CN105120666A - Seed treatment formulations - Google Patents

Abstract

The present invention generally relates to aqueous seed treatment formulations comprising from about 0.2 to about 15.0% of at least one insecticide, from about 0.1 to about 0.45% of at least one graft copolymer, at least one polyvinyl alcohol (PVA), and from about 5% to about 30% of at least one plasticizer. The present invention also relates to aqueous seed treatment formulations wherein the insecticides are clothianidin, metconazole and metalaxyl.

Description

Seed Treatment Preparations

related application

This application claims the benefit of U.S. Patent Application Serial No. 13/774,372, filed February 22, 2013, which claims the benefit of U.S. Patent Application Serial No. 13/328,643, filed December 16, 2011, which claims the U.S. Patent Application Serial No. 12/326,309, filed December 2, 2008 and published on July 31, 2012, U.S. Patent No. 8,232,229, which claims U.S. Provisional Application No. 60, filed December 3, 2007 /991,969, U.S. Provisional Application Serial No. 60/991,976, filed December 3, 2007, and U.S. Provisional Application Serial No. 60/991,985, filed December 3, 2007. The teachings of the above cited applications are incorporated herein by reference.

technical field

The present invention generally relates to aqueous seed treatment formulations for protecting plant propagation material from attack by pests.

Background technique

The practice of treating seeds or other plant propagation material with pesticide formulations is well known. Insecticides and fungicides are applied to the seeds to protect them from pests throughout the early stages of plant development in the soil. Two types of pesticide formulations are commonly used: wettable powders and aqueous suspensions.

Commercial seed treatment formulations require specialized equipment to apply them properly or to treat large volumes of seed. The seed treatment equipment (seed treater) incorporates commercially available formulations to prepare pesticide suspensions. Examples of seed processors include Gustafson RH-24, HC3000 etc. Commercial pesticide formulations are usually formulated as suspension concentrates. Seed treaters are also used to add adhesives, binders, polymers and/or colorants to pesticide suspensions to improve handling and safety. The additives reduce dusting, and the colorants alert agricultural workers to this chemical treatment.

The amount of additive and amount of pesticide per unit of seed that can be used in seed applications is limited by the coating and drying techniques available in commercial seed treatment equipment. Each crop can only absorb a limited amount of fluid beyond which the seed cannot be properly dried and/or handled in a seed processing facility or planting facility.

Furthermore, many existing formulations contain high concentrations of low molecular weight (LMW) surfactants. These LMW surfactants are usually added to stabilize the dispersion of the pesticide and provide a stable pumpable suspension for easy handling by processors. One problem associated with LMW surfactants is that they are known to increase stress on the seed and can reduce germination.

Furthermore, it is known that stable aqueous formulations are not readily available for certain insecticides with relatively high water solubility and/or low melting points. Metalaxyl (melting point 63-72 ℃ industrial grade, water solubility 8400ppm) is such a chemical substance. Obtaining a stable aqueous suspension of metalaxyl was very challenging because there was no good way to prevent the chemical from re-crystallizing out, causing physical instability during storage.

Another problem with using ad hoc mixtures of pesticides, polymers, colorants and other additives is the need to deposit and dry the required amount of pesticides and additives on the seed for multiple applications. Proper adhesion is essential for several applications.

In addition to being time consuming, the safety of these application mixtures is often unknown and uncertain. Often, fillers, such as talc, are required to reduce phytotoxicity or to improve seed drying and handling properties. As a result, handling becomes difficult and the biological efficacy of the seed treatment decreases.

There remains a need in the art for a ready-to-use and effective non-phytotoxic all-inclusive formulation that adheres the pesticide to the seed and eliminates the need for further addition of binders or polymers to the application mix by the seed treater . Ideally, such formulations would be processable in a single application in a continuous fluid without the need for fillers or anti-blocking powders.

Contents of the invention

The present invention provides an aqueous seed treatment comprising: a) at least one insecticide; b) at least one graft copolymer; c) at least one polyvinyl alcohol (PVA); and d) at least one plasticizer. In one embodiment, the insecticides include clothianidin, metconazole and metalaxyl.

In one embodiment, the present invention includes: a) about 0.2% to about 15.0% of at least one pesticide; b) about 0.1% to about 0.45% of at least one graft copolymer; c) at least one polyethylene alcohol (PVA); and d) from about 5.0 to about 30% of at least one plasticizer (all percentages are listed as % of 100% active by weight % of the total formulation).

In another embodiment, the graft copolymer can be 2500 (35% aqueous solution).

In another embodiment, the PVA can be 24-203 (24% aqueous solution).

In another embodiment, the liquid plasticizer may be propylene glycol or hexylene glycol. In another embodiment, the plasticizer may be a mixture of propylene glycol and hexylene glycol.

In another embodiment, solid plasticizers may be used in combination with liquid plasticizers. Suitable solid plasticizers include trimethylolpropane, sorbitol, urea, or any combination thereof.

In further embodiments, the formulations may comprise additional ingredients such as preservatives, anionic surfactants, thickeners, wetting agents, antifoaming agents, lubricants, polymer emulsions or colorants.

In one embodiment, the preservative may be an aqueous solution of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, for example CG/ICP.

In another embodiment, the anionic surfactant may be sodium lauryl sulfate, such as WA-Extra (30% in water).

In another embodiment, the thickener may be xanthan gum, such as CC.

In another embodiment the wetting agent may be 4894.

In another embodiment, the defoamer may be 104PG-50 or DowCorningAntifoamFG-10 or a combination of both. In another embodiment, preferably 104PG-50.

In another embodiment, the lubricant may be Lube156P or Lube 156PFP (25% emulsion in water).

In one embodiment, the colorant may be Red 48: 2.

In one embodiment, the polymer emulsion may be ethylene-vinyl acetate copolymer, such as E-200.

In another embodiment, the aqueous pesticide formulation may comprise (unless otherwise stated, 100% active substance by weight % of the total formulation): a) from about 2.0% to about 15.0% of at least one pesticide; b) about 0.1 to about 0.45% of at least one graft copolymer; c) about 0.5 to about 2.5% of at least one polyvinyl alcohol (PVA); d) about 20.0 to about 30.0% of at least one plasticizer e) about 0 to about 0.3% of at least one preservative (as provided); f) about 0 to about 2.0% of at least one anionic surfactant; g) about 0 to about 0.25% of at least A thickener; h) about 0 to about 0.25% of at least one wetting agent; i) about 0 to about 0.3% of at least one antifoaming agent (as provided); j) about 0 to about 2.0% of at least one lubricant; k) about 0 to about 5.0% of at least one polymer emulsion (as provided); and l) about 0 to about 15.0% of at least one colorant (as provided of).

In another embodiment, the aqueous pesticide formulation may comprise (unless otherwise stated, 100% active substance by weight % of the total formulation): a) about 4.25% of at least one pesticide; b) about 0.35% of at least one graft copolymer; c) about 1.2% of at least one PVA; d) about 25% of at least one plasticizer; e) about 0.14% of at least one preservative (as provided f) about 0.40% of at least one anionic surfactant; g) about 0.14% of at least one thickening agent; h) about 0.176% of at least one wetting agent; i) about 0.10% of at least one A defoamer (as provided); j) about 0.75% of at least one lubricant; k) about 3.0% of at least one polymer emulsion (as provided); and l) about 10% of At least one colorant (as supplied).

In another embodiment, the aqueous pesticide formulation may comprise (unless otherwise stated, 100% active substance by weight % of the total formulation): a) about 1.0 to about 12.0% clothianidin; b) about 0.2 - about 4.0% of metalaxyl; c) about 0.1 to about 2.0% of metconazole; d) about 0.1 to about 0.45% of at least one graft copolymer; e) about 0.5 to about 2.5% of at least one A polyvinyl alcohol (PVA); f) about 5.0-about 30.0% of at least one plasticizer; g) about 0-about 0.3% of at least one preservative (as provided); h) about 0- About 2.0% of at least one anionic surfactant; i) about 0 to about 0.25% of at least one thickener; j) about 0 to about 0.25% of at least one wetting agent; k) about 0 to about 0.3% of at least one antifoaming agent (as provided); l) about 0 to about 2.0% of at least one lubricant; m) about 0 to about 5.0% of at least one polymer emulsion (as provided and n) from about 0% to about 15.0% of at least one colorant (as provided).

In another embodiment, the aqueous pesticide formulation may comprise (unless otherwise stated, 100% active substance by weight % of the total formulation): a) about 3.01% clothianidin (97.5% active ingredient) b) about 0.907% of industrial metalaxyl (97.0% active ingredient); c) about 0.454% of industrial metconazole (97.0% of active ingredient); d) about 0.35% of at least one graft copolymer e) about 1.2% of at least one PVA; f) about 25.0% of at least one plasticizer; g) about 0.14% of at least one preservative (as provided); h) about 0.4% of at least An anionic surfactant; i) about 0.14% of at least one thickening agent; j) about 0.176% of at least one wetting agent; k) about 0.10% of at least one antifoaming agent (as provided ); l) about 0.75% of at least one lubricant; m) about 3.0% of at least one polymer emulsion (as provided); and n) about 10.0% of at least one colorant (as provided ).

All embodiments of the invention comprise sufficient water to form the desired viscosity of the formulation. The balance of each formulation to 100% by weight of the formulation may be water.

In a final embodiment, the invention relates to a method of preparing a formulation comprising preparing a thickener premix, preparing a mixture of metconazole and metalaxyl, preparing a clothianidin suspension and then mixing other ingredients, said thickener, Thickener premix, the mixture of metconazole and metalaxyl, and the clothianidin suspension. Another method of preparing a formulation involves preparing a thickener premix, preparing a suspension containing clothianidin, metalaxyl, and metconazole, and then mixing the other ingredients, the thickener premix, and the thiaconazole. Suspensions of chlorpyram, metalaxyl and metconazole.

The disclosed embodiments are simply exemplary embodiments of the inventive concepts disclosed herein and are not to be considered limiting unless so stated.

Detailed description of the invention

The present invention relates to an insecticide-containing formulation formulated to provide a ready-to-use agricultural mixture that remains stable during storage and provides excellent seed coating. The seed coating provides the seed with better protection from pests.

Applicants have found that the ready-to-use formulations of the present invention are stable and non-phytotoxic. The formulations of the present invention are particularly convenient for the end user since they do not require dilution prior to application to seeds.

Throughout the specification, the terms "plant propagation material" and "seed" are often used interchangeably.

The term "as provided" means that the weight of the ingredients of the formulation indicated by weight is present in the claimed invention in the form provided by the manufacturer to the consumer. This is not the same as 100% pure ingredient products.

The formulations according to the invention can be used for the preparation of suspension concentrates of insecticides, fungicides and mixtures thereof. The disclosed formulations can be used "as is", mixed with other additives, or diluted with water. They can be applied to seeds by themselves or together with other pesticides or additives.

At this point, the various components of the disclosed formulations will be discussed in detail.

insecticide

Insecticides, which can be used according to the present invention include insecticides; including but not limited to neonicotinoid insecticides such as clothianidin (available from Sumitomo Chemical Co.), imidacloprid, thiamethoxam, acetamiprid and thiacloprid; antibiotic insecticides such as abamectin, emamectin benzoate and spinosyn A and B; carbamate insecticides such as bentoxacarb, carbaryl Insecticides, carbofuran, pirimicarb, isoprocarb, methiocarb, thiodicarb; pyrethroid insecticides, such as fluprothrin, deltamethrin; phenylpyrazole insecticides, such as Etpronil, fipronil; organochlorine insecticides, such as endosulfan; organophosphorus (organophophorus) insecticides, such as muscarin; diamide insecticides, such as chlorantraniliprole, sulfluramid Bisamides; benzoylurea insecticides such as triflubenzuron, chlofluazuron, diflubenzuron, hexafluzuron, hexaflumuron, diflubenzuron, chlorfluazuron, chlofluazuron ; Insect Growth Regulators, such as Mitosan and similar classes of insecticides.

Insecticides that may be used in accordance with the present invention include fungicides including but not limited to antibiotic fungicides such as antimycin A1, methoxyacrylate fungicides such as azoxystrobin, kysoxastrobin, fluoxastrobin , kresoxim-methyl, carbamate fungicides such as benthiazil, carbendazim, dimethocarb, valitecarb, thiophanate-methyl, dicarboximide fungicides such as captafol, gram Benden, oxaconazole, folpet, iprodione, procymidone, vinclozolin, triazole fungicides such as bifentriazole, furconazole, cyproconazole, benzyl chloride triazole Alcohol, difenoconazole, diniconazole, econazole, fenconazole, fluquinazole, fenconazole, hexaconazole, imidazole, peconazole, metconazole (available from Kureha) , Prothioconazole, Silfluazole, Tebuconazole, Triadimefon, Fenpyrol, Fenconazole, Amide fungicides such as Boscalid, Wiltin, Cycloprodil, Dichlorocyandiamide Dicyclomet (dicyclomet), ethaboxam, formofuramide, fenhexamid, sulfamethanil, fluoramide, furamet, fenoxam, furamide, oxaxyl, pyroxazole, thiafuramide, Thialamid, benzamid, aromatic fungicides such as dimasan, chlorothalonil, imidazole fungicides such as cyazofamid, imidazolidin, imidazosin, aliphatic nitrogen fungicides such as cremoxuron Cyanide, morpholine fungicides such as dimethomorph, pyrimidine fungicides such as chlorpyrimidol, azanil, fluoropyrimidol, pyrimethanil, pyrrole fungicides such as seed dressing, fungicide Nitrile and pyridine fungicides such as fluazinam and fluopyram; benzimidazole fungicides such as furylbenzimidazole and thiabendazole; dithiocarbamate fungicides such as mancozeb , maneb, thiram, thiram zinc, quinoline fungicides such as quinoxyfin, aromatic fungicides such as pentachloronitrobenzene, miscellaneous (unclassified) fungicides such as pyridazol, dithiazide Agro, pentocuron, pyroquinone, tricyclazole, 2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy-N-methylacetamide, aromatic Hydrocarbons: chlorophenyl fungicides such as tolclofos-methyl, phenylamides: acylalanine fungicides such as metalaxyl (available from Nufarm Ltd. or LGLifeSciences, Ltd.), metalaxyl -M, benalaxyl, benalaxyl-M, and furalaxyl-M, and related types of fungicides.

The terms "insecticide" and "fungicide" are used broadly and are intended to cover all compounds that are active against insects and fungi. The compounds may belong to a wide variety of compound classes. The insecticides used in the formulations prepared according to the present invention may be combinations of insecticides and fungicides selected to control a large number of pests, insects and/or fungi through the use of one formulation. Furthermore, it is contemplated that formulations prepared according to the present invention may also contain adjunct insecticides which do not meet the requirements set forth in the present invention, provided that these adjunct insecticides are compatible with the formulation, such as by compatibility well known to those skilled in the art. determined by the test. For example, a water-soluble insecticide may be dissolved in the water carrier used in the formulation without affecting the dispersion of the initial solid insecticide which is the subject of this invention. Another example of a secondary insecticide is a sealed insecticide in which a water insoluble liquid or low melting point insecticide and/or fungicide is enclosed by a solid shell or encapsulated in a solid matrix and then added to the formulations described herein .

Mixtures of insecticides and fungicides are preferably used in the present invention. Mixtures are influenced by factors such as crop, geographic area, pest spectrum and pressure, and prevalence of resistance.

Presently preferred insecticides in the mixture are neonicotinoid insecticides such as clothianidin, triazole fungicides such as metconazole, and phenylamide:acylalanine fungicides such as metalaxyl.

As mentioned previously, it is difficult to obtain stable aqueous formulations containing metalaxyl, since metalaxyl forms unwanted crystals. The inventors have surprisingly found that the formulations of the present invention provide an excellent solution to this known problem in the art.

Polyvinyl alcohol (PVA)

Polyvinyl alcohol (PVA) is a water-soluble synthetic polymer. Many different grades of PVA are commercially available. While most available PVA polymers are useful in the present invention, preferred PVA grades are "extra low", "low" and "medium" viscosity grades. They are usually classified by the viscosity of a 4% PVA solution. The viscosity of these PVA grades is generally between about 2.5 cP (centipoise) and about 3.2 cP (centipoise) at 20°C. The most preferred grades are "extra low" and "low" viscosity grades.

The PVA encompassed by the present invention has an average molecular weight of from about 12,500 g/mole to about 125,000 g/mole. Each polymer grade has a molecular weight distribution. The weight average molecular weight is defined as the molecular weight multiplied by the weight fraction of molecules with that molecular weight, which is the sum of all molecular weights in the distribution, divided by the total molecular weight. Furthermore, the PVA polymer can be fully (98-100%), moderately (90-98%) or partially (70-90%) hydrolyzed. Partially hydrolyzed PVA polymers are most preferred. Modified or special grade PVA polymers may also be used. PVA in the viscosity range disclosed above can be carboxylated or sulfonated to introduce some anionic character which increases the viscosity and disperses the powder. These grades of PVA simply have some carboxyl ( _-CO2X groups) or sulfonate groups ( _-SO3X groups) added to the PVA chain, where X can be H or an alkali metal.

In a preferred embodiment, PVA is 24-203, which is commercially available from Sekisui Specialty Chemicals America.

graft copolymer

Graft copolymers are materials having polymer chains of one chemical composition grafted from a polymer backbone having a different chemical composition. Graft copolymers that may be used in accordance with the present invention include, but are not limited to, acrylic, methacrylic, acrylate, methacrylate, or methyl methacrylate polymers having additional moieties extending from the acrylate polymer backbone. A polymer chain, for example, a polyether such as polyethylene glycol.

In a preferred embodiment, the graft copolymer is a polymer having an acrylic acid, methacrylic acid, acrylate, methacrylate or methyl methacrylate backbone and hydrophilic Polyethylene glycol (PEG)-branched comb-branched polymers. In a two-dimensional representation, the PEG branches are drawn perpendicular to the (usually linear) acrylate polymer backbone and resemble the teeth of a comb, giving rise to the description of "comb-like branches". The comb-branched graft copolymers used in the present invention are proprietary materials and, therefore, the inventors are ignorant of the specific details of their composition and preparation.

In a preferred embodiment, the comb-like branched graft copolymer is 2500 (about 35% graft copolymer solution from Huntsman Corp.)

PVA-graft copolymer combination

Synergistic combinations of PVA and graft copolymers are blends of these two polymers. There are many advantages to using the PVA-graft copolymer combination.

First, the polymer combination coats the pesticide used in the formulation and provides a protective layer between the pesticide and the seed. This protective layer reduces any phytotoxicity the pesticide may have.

Second, the water soluble polymeric materials used in the formulations of the present invention provide for slower absorption and transfer of the insecticide into the seed. Prior art formulations typically use ingredients to enhance the uptake and transfer of the insecticide into the seed. However, rapid absorption can exacerbate any toxicity that surfactants and insecticides may have, thereby reducing germination.

Furthermore, the PVA-graft copolymer combination is very water soluble and safe to seeds. Film-coated seeds formed from the formulations of the invention are readily rehydrated by soil moisture. The membrane does not act as a limiting factor in the transport of moisture into the seed. The normal lipophilic layer of the seed is preserved and remains a controlling factor in seed water uptake. Thus, good seed germination and coating adhesion is maintained.

Furthermore, the PVA-graft copolymer combination is compatible with dispersant systems used in many commercial polymer emulsions. This compatibility allows for direct incorporation of polymer emulsions into seed treatment formulations without loss of stability at the point of manufacture.

plasticizer

As used herein, the term "plasticizer" refers to a substance used to modify the film produced by the formulation, to allow for faster drying, and to impart higher moisture sensitivity without the need to damage the seed during handling and Viscosity of fluidity in planting equipment.

The liquid plasticizers usable according to the invention are generally low molecular weight alkyl glycols or polyols (diols or triols) in which the alkyl groups are 2 to 6 carbon atoms in length. Preferred liquid plasticizers include propylene glycol and hexylene glycol.

Solid plasticizers can also be used in combination with liquid plasticizers. Specific examples of suitable solid plasticizers include, but are not limited to, trimethylolpropane, sorbitol, urea, or any combination thereof. Blends comprising liquid and solid plasticizers are presently preferred. Such blends may include propylene glycol, hexylene glycol, urea, and trimethylolpropane.

polymer emulsion

When adhesion requirements are high or when high coverage is required, polymer emulsions (or latex) based on polyvinyl acetate and/or ethylene vinyl acetate copolymers can be added to improve adhesion and seed appearance.

An advantage of the formulations of the present invention is that they are "all inclusive", ie they allow the addition of polymer emulsions at the time of formulation preparation rather than adding them at the site of application. Thus, package stability is not sacrificed and seed moisture uptake is not compromised.

The polymer emulsions useful in the formulations of the invention are stabilized by PVA and are therefore PVA compatible. Polymer emulsions can be added to formulations without causing "dispersant shock" which can lead to undesired increased viscosity or gelling. Furthermore, since the stabilizers used in formulation suspensions and polymer emulsions or latexes are similar, the dispersant does not flake off the latex particles or the insecticide particles when they are mixed together. The result is a stable low viscosity mixture. The mixture is capable of depositing pesticides and polymers on seeds without the need for additional ingredients.

Additionally, polymer emulsions can be used to prevent unwanted moisture barriers from forming around the seeds. Typically, films of latex dispersions containing sufficient amounts of PVA are redispersible in water. However, when LMW surfactants are present in seed treatment formulations, their micelles adsorb PVA, depleting the PVA available to encapsulate latex, polymer emulsions, or insecticide particles. Thus, a permanent non-redispersible film can be formed that acts as a moisture barrier. The PVA-grafted polymer combination forms a protective layer around the latex particles. This protective layer can then form a film that inhibits said film formation or allows it to redisperse. Therefore, no permanent moisture barrier is formed. Therefore, the formulation of the present invention can eliminate or alleviate the adverse effects of LMW surfactants on dispersion stability and seed germination existing in the prior art.

In a preferred embodiment, the E-200 (Celanese Ltd.) polymer emulsion.

Wetting agents and other additives

In one embodiment, the formulation includes a wetting agent. Most commercially available wetting agents can be used for the purposes of the present invention.

The concentration of wetting agent should be the minimum required to achieve good wetting and film formation. When a suitable wetting agent is added, the formulation should wet and form a good film. Typically, suitable wetting agents are functional in amounts of 0.2 wt% or less of the total formulation.

In a preferred embodiment, the wetting agent is manufactured by Huntsman Corporation 4894 (about 88% solids).

In another embodiment, the formulations of the present invention contain additives typical in similar formulations to improve wrapping and handling properties.

Preferred additives include:

Organic thickeners, e.g., manufactured by CPKelco CC (xanthan gum);

Lubricant, anti-blocking agent, such as available from Michelman Inc. Lube156P or Lube156PFP (wax emulsion).

Defoamers, such as those manufactured by Air Products and Chemicals, Inc. 104PG (50% solution of tetramethyl-5-decyne-4,7-diol in propylene glycol).

Preservatives, such as those available from Rohmand Haas Company CG/ICP (5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one in water); and

Anionic surfactants, such as those available from Stepan WA-Extra (Sodium Lauryl Sulfate).

Also, coloring agents may also be added to the disclosed formulations to mark pesticide-coated seeds. In a preferred embodiment, the colorant is used Red 48:2 (from Sun Chemical).

The invention also relates to methods of applying said formulations to seeds. Seed treatment application techniques are well known to those skilled in the art and they can be readily employed in the context of the present invention. The compositions of the invention can also be used as suspensions or soaks. Film coatings and wraps can also be used. Coating processes are well known in the art and employ techniques such as film coating, wrapping, dipping, and the like. The method of application of the compositions of the invention may vary, and the invention is intended to encompass any techniques that would come to use by those skilled in the art.

The invention also relates to a method of protecting seed from pests comprising applying to the seed an effective amount of a formulation of the invention.

The phrase "effective amount" of a formulation means a sufficient amount of the formulation to provide the desired effect. Generally, the formulation is used in an amount that does not inhibit seed reproduction and does not cause phytotoxic damage to the seed. The amount of the formulation will vary depending on the particular crop and other factors. The necessary amounts of such formulations are well within the ordinary skill in the art.

The two most common methods of application are suspension treatment and direct treatment. Each method is available with specialized seed treatment equipment. Direct Processors meter the formulation directly onto the seed without dilution. The suspension processor meter doses a water-diluted suspension formed from the seed treatment formulation.

As used herein, all numerical values referring to amounts, weight percents, etc., are defined as "about" or "approximately" each specific value, plus or minus 10%. For example, the expression "at least 5.0 wt%" is understood as "at least 4.5 wt% - 5.5 wt%". Accordingly, the scope of the claims includes amounts within 10% of the claimed value.

The following examples are intended to illustrate the invention and to teach those skilled in the art how to make and use the invention. They are not intended to limit the invention in any way.

Detailed ways

Example 1

Preparation of seed treatment formulations

Seed treatment formulations were prepared using the following procedure with the amounts listed in Table 1 below in percent by weight and pounds per gallon of finished product.

Table 1

preparation CC premix

First, by mixing deionized water and CG/ICP is added to a small mixing tank equipped with a high shear mixer to prepare 1.5% CC premix. With the mixer running at 3000rpm, add CC and mix for at least 1h to ensure CC for proper dispersion and hydration. The amounts of each added ingredient are listed in Table 2 below.

Table 2

Preparation of Metalaxyl/Meconazole Solution

Then, a solution of metalaxyl and metconazole was prepared. Add propylene glycol and hexylene glycol to a mixing tank equipped with a mixer. When mixing at a speed sufficient to maintain a vortex, add the metalaxyl and metconazole. The solution was mixed until it was clear and homogeneous. Optionally, the solution can be heated to 40°C to speed up the rate of dissolution, but the temperature of the solution should not exceed 50°C. The amounts of each added ingredient are listed in Table 3 below.

table 3

Preparation of Clothianidin Suspension Concentrate

Preparation of Clothianidin Suspension Concentrate. Add deionized water to a mixing tank equipped with a high shear mixer. While mixing at a speed maintaining a vortex, add 2500, 4894 and 104PG-50. The mixture was mixed for 10 min or until it was homogeneous. Then, add the section Premix and mix for 20 min or until it is homogeneous. The mixer speed was then increased to provide high shear and vortex while gradually adding Clothianidin. The slow clothianidin addition rate avoided accumulation of powder on the surface. The suspension was mixed for an additional 20 min or until clothianidin was completely dispersed. Optionally, the suspending agent can be recirculated through an in-line high speed mixer to facilitate the dispersion process. The amounts of the ingredients are listed in Table 4 below.

Table 4

The clothianidin suspension was then milled to the target median particle size using a small media mill equipped with 0.8-1.0 mm ceramic media. For example, zirconium silicate or zirconium oxide may be used. Any equivalent small media mill that can achieve the desired particle size can also be used.

Prepare finished products

Finally, the finished product is prepared. Add deionized water to the main mix tank equipped with a high shear mixer. Under Set Rate to Keep Vortex, add 24-203 and mix until homogeneous or 15min. fully diluted 24-203 to prevent PVA precipitation. When mixing, add 2500, 4893 and 104PG-50 into the tank. then add Lube156P and E-200 into the tank.

The mixer speed was then increased to provide high shear and vortex. Slowly add clothianidin suspension to the tank over a period of at least 15 min. Then, the metalaxyl and metconazole solutions were slowly added to the tank. The mixture was stirred under high shear for at least 15 min.

While running the mixer at low shear with a vortex, add WA-Extra and Red 48: 2. The mixture was then mixed for 30 min or until homogeneous. Finally, add CC premix and mix until formulation is homogeneous. Additional water may be added to adjust viscosity if necessary. The amount of each added ingredient is listed in Table 5 below.

table 5

Example 2

Preparation of seed treatment formulations

Seed treatment formulations were prepared using the following procedure with the amounts listed in Table 6 below in percent by weight and pounds per gallon of finished product.

Table 6

preparation CC premix

First, by mixing deionized water and CG/ICP is added to a small mixing tank equipped with a high shear mixer to prepare 1.5% CC premix. With the mixer running at 3000rpm, add CC and mix for at least 1h to ensure CC for proper dispersion and hydration. The amount of each added ingredient is listed in Table 7 below.

Table 7

Preparation of Clothianidin/Metalaxyl/Meconazole Suspension Concentrate

The three active ingredient suspensions were prepared. Add deionized water to a mixing tank equipped with a high shear mixer. While mixing at a speed maintaining a vortex, add 2500, 4894, DowCorningFG-10 defoamer and 104PG-50. The mixture was mixed for 10 min or until it was homogeneous. Then, add the section Premix and mix for 20 min or until it is homogeneous. The mixer speed was then increased to provide high shear and vortex while clothianidin, metalaxyl and metconazole were gradually added. The slow rate of addition of the solid material avoids accumulation of powder on the surface. The suspension was mixed for an additional 20 min or until the solid active ingredient was completely dispersed. Optionally, the suspending agent can be recirculated through an in-line high speed mixer to facilitate the dispersion process. The amounts of each added ingredient are listed in Table 8 below.

Table 8

The suspension was then milled to the target median particle size using a small media mill equipped with 0.8-1 mm ceramic media. For example, zirconium silicate or zirconium oxide may be used. Any equivalent small media mill that can achieve the desired particle size can also be used.

Prepare finished products

Finally, the finished product is prepared. Add deionized water to the main mix tank equipped with a high shear mixer. Under Set Rate to Keep Vortex, add 24-203 and mix until homogeneous or 15min. fully diluted 24-203 to prevent PVA precipitation. While mixing, add propylene glycol, hexylene glycol, trimethylolpropane, urea, and the remaining 2500, 4894 and 104PG-50 into the tank. then add Lube156P and E-200 into the tank.

The mixer speed was then increased to provide high shear and vortex. Slowly add clothianidin/metalaxyl/metconazole suspension to the tank over a period of at least 15 min. Then, the metalaxyl and metconazole solutions were slowly added to the tank. The mixture was stirred under high shear for at least 15 min.

While running the mixer at low shear with a vortex, add Red 48: 2. The mixture was then mixed for 30 min or until homogeneous. Finally, add the margin of CC premix and mix until formulation is homogeneous. Additional water may be added to adjust viscosity if necessary. The amount of each added ingredient is listed in Table 9 below.

Table 9

Example 3

Preparation of seed treatment formulations

Seed treatment formulations were prepared using the following procedure with the amounts listed in Table 10 below in percent by weight and pounds per gallon of finished product.

Table 10

preparation 203 20% solution

First, prepare 20% 203 aqueous solution. Deionized water was added to a small mixing tank capable of heating its contents to at least 100°C. While mixing at a rate maintaining a vortex, add solids 203 to the groove. The mixture was then heated to 90 °C with continuous mixing until 203 was completely dissolved. The mixture was cooled to ambient temperature. The amount of each added ingredient is listed in Table 11 below.

Table 11

preparation CC premix

Then, by adding deionized water and CG/ICP is added to a small mixing tank equipped with a high shear mixer to prepare 1.5% CC premix. With the mixer running at 3000rpm, add CC and mix for at least 1h to ensure CC for proper dispersion and hydration. The amount of each added ingredient is listed in Table 12 below.

Table 12

Preparation of Clothianidin/Metalaxyl/Meconazole Suspension Concentrate

The three active ingredient suspensions were prepared. Add deionized water to a mixing tank equipped with a high shear mixer. While mixing at a speed maintaining a vortex, add 2500, 4894 and 104PG-50. The mixture was mixed for 10 min or until it was homogeneous. Then, add the section Premix and mix for 20 min or until it is homogeneous. The mixer speed was then increased to provide high shear and vortex while clothianidin, metalaxyl and metconazole were gradually added. The slow rate of addition of the solid material avoids accumulation of powder on the surface. The suspension was mixed for an additional 20 min or until the solid active ingredient was completely dispersed. Optionally, the suspending agent can be recirculated through an in-line high speed mixer to facilitate the dispersion process. The amounts of each added ingredient are listed in Table 13 below.

Table 13

The suspension was then milled to the target median particle size using a small media mill equipped with 0.8-1 mm ceramic media. For example, zirconium silicate or zirconium oxide may be used. Any equivalent small media mill that can achieve the desired particle size can also be used.

Prepare finished products

Finally, the finished product is prepared. Add deionized water to the main mix tank equipped with a high shear mixer. At the rate set to keep swirling, add 20% 203 solution and mix until homogeneous or 15min. fully diluted 24-203 solution to prevent PVA precipitation. When mixing, add propylene glycol, trimethylolpropane, urea and balance of 2500, 4894 and 104PG-50 into the tank. then add Lube156P and E-200 into the tank.

The mixer speed was then increased to provide high shear and vortex. Slowly add clothianidin/metalaxyl/metconazole suspension to the tank over a period of at least 15 min. The mixture was stirred under high shear for at least 15 min.

While running the mixer at low shear with a vortex, add the balance of CC premix and mix until formulation is homogeneous. Additional water may be added to adjust viscosity if necessary. The amount of each added ingredient is listed in Table 14 below.

Table 14

Example 4

Preparation of seed treatment formulations

Seed treatment formulations were prepared using the following procedure with the amounts listed in Table 15 below in percent by weight and pounds per gallon of finished product.

Table 15

preparation 203 20% solution

First, prepare 20% 203 aqueous solution. Deionized water was added to a small mixing tank capable of heating its contents to at least 100°C. While mixing at a rate maintaining a vortex, add solids 203 to the groove. The mixture was then heated to 90 °C with continuous mixing until 203 was completely dissolved. The mixture was cooled to ambient temperature. The amount of each added ingredient is listed in Table 16 below.

Table 16

preparation CC premix

Then, by adding deionized water and CG/ICP is added to a small mixing tank equipped with a high shear mixer to prepare 1.5% CC premix. With the mixer running at 3000rpm, add CC and mix for at least 1h to ensure CC for proper dispersion and hydration. The amount of each added ingredient is listed in Table 17 below.

Table 17

Preparation of Metalaxyl/Meconazole Solution

Prepare a solution of metalaxyl and metconazole. Add propylene glycol and hexylene glycol to a mixing tank equipped with a mixer. When mixing at a speed sufficient to maintain a vortex, add the metalaxyl and metconazole. The solution was mixed until it was clear and homogeneous. Optionally, the solution can be heated to 40°C to speed up the rate of dissolution, but the temperature of the solution should not exceed 50°C. The amount of each added ingredient is listed in Table 18 below.

Table 18

Preparation of Clothianidin Suspension Concentrate

Preparation of Clothianidin Suspension Concentrate. Add deionized water to a mixing tank equipped with a high shear mixer. While mixing at a speed maintaining a vortex, add 2500, 4894 and 104PG-50. The mixture was mixed for 10 min or until it was homogeneous. Then, add the section Premix and mix for 20 min or until it is homogeneous. The mixer speed was then increased to provide high shear and vortex while gradually adding Clothianidin. The slow rate of addition of solid material avoids accumulation of powder on the surface. The suspension was mixed for an additional 20 min or until clothianidin was completely dispersed. Optionally, the suspending agent can be recirculated through an in-line high speed mixer to facilitate the dispersion process. The amounts of each ingredient are listed in Table 19 below.

Table 19

The suspension was then milled to the target median particle size using a small media mill equipped with 0.8-1 mm ceramic media. For example, zirconium silicate or zirconium oxide may be used. Any equivalent small media mill that can achieve the desired particle size can also be used.

Prepare finished products

Finally, the finished product is prepared. Add deionized water to the main mix tank equipped with a high shear mixer. At the rate set to keep swirling, add 20% 203 solution and mix until homogeneous or 15min. fully diluted 24-203 solution to prevent PVA precipitation. When mixing, add 2500, 4894 and 104PG-50 into the tank. then add Lube156P into the groove.

The mixer speed was then increased to provide high shear and vortex. Slowly add clothianidin suspension to the tank over a period of at least 15 min. Then, the metalaxyl and metconazole solutions were slowly added to the tank. The mixture was stirred under high shear for at least 15 min.

then add Red 48: 2. Finally, add the margin of CC premix and mix until formulation is homogeneous. Additional water may be added to adjust viscosity if necessary. The amount of each added ingredient is listed in Table 20 below.

Table 20

Example 5

The formulations of the invention were tested for seed safety and efficacy. The formulations of the invention provide excellent seed safety and effective protection against seed and seedling diseases and insects. Furthermore, the seed treatment reduces the dust-off of active ingredients and inert substances from the treated seeds. Efficacy was compared to untreated seed and to commercial seed treatment standards well known to those familiar with the seed industry.

seed safety

Cold, mild and cold germination tests of treated wheat seeds were performed using standard methods used in the seed industry to verify that the formulations of the present invention are safe for the seeds. Germination was measured 6 months after treatment and the results are shown in Table 21 below. The results of the three trials showed that the formulation of Example 2 did not reduce germination, but gave germination values equal to untreated seeds.

Table 21

Study on Germination of Winter Wheat

Wheat and barley seeds treated with the same seed treatment were stored for three years after treatment. Warm germination tests showed that the formulation of Example 2 was seed safe and similar to untreated seeds over three years of storage. No negative effects were observed in germination tests.

Table 22

Anti-seed/seedling disease efficacy

Experiment 1

In a field study aimed at evaluating the field performance and seedling protection of the formulation of Example 2 against wheat crown rot ( Fusarium pseudogramearum ), an inoculum of the pathogen was placed in a sowing furrow with wheat seeds at planting. Untreated seeds were planted with and without inoculum to assess disease effects on stand establishment, seedling vigor (height and plant health) and yield. The study showed that the formulation of Example 2 had a significant stand improvement over the untreated inoculated treatment, and the product applied at both ratios had the same stand establishment as the untreated uninoculated treatment. Plant height and vigor ratings for the formulation of Example 2 were also significantly better than and equal to the untreated, inoculated treatment. The final yield evaluation of the treatments demonstrated the efficacy of the fungicide protection provided in the formulation of Example 2 in the control of Triticum spp., with an increase of 11.4 - 11.7 Bu/A over the untreated inoculated treatments.

Table 23

Experiment on Spring Wheat Inoculated with Wheat Crown Rot

test 2

In field trials the formulation of Example 2 provided excellent activity against barley sheaf smut caused by the pathogen, Ustilago solani. Stand establishment among treatments did not show significant differences. Yield data from the study showed that the formulation of Example 2 provided a numerical increase of 3.16-5.33 Bu/A relative to untreated barley.

Table 24

Trial on spring barley smut (Smut smut)

Anti-seed/seedling insect efficacy

Wireworms inhabit field soils and feed on seeds and germinating seedlings, causing plant damage that causes loss of crop field stand establishment. In spring wheat trials conducted in which needleworms had been found in the field, untreated wheat stands were significantly inferior to treatments of all fungicides, insecticides or combinations of fungicides and insecticides. When the seeds were treated with metalaxyl or metconazole, there was a significant increase of ¹ plant per 0.25m2. Clothianidin alone treated 2.7 more plants than untreated. The formulation of Example 2 at both ratios tested provided the best stand establishment of the treatments evaluated, giving a significant gain of 5.2 plants over no treatment and significantly better than the fungicide alone or Clothianidin alone.

Table 25

Spring wheat experiment. When planting, the field soil naturally breeds needleworms in large numbers.

Dust removal of active/inert substances for reduced treatment of seeds

Dust retention measurements on treated seeds were performed with a Heubach duster. Such a method allows the evaluation of formulations in terms of seed coat retention of active ingredients, eliminating dust in the environment during handling. The formulation of Example 2 had dust values equal to or less than untreated seeds.

Table 26

Heubach dust gauge measurements of treated Jagger wheat.

Yield Performance Studies

The following table provides the yield performance in the winter wheat trials. Aphids are considered pests in field trials. The formulation of Example 1 provided increased yield through effective control of the pest.

Table 27

Research on winter wheat. Aphids are regarded as field trial pests.

Claims (21)

1. a water-based seed treatment formulations, it comprises (except as otherwise noted, in % by weight 100% active substances of total preparation):

A) at least one insecticide of about 0.2-about 15.0%;

B) at least one graft copolymer of about 0.1-about 0.45%;

C) at least one polyvinyl alcohol (PVA); With

D) at least one plasticizer of about 5.0-about 30%.

2. preparation according to claim 1, wherein said insecticide is clothianidin.

3. preparation according to claim 2, also comprises insecticide metconazole.

4. preparation according to claim 3, also comprises insecticide metalaxyl.

5. preparation according to claim 1, wherein said graft copolymer is

6. preparation according to claim 1, wherein said PVA is

7. preparation according to claim 1, wherein said at least one plasticizer is the mixture of propane diols and hexylene glycol.

8. preparation according to claim 1, also comprises at least one thickener, wetting agent, defoamer, lubricant, polymer emulsion, preservative, anion surfactant or colouring agent.

9. preparation according to claim 8, wherein said thickener is xanthans.

10. preparation according to claim 9, wherein said thickener is

11. preparations according to claim 8, wherein said wetting agent is

12. preparations according to claim 8, wherein said defoamer is

13. preparations according to claim 8, wherein said lubricant is 156P.

14. preparations according to claim 8, wherein said colouring agent is

15. preparations according to claim 8, wherein said polymer emulsion is ethylene-vinyl acetate copolymer.

16. preparations according to claim 15, wherein said polymer emulsion is

17. 1 kinds of aqueous agricultural-chemical preparations, it comprises (except as otherwise noted, in % by weight 100% active substances of total preparation):

A) at least one insecticide of about 2.0-about 15.0%;

B) at least one graft copolymer of about 0.1-about 0.45%;

C) at least one polyvinyl alcohol (PVA) of about 0.5-about 2.5%;

D) at least one plasticizer of about 20.0-about 30.0%;

E) at least one preservative (as provided) of about 0-about 0.3%;

F) at least one anion surfactant of about 0-about 2.0%;

G) at least one thickener of about 0-about 0.25%;

H) at least one wetting agent of about 0-about 0.25%;

I) at least one defoamer (as provided) of about 0-about 0.3%;

J) at least one lubricant of about 0-about 2.0%;

K) at least one polymer emulsion (as provided) of about 0-about 5.0%;

L) at least one colouring agent (as provided) of about 0-about 15.0%; With

M) surplus of described preparation is water, to total 100 % by weight.

18. aqueous agricultural-chemical preparations according to claim 17, it comprises (except as otherwise noted, in % by weight 100% active substances of total preparation):

A) at least one insecticide of about 4.25%;

B) at least one graft copolymer of about 0.35%;

C) at least one PVA of about 1.2%;

D) at least one plasticizer of about 25.0%;

E) at least one preservative (as provided) of about 0.14%;

F) at least one anion surfactant of about 0.4%;

G) at least one thickener of about 0.14%;

H) at least one wetting agent of about 0.176%;

I) at least one defoamer (as provided) of about 0.10%;

J) at least one lubricant of about 0.75%;

K) at least one polymer emulsion (as provided) of about 3.00%; With

L) at least one colouring agent (as provided) of about 10%; With

M) surplus of described preparation is water, to total 100 % by weight.

19. 1 kinds of aqueous agricultural-chemical preparations, it comprises (except as otherwise noted, in % by weight 100% active substances of total preparation):

A) clothianidin of about 1.0-about 12.0%;

B) metalaxyl of about 0.2-about 4.0%;

C) metconazole of about 0.1-about 2.0%;

D) at least one graft copolymer of about 0.1-about 0.45%;

E) at least one polyvinyl alcohol (PVA) of about 0.5-about 2.5%;

F) at least one plasticizer of about 5.0-about 30.0%;

G) at least one preservative (as provided) of about 0-about 0.3%;

H) at least one anion surfactant of about 0.1-about 2.0%;

I) at least one thickener of about 0-about 0.25%;

J) at least one wetting agent of about 0-about 0.25%;

K) at least one defoamer (as provided) of about 0-about 0.3%;

L) at least one lubricant of about 0-about 2.0%;

M) at least one polymer emulsion (as provided) of about 0-about 5.0%;

N) at least one colouring agent (as provided) of about 0-about 15.0%;

O) surplus of described preparation is water, to total 100 % by weight.

20. aqueous agricultural-chemical preparations according to claim 19, it comprises (except as otherwise noted, in % by weight 100% active substances of total preparation):

A) the industrial clothianidin (active ingredient of 97.5%) of about 3.01%;

B) the industrial metalaxyl (active ingredient of 97.0%) of about 0.907%;

C) the industrial metconazole (active ingredient of 97.0%) of about 0.454%;

D) at least one graft copolymer of about 0.35%;

E) at least one PVA of about 1.2%;

F) at least one plasticizer of about 25.0%;

G) at least one preservative (as provided) of about 0.14%;

H) at least one anion surfactant of about 0.4%;

I) at least one thickener of about 0.14%;

J) at least one wetting agent of about 0.176%;

K) at least one defoamer (as provided) of about 0.10%;

L) at least one lubricant of about 0.75%;

M) at least one polymer emulsion of about 3.00%;

N) at least one colouring agent (as provided) of about 10.0%; With

O) surplus of described preparation is water, to total 100 % by weight.

The method of 21. preparation preparation according to claim 20, it comprises

A) thickener pre-composition is prepared;

B) mixture of metconazole and metalaxyl is prepared;

C) clothianidin suspending agent is prepared; With

D) mixture and the clothianidin suspension of described thickener pre-composition, metconazole and metalaxyl is mixed.