid for a particular spray composition and spraying operation can be easily determined using routine experimental testing procedures known in the art. For many spray compositions, amounts of the composition of the present invention ranging from 0.01 to 5, preferably 0.05 to 1 weight percent, can be incorporated therein, generally yielding good spreading and adhesion results. Accordingly, the present invention comprises MSO and / or COC, preferably containing the polysiloxane described herein at a concentration of 1-20% in MSO or COC. The MSO or COC can be diluted with water by the end user for agricultural purposes to create an emulsion or spray solution. The MSO or COC will typically constitute 0.1 to 2 percent of this end-use emulsion or spray solution.

[0057] In addition to the composition of the present invention, agricultural sprays may contain one or more known and conventional active ingredients or pesticides of agricultural compositions, such as pesticides, fertilizers, and micronutrients.

[0058] A pest control spray contains at least one pesticide. Optionally, the pest control spray may also contain excipients, surfactants, solvents, foam regulators, adhesion aids, biological formulations, micronutrients, fertilizers, etc. The term "pesticide" means any compound used to destroy pests, such as rodenticides, insecticides, acaricides, mite control agents, fungicides, herbicides, etc. Specific examples of pesticides that can be used 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.

[0059] Specific examples of herbicides and plant growth regulator compounds that can be incorporated into spray compositions include, but are not limited to, phenoxyacetic acid, phenoxypropionic acid, phenoxybutyric acid, benzoic acid, triazines and s-triazines, substituted ureas, uracil, bentazon, desmedifam, metazole, fenmedifam, pyridate, amitorol, chromazon, fluridone, norflurazone, dinitroaniline, isopropaline, oryzalin, pendimethalin, prodiamine, trifluralin, glyphosate, sulfonylurea, imidazolinone, cretodym, diclofop-methyl, phenoxapropethyl, fluadifop-p-butyl, haloxyfop-methyl, quizaropop, cethoxydim, diclobenyl, isoxaben, and bipyridilium compounds. The 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.

[0060] Specific examples of bactericidal compositions include, but are not limited to, Aldimorph, Tridemorph, Dodemorph, Dimethomorph; Flusilazole, Azaconazole, Cyproconazole, Epoxyconazole, Fluconazole, Propiconazole, Tebuconazole, etc.; Imazalil, Thiophanate, Benomylcarbendazim, Chlorothiaronil, Dichloran, Trifloxystrobin, Fluoxystrobin, Dimoxystrobin, Azoxystrobin, Flucalanil, Prochloraz, Flusulfamide, Famoxadone, Captan, Maneb, Mancozeb, Dodicin, Dozin, Metalaxyl, etc.

[0061] Specific examples of insecticides, larvicides, acaricides, and ovicide compounds that can be incorporated into aqueous spray compositions include, but are not limited to, Bacillus thuringiensis (or Bt), spinosad, abamectin, doramectin, lepimectin, pyrethrin, carbaryl, primicarb, aldicarb, methomyl, amitraz, boric acid, chlordimeform, novalon, bistrifluorone, triflumulon, diflubenzuron, imidacloprid, diazinon, acephate, endosulfan, kerebane, dimethoate, azinphosethyl, azinphosmethyl, izoxathion, chlorpyrifos, clofentezine, lambdasihalotrin, permethrin, bifenthrin, and cypermethrin.

[0062] Fertilizers and micronutrients include, but are not limited to, zinc sulfate, ferrous sulfate, ammonium sulfate, urea, ammonium urea 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, iron sulfate, calcium sulfate, sodium molybdate, and calcium chloride.

[0063] Buffers, preservatives, and other standard agricultural excipients known in the art may also be included in the spray composition.

[0064] Agricultural spray compositions can be prepared either as tank mixes or "canned" formulations by combining one or more of the above-mentioned spray components with the compositions of the present invention in any combination and / or order in a manner known in the art, such as by mixing them in water.

[0065] The present invention also includes agricultural compositions of the present invention that are applied to and used for treating crops, landscape and ornamental plants, trees and pastures. They can also be used in forestry applications and golf courses, to name a few. Crops include, for example, vegetable crops such as broccoli, cabbage, kale, spinach, onions and peppers; legumes such as beans, lentils, peas and soybeans; grains such as wheat, corn, barley, rye, rice and oats; flower crops such as roses, tulips, daisies, daffodils, gerberas, sunflowers, orchids, jasmine and carnations; and root vegetables such as potatoes, beets, turnips, parsnips, radishes and carrots. Crops may also include fruits, such as citrus fruits, apples, tomatoes, grapes, watermelons, pears, raspberries, blueberries, plums, peaches, bananas, pineapples, strawberries, plantains, kiwis, and mangoes; and nut trees, such as almonds, chestnuts, hazelnuts, hickory nuts, macadamia nuts, pecans, pine nuts, pistachios, and walnuts. The agricultural composition can also be applied to and used on pastures such as clover, alfalfa, and grasses, as well as on crops such as pumpkins, tubers, zucchini, and coconut, palm, and cocoa trees.

[0066] The agricultural composition of the present invention can be applied and used in combination with herbicides to control weeds such as: Anoda cristata, Momordica charantia, Hordeum vulgare, Echinochloa crus-galli, Bassia hyssopifolia, Cardamine spp., Poa bulbosa, Brom (Bromus tectorum), Bromus japonicas, Ranunculus spp., California foxtail (Alopecurus carolinianus), Geranium carolinianum, Ricinus communis, Chamomile (Anthemis cotula), and Cheet (Bromus (secalinus), chervil (Anthriscus cerefolium), chickweed (Cerastium vulgatum), cocklebur (Xanthium strumarium), coreopsis tinctoria, volunteer corn (Zea mays), crabgrass (Digitaria spp.), dwarf dandelion (Krigia virginica), eastern manna grass (Glyceria spp.), eclipta prostrata, phaechlea dandelion (Pyrrhopappus carolinianus), phaechlea flax (Camelina microcarpa), fiddleneck (Amsinckia spp.), lacewing plant (Thlaspi arvense), fleabane (Erigeron annuus), and wild daisy (Conyza) bonariensis), Erigeronstrigosus, Richardia scabra, Foxtail (Setaria spp.)), goat's wheat (Aegilops cylindrical), goosegrass (Eleusine indica), ragwort (Senecio vulgaris), henbit (Lamium amplexicaule), dwarf coneflower (Conyza canadensis), straw grass (Rottboellia cochinchinensis), halepense (Sorghum halepense), jungle rice (Echinochloacolona), knotweed (Polygonum spp.), broom cypress (Kochia scoparia), white lamb (Chenopodium album), medusa head (Taeniatherum caput-medusae), morning glory (Ipomoea spp.)), mustard blue (Chorispora tenella), mustard greens (Sisymbrium altissimum), mustard wild (Sinapisarvensis), wild oats (Avena fatua), giant sorghum (Panicum dichotomiflorum), blue amaranth (Amaranthus retroflexus), narrow blue amaranth (Amaranthus hybridus), spiny lettuce (Lactuca serriola), terrestrial lily (Tribulus terrestris), purslane (Portulaca oleracea), ragweed (Ambrosia artemisiifolia), giant ragweed (Ambrosia trifida), narrow lettuce (Sisymbrium irio), sea blite (Salsola tragus), rye (Secale cereal), Italian ryegrass (Lolium perenne), chestnut burr (Cenchrus) Spinifex), Sesbania hemp (Sesbania herbacea), Shatter cane (Sorghum bicolor), Shepherd's purse (Capsella bursa-pastoris), Senna obtusifolia, Signal grass broadleaf (Urochloa platyphylla), Smartweed (Pennsylvania Polygonum pensylvanicum), Sonchus oleraceus (Sonchus oleraceus), Bidens bipinnata, Veronica arvensis, Insect grass (Veronica peregrina), Sprout top (Leptochloa spp.), Spaghetti annual (Chamaesyce spp.)), spurred prostrata (Chamaesyce humistrata), spurred spotted grass (Chamaesycemaculate), spurred umbrella grass (Holosteum umbellatum), stink grass (Eragrostis cilianensis), sunflower (Helianthusannuus), tans mustard pinnata (Descurainia pinnata), teaweed / prickly fern (Sida spinosa), Texas panicum (Panicum spp.), vine (Abutilon theophrasti), bean lacewing grass (Lepidium virginicum), wheat (Triticum aestivum), witch grass (Panicum capillare), woolly cup grass (Eriochloavillosa), spring-blooming mustard (Barbarea vulgaris).

[0067] Additional plants to which the agricultural compositions according to the present invention apply include perennial plants such as alfalfa, anise / fennel, bluegrass, kentucky cypress, clover, dandelion, poison ivy, milkweed, hemlock, thistle, and grass. Trees include alder, ash, beech, aspen, cherry, elderberry, elm, hickory, honeysuckle, kudzu, maple, oak, pine, spruce, lacquer tree, fern, creeper, and poplar. [Examples]

[0068] The attributes of aspects and preferred embodiments of the present invention will be described with reference to the following examples, which are presented for illustrative purposes only and should not be construed as limiting. Furthermore, unless otherwise indicated, R is used as in these embodiments. 1 From R 10 Each of these can be considered a methyl group. Product Description Table 1-4 describes the products used in the following examples. [Table 1]

[0069] [Table 2]

[0070] [Table 3]

[0071] [Table 4]

[0072] Spread judgment The spreading ability of various compositions and formulations was evaluated by applying a drop (10 microliters) of the emulsion (or other material) to a clean, flat polystyrene dish. The diameter of the resulting droplet was measured after 30 seconds. Each solution was tested 2 to 4 times, and the average diameter was calculated. Alternatively, the spreading ability was also evaluated by applying a drop (10 microliters) of the sample to be evaluated to the surface of a leaf. Unless otherwise specified, the area of ​​the resulting droplet was measured after 3 minutes. Each sample was tested 2 to 4 times, and the average diffusion area was calculated.

[0073] Effect of PDMS oil on surface tension when blended with oil-based stocks Low surface tension correlates with improved droplet adhesion and spreading, making it beneficial for agricultural pesticide applications. The effect of polydimethylsiloxane (PDMS) oil on surface tension when compounded with various oil-based stocks was evaluated, and the results are shown in Figures 1, 2, and 3. These results are on a logarithmic scale, and straight lines actually indicate nonlinear results. Thus, the results demonstrate that the addition of small amounts of silicone oil results in a significant reduction in the equilibrium surface tension imbalance.

[0074] As shown in Figure 1, the surface tension of oil MO-1 decreased from 30 to 26 mN / m (a decrease of more than 10%) with the addition of only 1% of OSIL-2, a 10 cSt polydimethylsiloxane (PDMS) oil identified as element 1410A, which has an equilibrium surface tension slightly below 20. With the addition of only 10% of OSIL-2 silicone oil, the surface tension of the mixture decreased to 23 mN / m, more than half the difference in surface tension (30 and 20). All percentages used herein are calculated on a weight basis. Similarly, as shown in Figure 2, the addition of 10% (by weight) of OSIL-1, a 5 cSt PDMS oil, to MO-1 decreased the equilibrium surface tension of the product from 29.1 mN / m to 24.3 mN / m. When 10% by weight of OSIL-3, a 20 cSt PDMS oil, was added to MO-3, the surface tension of the product decreased from 30 mN / m to 22.8 mN / m.

[0075] Figure 3 shows that adding the low molecular weight silicone oil OSIL-2 to esterified seed oil MS-1 significantly reduces the surface tension with a relatively small amount of silicone oil. The addition of 1% OSIL-1 reduced the surface tension of soybean methyl from approximately 30 mN / m to approximately 26 N / m, and 10% reduced it to approximately 23 mN / m.

[0076] The effects of the low molecular weight, low viscosity PDMS oil according to the present invention on leaf surface adhesion and dynamic surface tension were evaluated by incorporating crop oil concentrates (COCs). The surfactant mixture SURF-1, defined in Table 5, was used in each formulation. The commercially available nonionic surfactant, Tergitol® 15-S-5, was added to two samples to increase the HLB value of the surfactant package. Tergitol® 15-S-3 and Tergitol® 15-S-5 are ethoxylates of a mixture of C11-C15 secondary alcohols at 3 and 5 moles, respectively. Tergitol® TMN-3 is an ethoxylate of 3 moles of trimethylnonyl alcohol. The results are summarized in Table 6.

[0077] [Table 5]

[0078] The data in Table 6 show that the addition of PDMS oil (OSIL-2) according to the present invention to crop oil concentrate (COC) formulations surprisingly resulted in a significant, sometimes very large, increase in spreading on both poinsettia and philodendron leaves. This was surprising because the spreading of COC or MSO dispersions is usually driven by the surface tension of the aqueous phase of the sprayed droplets, rather than the equilibrium surface tension of the dispersed oil phase. As shown in Figure 4, the dynamic surface tension curves (DST) of the sprayed aqueous solutions from SIL-1 to SIL-5 were all essentially the same and all significantly lower than the DST curve of the COC-1 dispersion. Therefore, it was expected that SIL-1 to SIL-5 would give similar diffusion areas to plant leaves, and that all five would spread significantly more than the COC-1 dispersion. As expected, the COC-1 dispersion was the least effective spreader. However, surprisingly, all formulations containing polysiloxane OSIL-2 spread significantly more than the corresponding formulations without silicone oil.

[0079] The benchmark crop oil concentrate, SIL-3, was prepared by compounding an 11.25% SURF-1 surfactant package with MO-1. In SIL-1, 10% OSIL-2 was added, replacing an equal amount of MO-1. As shown in Table 6, SIL-1 containing OSIL-2 nearly doubled the adhesion of the SIL-3 benchmark to poinsettias and increased adhesion to philodendron leaves by 12.5 percent.

[0080] A second benchmark COC formulation, SIL-5, was formulated. SIL-5 contains the SURF-1 surfactant package and a small amount of the surfactant NIS-2 to enhance the HLB (hydrophilic-to-lipophilic balance) of the entire surfactant package. Polysiloxane OSIL-2 was added to this formulation to create the COC formulation SIL-2. SIL-4 is a similar formulation containing SURF-1, NIS-2, and OSIL-2. From Table 6, it can be seen that the polysiloxane-containing formulations SIL-2 and SIL-4 show 7.6 to 8 times greater spreading on poinsettia leaves and 1.7 to 3.6 times greater spreading on philodendron leaves than the benchmark SIL-5, which does not contain polysiloxane oil.

[0081] [Table 6] In summary, all experimental COC formulations SIL-1 through SIL-5 showed significantly enhanced diffusion compared to a 1% solution of COC-1, a commercially available crop oil concentrate. Furthermore, while the dynamic surface tension curves for SIL-1 through SIL-5 were essentially identical, formulations containing polysiloxane showed unexpectedly significant improvements in diffusion properties. This indicates that the improved adhesion is not simply a result of reduced surface tension, but rather an unexpected consequence of the silicone oil of the present invention, particularly when combined with the surfactant NIS-2. Thus, the addition of OSIL-2 did not significantly affect the DST (dynamic surface tension) of these experimental COC 1% solutions, but unexpectedly increased adhesion (see Table 6).

[0082] Tables 7 and 8 below show the effects of different PDMS oils according to the present invention on leaf surface spreading in experimental COC formulations combined with different surfactants. As shown in these tables, when tested on the leaves of philodendron, bamboo, broccoli, and poinsettia, the addition of silicone oils according to the present invention resulted in a significant improvement in spreading with all surfactants. COC formulations SIL-21 and SIL-22 demonstrate that the improvement in spreading seen with the addition of OSIL-2 also occurs when the COC is formulated with a different oil base stock, in this case Parol® 80 (MO-2) instead of Orchex® 796 (MO-1).

[0083] When silicone oils were combined with surfactants NIS-2 (SIL-7 and SIL-8), NIS-1 (SIL-16), NIS-4 (SIL-10), and NIS-6 (SIL-18), the greatest increase in leaf surface adhesion was observed. As can be seen when comparing SIL-7 and SIL-8, the 50cStPDMS oil (OSIL-4, element 14 PDMS 50) used in formulation SIL-8 appeared to be at least as effective as OSIL-2, if not superior. However, higher viscosity silicone oils are more difficult to solubilize and / or emulsify in crop oil concentrate formulations.

[0084] [Table 7] [Table 8]

[0085] The data in Table 9 shows that SIL-23, a COC formulation containing OSIL-1, increased the diffusion onto the leaf surfaces of bamboo, philodendron, and poinsettia by approximately three times compared to SIL-6, a benchmark that does not contain silicone oil.

[0086] [Table 9]

[0087] Table 10 below summarizes the results of spreading examples conducted using 0.5% solutions of SIL-6 and SIL-7 (MO-1 from Calumet Specialty Chemicals, a paraffinic hydrocarbon oil, COC made with Orchex 796) and SIL-24 and SIL-25 (MS-1 from Chemical Associates, A Division of Univar USA, Inc., a soybean methyl oil, MSO made with CA3050). For both base stocks, the addition of silicone oil (OSIL-2) according to the present invention significantly improved the leaf surface spreading characteristics of the product.

[0088] [Table 10]

[0089] Table 11 summarizes the results of spreading examples performed with 1.0% solutions of formulations containing OSIL-3, 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 of these products are based on MO-1. Formulation SIL-27 was used as a benchmark for SIL-28. Both of these products are based on MO-3. In both oil-based stocks, the addition of the silicone oil according to the present invention significantly improved the leaf surface spreading properties of the product compared to the same mineral oil containing only the nonionic surfactant NIS-2.

[0090] [Table 11]

[0091] Adhesion tests conducted using 0.5% aqueous solutions of Sil-6 and SIL-7 demonstrated a significant enhancement of adhesion of the formulations according to the present invention to leaves. Solution droplets were produced using a syringe pump and a Nisco Encapsulation Unit (Var J1) J1 with a nozzle having an inner diameter of 0.41 mm. The data in Table 12 show that when PDMS oil OSIL-2 was added to the COC formulation (SIL-6), the number of droplets adhering to the grass leaf surface increased approximately threefold, from 16.3% (SIL-6) to 45.9% (SIL-7). As seen in Figure 10, both of these COC formulations exhibited essentially the same dynamic surface tension. Therefore, the enhanced adhesion observed here was unexpected, given the understanding that droplet adhesion increases with decreasing dynamic surface tension (DST).

[0092] [Table 12]

[0093] Similar droplet adhesion studies were conducted using methylated seed oil (MSO) formulations, both 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 mounted on a 22.5-degree incline. Next, the percentage of impact droplets that adhered to the cabbage leaf surface was measured. As with the petroleum (mineral oil) based COC in Table 12, the addition of silicone oil to the MSO unexpectedly significantly improved droplet adhesion to the cabbage leaf surface. The results are summarized in Table 13 below.

[0094] [Table 13]

[0095] Referring to Table 14 below, Silwet641 (OSS-1) is a surfactant mixture based on a superspreader (trisiloxane alkoxylate) organosilicone and several nonionic surfactants. It is typically added to MSO base stocks at concentrations ranging from 10 to 20%. Sample SIL-29 in Table 14 is a formulation of 20 wt% OSS-1 and 80 wt% MS-1. Sample SIL-30 is a formulation containing 20 wt% OSS-1, 70 wt% MS-1 and 10 wt% OSIL-2. Silwet641 is often referred to as a superspreader and is considered to provide superior spreading properties. The data in Table 14 and Figures 5 and 6 show that the addition of the silicone oil according to the present invention reduces the equilibrium surface tension, which increases the emulsion stability of the added MSO concentrate and, surprisingly, increases the diffusion diameter of the product. In Figure 6, note that TSI measures emulsion separation, and a lower TSI corresponds to higher emulsion stability.

[0096] [Table 14]

[0097] Similar studies were conducted by adding silicone oil to MSO adjuvant formulations and evaluating the spray range of the products. Instead of measuring the diffusion diameter on hydrophobic surfaces, twelve sprays were performed using 0.5% spray solutions of samples SIL-31 and SIL-32. The solutions were sprayed at a pressure of 20 psig using a Unijet® 8002E flat fan nozzle. These spraying conditions correspond to a field spray rate of 100 L / ha. For each spray, the coverage achieved on a square 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 adding the low molecular weight silicone oil (polysiloxane) according to the present invention to an MSO formulation containing SIL-32 (including OSIL-2) resulted in increased spray coverage, providing better coverage than SIL-31 without PDMS oil.

[0098] [Table 15]

[0099] The effect of the composition of the present invention on droplet adhesion of spray solutions was tested on barnyard grass (Echinochloa crus-galli), which is difficult to wet, according to the methodology described above by Gaskinet 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 spraydroplet shatter, adhesion or bounce, In: Baur P, Bonnet M, editors. Proceedings 9th International Symposium on Adjuvants and Agrochemicals. ISAA978-90-815702-1-3; 2010). A droplet with a diameter of approximately 400 μm impacted a leaf mounted at a 22.5-degree angle from the horizontal, from a height of 53 cm. The adhesion of the droplet was compared to the dynamic surface tension of each formulation. The compositions of samples SIL-33 to SIL-36 are shown in Table 16.

[0100] [Table 16]

[0101] The adaxial leaf surface of barnyard grass is very poor to wet. Therefore, this is a good target for comparative droplet adhesion studies. Table 17 shows droplet adhesion reported as the percentage of impact droplets retained on the leaf surface. As seen in Table 17, the composition of the present invention resulted in an unexpectedly large increase in droplet adhesion compared to the commercially available benchmark AgroSpred820 (20 wt% Silwet 641, 80 wt% MSO) and compared to the SIL-34 benchmark without PDMS oil. This unexpected improvement is associated with the use of 10 cSt of PDMS oil OSIL-2. Given the negligible difference from the slight difference observed in DST at typical impact times (between 50 and 250 milliseconds), the level of improvement exceeding a twofold increase in droplet adhesion is a surprising and unexpected result.

[0102] [Table 17] The effect of low MW PDMS oil on the foam volume of MSO concentrate was also tested. Figure 7 shows the foam volume measured by a spurge test. In this test, nitrogen was bubbling into the spray solution at a rate of 1.0 L / min for 1 minute using metal frit. Foam volume was measured at initial (when foaming stops), 1, 2, 5, and 10 minutes. As can be seen, the low molecular weight PDMS oil reduced the foam level to a level lower than that achievable using a high-performance defoamer (e.g., SAG-1572 available from Momentive Performance Materials). This result was unexpected, as the presence of trisiloxane alkoxylate negates the effect of commercially available defoamers at typical usage rates, and is related to the low equilibrium surface tension provided by the organosilicon superspreader.

[0103] As described above, adding low concentrations (1-20%) of low molecular weight, low viscosity polydimethylsiloxane (silicone oil) according to the present invention to COC and MSO significantly reduced the surface tension of the petroleum and seed oil base stocks. The presence of silicone oil also enhanced the adhesion of sprayed COC and MSO droplets to the leaf surface. Furthermore, the addition of these low molecular weight silicone oils to crop oil concentrates and MSO unexpectedly greatly improved adhesion on various leaf surfaces, while simultaneously improving emulsion stability and reducing foam volume.

[0104] It should be noted that a limiting factor may be the low solubility of PDMS oil in crop oil-based stocks. The following results show the investigation of the effects of various alkyl-silicone oils on the performance of COC and MSO. All alkyl-silicone oils evaluated here showed good solubility in both mineral oil and methylated seed oil, and significantly reduced the equilibrium surface tension of the resulting COC and MSO. Furthermore, all alkyl-silicone oils promoted the adhesion of COC and MSO to plant leaves. The alkyl-modified silicones tested are listed below.

[0105] Alkyl-modified silicone. The alkyl group is either C8 or C12. [ka] [ka]

[0106] The solubility of alkyl silicone oils in typical mineral oils and methylated seed oils was first measured. Next, the effect of alkyl-silicones on the equilibrium surface tension of formulations with crop oil-based stocks was measured. Finally, the spreading properties of simple COC and MSO formulations containing alkyl-modified silicone oils were measured.

[0107] OSIL-5, OSIL-6, OSIL-7, and OSIL-8 all showed good solubility in MO-1. Next, the equilibrium surface tensions of these pure alkyl silicone oils were measured. They had surface tensions between 22 and 23 mN / m (see Table 18), which is significantly lower than the surface tension of pure MO-1, which is 29.9 mN / m.

[0108] The effect of alkyl silicone concentration on the equilibrium surface tension of MO-1 was measured. Adding 10% OSIL-5 to MO-1 significantly reduced the surface tension from 29.9 to approximately 26 mN / m. For OSIL-6 through OSIL-8, adding 10% alkyl silicone to MO-1 reduced the surface tension to less than 24 mN / m. This is similar to the reduction in surface tension achieved when OSIL-2 is added to MO-1. Although the compositions of the present invention can reduce the equilibrium surface tension of pure oil formulations, it was observed that such reductions were not always observed in aqueous dispersions of each oil-based formulation. Furthermore, no significant variation in dynamic surface tension (DST) was observed in spray solutions containing COC or MSO with or without the compositions of the present invention. Since droplet adhesion usually correlates with dynamic surface tension, those skilled in the art would expect comparable droplet adhesion for these formulations; however, incorporating the compositions of the present invention increased droplet adhesion despite no significant reduction in DST. This observation was unexpected and surprising. Table 18 summarizes the solubility data of alkyl silicones in MSO and EST measurements. Figure 8 shows the surface tension versus alkyl silicone concentration curve.

[0109] [Table 18]

[0110] The effect of alkyl silicones according to the present invention on spreading was measured by formulating samples of crop oil concentrates (COCs) based on MO-1 and 10% nonionic surfactant NIS-2. A 10:90 surfactant-in-oil formulation was used as a benchmark. Table 19 shows the spreading of the COC formulations and 1% dispersions of these products. All COC formulations containing alkyl silicone oil diffused significantly more on philodendron and bamboo leaves than the NIS-2 / MO-1 control (SIL-41).

[0111] [Table 19]

[0112] Similar datasets were generated to examine how these four alkyl silicones behave in MS-1. Table 20 shows the solubility and equilibrium surface tension of MS-1 and the alkyl silicones compounded with it. All four products showed good solubility in soybean methyl base oil. The effects of different concentrations of alkyl silicones OSIL-6 and OSIL-7 on the equilibrium surface tension of MS-1 were measured, and both alkyl silicones reduced the surface tension of MS-1 by more than 5 mN / m at a concentration of 10 percent.

[0113] [Table 20]

[0114] Methylated seed oil concentrates (MSOs) based on MS-1 were prepared. They contained 10% by weight of NIS-2, 10% by weight of alkyl silicone, and 80% by weight of MS-1. A 10:90 formulation of surfactant NIS-2 in seed oil MS-1 was used as a benchmark. The spreading of the MSO formulations and 1% dispersions of these products is shown in Table 21. Both MSO formulations containing alkyl silicone diffused significantly better than the SIL-44 benchmark after 15 and 120 minutes of spreading (except for the SIL-42 dispersion, which was comparable to the control against philodendron after 2 hours).

[0115] [Table 21]

[0116] Table 22 shows the effects of OSIL-9 and OSIL-10 on the equilibrium surface tension of MO-1. Both of these alkyl silicones significantly reduce the surface tension of oil at relatively low concentrations.

[0117] [Table 22]

[0118] Samples of crop oil concentrates containing OSIL-9 and OSIL-10 were prepared. A 10:90 formulation of NIS-2 in MO-1 was again used as a benchmark. The adhesion of 1% dispersions of these products was measured on polystyrene plates, philodendron leaves, and bamboo leaves. The results are summarized in Table 23. Composition SIL-45 of the present invention showed significantly better adhesion than the benchmark sample SIL-47. Composition SIL-46 of the present invention also showed significantly better adhesion on the leaf surface than the SIL-47 benchmark.

[0119] [Table 23]

[0120] OSIL-9 and OSIL-10 were also evaluated using MS-1. Both products showed good solubility in seed oil. The effects of different concentrations of these two alkyl silicones on the equilibrium surface tension of soybean methyl were measured and are shown in Table 24.

[0121] [Table 24]

[0122] MSO concentrates were formulated with 10 wt% NIS-2, 10 wt% OSIL-10, and 80 wt% MS-1. A 10:90 formulation of NIS-2 surfactant in seed oil MS-1 was used as a control. Table 24 shows the adhesion of the formulations and 1% dispersions of these products. Alkyl silicone-containing formulation SIL-48 showed very good adhesion on all tested surfaces and was far superior to the control formulation SIL-49.

[0123] [Table 25]

[0124] Figure 9 shows the droplet adhesion of several compositions of the present invention tested on poinsettia leaves. The results are expressed as the average percentage of impact droplets retained on the leaf surface. As can be seen, the compositions of the present invention result in significantly higher droplet adhesion rates than the reference COC formulation.

[0125] The following examples include alkyl silicones in MSO formulations containing organosilicone superspreaders. The evaluated MSO samples consisted of 70 wt% MS-1, 20 wt% OSS-1, and 10 wt% alkyl-modified silicone. These MSO compositions are shown in Table 26. Table 26 also shows the effect of alkyl silicones on the foam volume of seed oil concentrates containing organosilicone superspreaders. As can be understood, the compositions of the present invention, when combined with organosilicone superspreaders in seed oil concentrates, result in lower foam volume.

[0126] [Table 26]

[0127] Example A. Solubility of low-HLB ethoxylated alcohol and silanol in crop oils The silanol component of the present invention in various nonionic surfactants (R 1 and R 4Table 27 below shows examples of the solubility of (where is OH). Compounds containing silanol (from Formula 1 and Table 1) and alcohol ethoxylate (NIS from Table 2) can be prepared by physically combining the two components in a 1:1 ratio in a 50 mL jar and mixing with a magnetic stirring rod until homogeneous (about 10 minutes at ambient temperature). The mixtures were visually observed for their initial appearance and phase stability after 24 hours.

[0128] Table 27 shows that when the silanol component has a viscosity of less than 45 cSt (i.e., OSIL-12), NIS with an HLB of 9.0 or less provides a clear (visual) and stable (no phase separation) mixture. Furthermore, compositions containing a silanol component with a viscosity between 45 and 85 cSt (OSIL-13), when combined with an NIS component having an HLB of 9.0 or less, gave a clear initial appearance. However, while the formulation containing OSIL-13 and NIS-9 remained stable after 24 hours, the formulation showed signs of separation after 24 hours. Furthermore, all formulations consisting of OSIL-14 (viscosity between 90 and 120 cSt) and an NIS component showed a cloudy appearance and separation after 24 hours. This indicates that the HLB of NIS, as well as the viscosity of the silanol component in this invention, play a role in the solubility of the mixture. Furthermore, the Si-OH content increases with decreasing viscosity, thereby providing polar groups that bond with the alkylene oxide groups of NIS. Therefore, the viscosity of the silanol component may indirectly contribute to solubility.

[0129] [Table 27]

[0130] Example B. Solubility in agricultural oils Furthermore, the silanol components of the present invention show 50% solubility in methylated seed oils when the viscosity is ≤85 cSt (OSIL-12 and OSIL-13), and insolubility when the viscosity exceeds 90 cSt (OSIL-14). However, no silanol components were found to be 50% soluble in paraffinic mineral oil (MO-1) (Table 28).

[0131] [Table 28]

[0132] Example C. Spreading properties of silanol / surfactant formulations The spreading properties of 1:1 mixtures of the silanol component of the present invention and various NIS components were evaluated by applying 10 μL drops of a 0.25% aqueous dispersion onto a polystyrene petri dish (low-energy surface) and measuring the diffusion diameter after 1 minute. Table 29 below shows that adding the silanol component of the present invention to an NIS component (1:1) increases spreading by 14% to 28%. Although the total NIS resulting from the 0.25% dispersion is only 0.125% NIS, the spreading is enhanced, indicating that the silanol component of the present invention promotes the spreading of aqueous dispersions containing NIS.

[0133] [Table 29]

[0134] Example D. Effect of oil formulation on the performance of topramezone in barnyard grass The effect of adjuvants on the performance of a 30% OD formulation of topramezon (herbicide) was measured in barnyard grass (Echinachloa crus-galli). Barnyard grass (BYDG) was cultivated in an environmental chamber at 20 to 25°C. Plants were treated with a spray solution containing either 0.33% herbicide alone or 0.2% or 0.4% adjuvant (see Table 30). Treatment was applied at a spray rate equivalent to 450 L / ha, and plants were evaluated for weed control (compared to untreated check) at 4, 7, 13, and 15 DAT (days after treatment). Weed control was determined by visual observation on a scale of 0 to 100% compared to "untreated check".

[0135] Table 30 shows that the compositions of the present invention can be used as agricultural oils, thereby replacing vegetable oils with organosilicone oils (OSIL-11 in this example). All treatments including the adjuvant improved the performance of the herbicide formulations. However, the strongest reactions were obtained with treatments 6 and 11, which included the adjuvant compositions of the present invention.

[0136] [Table 30]

[0137] Example E. Spray test on citrus red mites (Paonychuscitri) A spray test was conducted on citrus trees (orange trees) to determine the effect of the composition of the present invention (OSIL-11 / NIS-11) on the control of the citrus mite (Panonychus citri) compared with a crop oil formulation, Crop Oil A (a mixture of mineral oil (90%) and trisiloxane alkoxylate containing 10% nonionic surfactant). Furthermore, a comparison was made between (OSIL-11 / NIS-11) + Movento insecticide and Movento alone. The active ingredient of Movento (Bayer Crop Science) is spirotetramat (22.4% SC). Therefore, the citrus trees were treated with an aqueous dispersion of either 0.5% Crop Oil A (Treatment A) or 1:1 formulations of 0.2%, 0.1%, and 0.067% OSIL-11 / NIS-11 (Treatments 1-3). Furthermore, treatment was carried out using either Movento (0.025%) containing 0.067% OSIL-1 / NIS-11 (treatment 4), or Movento alone (treatment 5). Treatment 6 was a check of the untreated area.

[0138] The spray treatment was applied in a randomized block design with 2 L / tree, repeated three times per treatment. Table 31 below shows that all treatments containing either crop oil A or the OSIL-11 / NIS-11 formulation resulted in significant improvements compared to Movento insecticide alone at 1, 3, and 7 DAT (days after treatment). However, treatments containing OSIL-11 / NIS-11 alone or with Movento at the lowest dose (0.067%, treatments 3 and 4) were no different from Movento alone at 14 DAT.

[0139] Furthermore, treatments 1-3 yielded similar results to crop oil A, but with less than half the concentration (i.e., treatment 2 was five times less).

[0140] [Table 31]

[0141] Example F. Effect of polysiloxane on surface tension The effect of polysiloxane (silanol) on the surface tension of methyl soyate (MSO) was evaluated using the WilhelmyPlate method with a Kruss surface tensimeter equipped with a platinum blade as a sensor. Mixtures of the present invention with MSO and various proportions of silanol components (OSIL-12 and OSIL-13) were prepared by combining the two components in a beaker and mixing until homogeneous.

[0142] Table 32 below shows that including even 1% of either OSIL-12 or OSIL-13 significantly reduces the surface tension of the MSO. Surface tension decreased with the corresponding increase in the silanol component. Obtaining low surface tension in the oil phase can be important for spray droplet adhesion, as shown in paragraph 00124 above, “Effect of PDMS Oil on Surface Tension When Formulated with Oil-Based Stocks” and Figure 2 (see also paragraph 00124 and Figure 9). As described in paragraph 00124 above, Figure 9 shows droplet adhesion of several compositions of the present invention tested on poinsettia leaves. Results are expressed as the average percentage of impact droplets retained on the leaf surface. To be understood, the compositions of the present invention result in significantly higher droplet adhesion rates than benchmark COC formulations. [Table 32]

[0143] While the present invention has been described with reference to specific embodiments, those skilled in the art will understand that various modifications can be made and equivalents can be substituted for elements without departing from the scope of the invention. The present invention is not limited to the specific embodiments disclosed, but is intended to include all embodiments included in the appended claims.

Claims

1. An organosilicone-based agricultural composition comprising (a) 5% to 95% oil components of the composition, (b) a surfactant, and (c) a combination of polysiloxanes having an average molecular weight of 4,000 g / mol or less and a viscosity of 50 cSt or less at 25°C, Here, polysiloxane is soluble or dispersible in oil components and has general formula (I), M １ D ｘ D １ ｙ M ２ (I) Here 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 and R ４ R is hydroxyl (OH), ８ , or OR ８ Selected independently of; R ２ , R ３ , R ５ and R ６ These are independently selected from monovalent alkyl hydrocarbon radicals with 1 to 18 carbon atoms and aryl or alkaryl hydrocarbon radicals with 6 to 14 carbon atoms; R ７ is hydroxyl (OH), OR ８ , a monovalent hydrocarbon radical consisting of 1 to 4 carbon atoms, -OSi(R ８ ) ３ , or - (OSiR ８ R ８ ) ｆ OSi(R) ８ ) ２ Selected from OZ, where Z is H or R ８ And the subscript f is from 0 to 8; R ８ It is a monovalent hydrocarbon radical consisting of 1 to 4 carbon atoms; R ９ and R １０ These are independently selected from monovalent hydrocarbon radicals with 1 to 18 carbon atoms and aryl or alkaryl hydrocarbon radicals with 6 to 14 carbon atoms, and An agricultural composition having the subscript y = 0, and x between 3 and 50, provided that x + y is between 3 and 50.

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

3. The agricultural composition according to claim 1, wherein the combination results in at least 50% improved spreading or adhesion to the leaf surface compared to the same composition without polysiloxane.

4. The agricultural composition according to claim 1, wherein the oil component is mineral oil, paraffinic crop oil, vegetable oil, or esterified seed oil, and the polysiloxane is polydimethylsiloxane or organically modified polysiloxane.

5. R ８ The agricultural composition according to claim 1, wherein is selected from monovalent hydrocarbon radicals with 1 to 4 carbon atoms.

6. The agricultural composition according to claim 1, wherein x + y is between 5 and 50.

7. R １ From R ８ The agricultural composition according to claim 1, wherein is methyl.

8. The agricultural composition according to claim 7, wherein y = 0 and x is from 5 to 25.

9. The agricultural composition according to claim 1, wherein the polysiloxane has a viscosity of 20 cSt or less at 25°C.

10. The agricultural composition according to claim 9, wherein the polysiloxane has a molecular weight of 2,000 g / mol or less.

11. R １ and R ４ However, it is a monovalent alkyl hydrocarbon radical with 1 to 18 carbon atoms, or an aryl or alkaryl hydrocarbon radical with 6 to 14 carbon atoms, and R ２ , R ３ , and R ５ From R １０ The agricultural composition according to claim 1, wherein is methyl.

12. The agricultural composition according to claim 10, wherein x + y is between 5 and 50.

13. R １０ is a monovalent alkyl hydrocarbon radical with 1 to 18 carbon atoms, or an aryl or alkaryl hydrocarbon radical with 6 to 14 carbon atoms, and R １ From R ９ The agricultural composition according to claim 1, wherein is methyl.

14. The agricultural composition according to claim 13, wherein x + y is between 5 and 50.

15. R １ OH is and R ４ and R ７ The agricultural composition according to claim 1, wherein is methyl.

16. R １ and R ４ OH is and R ７ The agricultural composition according to claim 1, wherein is methyl.

17. R １ , R ４ and R ７ The agricultural composition according to claim 1, wherein each of them is an OH group.

18. R 1, R ４ and R ７ The agricultural composition according to claim 1, wherein each of the elements is not an OH group.

19. The composition comprises 5% to 95% oil component (a), 1% to 50% surfactant (b), and 1% to 95% polysiloxane component (c); Here R １ and R ４ is hydroxyl (OH); R ７ However, it is independently selected from hydroxyl (OH) or monovalent hydrocarbon radicals with 1 to 4 carbon atoms; R ８ However, it is a monovalent hydrocarbon radical consisting of 1 to 4 carbon atoms; The agricultural composition according to claim 1, wherein x is between 4 and 50 and y is 0.

20. The agricultural composition according to claim 1, comprising a C4 to C18 alcohol alkoxylate surfactant.

21. The agricultural composition according to claim 1, comprising a solvent selected from d-limonene, triacetin, isopropyl myristate, and esterified seed oil.

22. The agricultural composition according to claim 1, comprising an oil carrier selected from the group consisting of petroleum, mineral oil, paraffinic mineral oil, vegetable oil, esterified vegetable oil, and esterified seed oil.

23. A method for improving the spreading or adhesion properties of an agricultural composition comprising (a) 5% to 95% oil components and (b) a surfactant, wherein the combination exhibits a 10% improvement in adhesion or spreading compared to the same composition without polysiloxane or organo-modified polysiloxane, and the general formula (I) having a molecular weight of less than 4,000 g / mol and a viscosity of 50 cSt or less at 25°C. M １ D ｘ D １ ｙ M ２ (I) Here 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 and R ４ R is hydroxyl (OH), ８ , or OR ８ Selected independently of; R ２ 、R ３ 、R ５ and R ６ are independently selected from monovalent alkyl hydrocarbon radicals of 1 to 18 carbons and aryl or alkaryl hydrocarbon radicals of 6 to 14 carbon atoms; R ７ is hydroxyl (OH), OR ８ , a monovalent hydrocarbon radical consisting of 1 to 4 carbon atoms, -OSi(R ８ ) ３ , or - (OSiR ８ R ８ ) ｆ OSi(R) ８ ) ２ Selected from OZ, where Z is H or R ８ And the subscript f is from 0 to 8; R ８ It is a monovalent hydrocarbon radical consisting of 1 to 4 carbon atoms; R ９ and R １０ These are independently selected from monovalent hydrocarbon radicals with 1 to 18 carbon atoms and aryl or alkaryl hydrocarbon radicals with 6 to 14 carbon atoms, and The subscript y = 0, and x is between 3 and 50, provided that x + y is between 3 and 50. A method comprising adding a polysiloxane or an organically modified polysiloxane to a formulation.

24. A pesticide composition comprising a physiologically active ingredient and the agricultural composition described in claim 1.

25. A plant to which the pesticide composition described in claim 24 has been applied.

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