Wettable powder and water dispersible granules
Blockage during spore germination and application is solved by using sulfonated naphthalene formaldehyde condensate and polyethylene glycol side chain acrylic copolymer combined with mineral fillers in biopesticide and biofertilizer formulations. These problems have improved the survival and application efficiency of spores.
Patent Information
- Application Number
- CN202380043162.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2022-05-27
- Filing Date
- 2023-05-26
- Publication Date
- 2024-12-27
AI Technical Summary
Existing microorganism-based biopestic and biofertilizer formulations are prone to spore germination under high water content, short storage period, and there are problems of nozzle blockage, unevenness and low dispersion during the application process, which affects their effectiveness.
Wettable powders (WP) and water dispersed granules (WDG), where the dispersant is a sulfonated naphthalene formaldehyde condensate and polyethylene glycol side chain acrylic copolymer, combined with mineral fillers such as coated mica, kaolin or dioxide Silicon, a formulation formed to improve the wettability and dispersion of the spores.
It significantly improves the survival and application efficiency of spores, reduces nozzle blockage and inhomogeneity problems, extends the shelf life of spores, and maintains efficient dispersion during field use.
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Abstract
Description
[0001] The present invention relates to microbial wettable powders and water dispersible granules for use in agrochemical and agronomically active formulations. The invention also includes methods of treating crops with said formulations.
[0002] The use of biological control agents in the agricultural products industry is a growing area due to their effectiveness in crop protection and crop enhancement and because they offer a sustainable alternative to conventional methods. Recently, the number of companies interested in developing and producing biopesticide and biofertilizer formulations based on microorganisms such as fungi and bacteria has increased significantly.
[0003] In the case of formulations of microorganisms, the best species, strain and structure are usually selected to provide the best efficacy (agronomic effectiveness) and stability (shelf life). Fungi are usually formulated in conidial form (spores) because of their optimal survival over time, but it is necessary to formulate them in oils or solids because water content above a certain level can promote undesirable germination of spores during storage and reduce the shelf life of the formulation in the package.
[0004] However, these types of solid-based formulations bring several technical problems that make their market expansion difficult. These technical problems include maintaining formulation quality, poor water dispersibility, low wettability (e.g., due to the hydrophobic nature of spores), problems during application such as nozzle clogging, low opening speed in water, poor dispersibility in tank mixing, non-uniformity in field application and medium / long-term stability of microorganisms in formulations. All these problems can drastically affect the final quality of biopesticides and / or biofertilizers, affecting the quality of the product applied in the field and the effectiveness of biopesticides or biofertilizers when contacting target pests / diseases.
[0005] Therefore, the present invention seeks to provide wettable powders (WP) and water dispersible granules (WDG) suitable for use with biological pesticides or biological fertilizers, for compounds formed thereof, wherein the WP and WDG are able to overcome the problems described above. Additionally, the present invention seeks to provide WP and WDG, which have improved wettability and opening speed without significantly affecting the viability of the microbial biological pesticide or biological fertilizer and its efficacy in the field. The present invention provides the use of WP / WDG, which is used to be diluted for use on field sprays or as seed treatment agents.
[0006] According to a first aspect of the present invention, there is provided a wettable powder (power) or a water dispersible granule, comprising:
[0007] (i) a dispersant selected from sulfonated naphthaldehyde condensates; acrylic copolymers having end-capped polyethylene glycol side chains on a polyacrylic acid backbone; copolymer dispersants comprising copolymers of acrylic acid, hydrophobic monomers, alkyl acrylates of monoalkyl polyethylene glycols and optionally strong acid derivatives of (meth)acrylic acid; nonionic graft copolymers of acrylates and alkylene oxides; or lignin sulfonates;
[0008] (ii) Mineral-based fillers selected from:
[0009] Mica particles coated with metal oxides; or
[0010] Kaolin, silica, or calcium carbonate;
[0011] Having a particle size of 1 µm to 100 µm and a bulk density of 0.2 g / mL to 0.6 g / mL; and
[0012] (iii) at least one microorganism selected from fungal spores, or microorganisms having biopesticide or biofertilizer effects.
[0013] According to a second aspect of the present invention, there is provided a wettable powder or a water dispersible granule, comprising:
[0014] (i) a dispersant selected from sulfonated naphthaldehyde condensates; acrylic copolymers having end-capped polyethylene glycol side chains on a polyacrylic acid backbone; copolymer dispersants comprising copolymers of acrylic acid, hydrophobic monomers, alkyl acrylates of monoalkyl polyethylene glycols and optionally strong acid derivatives of (meth)acrylic acid; nonionic graft copolymers of acrylates and alkylene oxides; or lignin sulfonates;
[0015] (ii) a mineral-based filler selected from particles having a particle size of 1-60 µm, a bulk density of 0.2-0.6 g / ml and optionally a water absorption capacity greater than 50%; and
[0016] (iii) at least one microorganism selected from fungal spores, or microorganisms having biopesticide or biofertilizer effects.
[0017] According to a third aspect of the present invention, there is provided a premix suitable for forming the wettable powder or water dispersible granules of the first aspect, the premix comprising
[0018] A dispersant selected from sulfonated naphthaldehyde condensates; acrylic copolymers having end-capped polyethylene glycol side chains on a polyacrylic acid backbone; copolymer dispersants comprising copolymers of acrylic acid, hydrophobic monomers, alkyl acrylates of monoalkyl polyethylene glycols and optionally strong acid derivatives of (meth)acrylic acid; nonionic graft copolymers of acrylates and alkylene oxides; or lignin sulfonates,
[0019] and mineral-based fillers selected from:
[0020] Mica particles coated with metal oxides; or
[0021] Kaolin, silica, or calcium carbonate;
[0022] With particle size ranging from 1µm to 100µm and bulk density ranging from 0.2 g / mL to 0.6 g / mL.
[0023] According to a fourth aspect of the present invention, there is provided a method for preparing the wettable powder or water dispersible granules of the first aspect, the method comprising mixing the premix according to the second aspect with at least one microorganism selected from microorganisms or fungal spores having a biopesticide or biofertilizer effect.
[0024] According to a fifth aspect of the present invention, there is provided a formulation suitable for application to plants, the formulation comprising a dilute suspension of the wettable powder or water dispersible granules of the first aspect.
[0025] According to a sixth aspect of the present invention, there is provided a seed treatment formulation, the formulation comprising the wettable powder or water dispersible granules of the first aspect.
[0026] According to a seventh aspect of the present invention, there is provided a method for treating seeds to control pests and diseases, the method comprising applying the formulation of the fifth aspect to the seeds.
[0027] According to an eighth aspect of the present invention, there is provided a method of treating plants to control pests and diseases, the method comprising applying a diluted formulation of the first aspect to the plants or to the immediate vicinity of the plants.
[0028] According to a ninth aspect of the present invention, there is provided a method for improving the viability of at least one beneficial microorganism on an agricultural target, comprising the steps of combining the beneficial microorganism selected from microorganisms or fungal spores having a biopesticide or biofertilizer effect with at least one dispersant and a mineral-based filler as defined in the first aspect on the agricultural target.
[0029] It has been found that the use of dispersants with fillers and with biopesticides provides better wettability to fungal spores formulated as wettable powders or water dispersible granules, allowing better homogenization in tank mixes and reducing problems in application. The formulation can also be used with or instead of dry powders in the final stages of seed treatment (depending on the required spore dosage). It has been observed that the use of dispersants and fillers as described in the present application can improve the survival of biopesticides or biofertilizers in WP and WDG.
[0030] As used herein, the terms 'for example', 'for example', 'such as' or 'including' are intended to introduce examples that further clarify the general subject matter. Unless otherwise specified, these examples are only provided to assist in understanding the applications described herein and are not intended to be limiting in any way.
[0031] It should be understood that in describing the number of carbon atoms in a substituent (e.g., 'C 1 To C 6 When the number of carbon atoms in a substituent is, for example, an alkyl group, the number refers to the sum of the number of carbon atoms in the substituent, including the number of carbon atoms present in any branching groups. Additionally, when describing the number of carbon atoms in, for example, a fatty acid, this refers to the total number of carbon atoms including the carboxylic acid and any branching groups.
[0032] When microorganisms are mentioned in the present application, they include in particular fungi and bacteria which are in solid form and have relevant applications in agriculture as biological control agents, biopesticides or biofertilizers.
[0033] The dispersant is preferably selected from any suitable dispersant, including dispersants such as sulfonated naphthaldehyde condensates; acrylic copolymers such as comb copolymers having end-capped polyethylene glycol side chains on a polyacrylic acid backbone; copolymer dispersants comprising copolymers of acrylic acid, hydrophobic monomers, alkyl acrylates of monoalkyl polyethylene glycols, and optionally strong acid derivatives of (meth)acrylic acid; nonionic graft copolymers of acrylates and alkylene oxides; or lignin sulfonates.
[0034] The dispersant may preferably be selected from water-dispersible styrene (meth) acrylic copolymers. The water-dispersible styrene (meth) acrylic copolymers used in the present invention are sometimes referred to as polymeric dispersants hereinafter. The polymeric dispersant is a styrene (meth) acrylic copolymer. The repeating units in the copolymer are conveniently regarded as the residues of the monomer components.
[0035] The (meth)acrylic acid monomer can be acrylic acid, methacrylic acid, crotonic acid or a mixture of two or more of these. The (meth)acrylic acid monomer can be or include a (meth)acrylic acid-based monomer, which is a derivative of (meth)acrylic acid that includes a strong acid, particularly a sulfuric acid or sulfonic acid group (or a salt thereof). Examples of such monomers include acrylamidomethylpropyl sulfonate (AMPS) and (meth)acrylate isethionate. When present, the strong acid-modified monomer typically constitutes 1 to 30 mol %, more typically 2 to 20 mol %, and suitably 5 to 15 mol % of the acrylic acid monomer in the copolymer.
[0036] The styrene monomer can be and suitably is original styrene or substituted styrene, in particular a hydrocarbyl (suitably alkyl) substituted styrene, wherein the substituent is on the vinyl group of styrene or on the aromatic ring, such as alpha-methylstyrene and vinyltoluene. Like (meth) acrylic monomers, the styrene monomer can be or include a styrene monomer, which includes a strong acid, in particular a sulfonic acid substituent. When present, the strong acid-modified monomer typically constitutes 1 to 30 mol %, more typically 2 to 20 mol %, and suitably 5 to 15 mol % of the styrene monomer in the copolymer.
[0037] In the water-dispersible styrene (meth) acrylic copolymers used in the present invention, the molar ratio of the residues of (meth) acrylic acid monomers to the residues of styrene monomers is generally 20: 1 to 1: 5, more typically 10: 1 to 1: 2 and especially 3: 1 to 1: 1. Generally speaking, accordingly, the weight proportions of the monomer residues are generally 93 to 10%, more typically 87 to 25%, especially 67 to 40% (meth) acrylic acid monomers and 7 to 90%, more typically 13 to 75%, especially 33 to 60% styrene monomers.
[0038] Other monomers can be included, such as acidic monomers such as itaconic acid or maleic acid or anhydride; strongly acidic monomers such as methallyl sulfonic acid (or salt); or non-acidic acrylic monomers such as acrylic acid esters, which may be alkyl esters, especially C 1 To C 6 Alkyl esters such as methyl methacrylate, butyl methacrylate or butyl acrylate, or hydroxyalkyl esters, especially C 1 To C 6 Hydroxyalkyl esters such as hydroxyethyl methacrylate or hydroxypropyl methacrylate; or vinyl monomers such as vinyl acetate. Generally, the proportion of the other monomers relative to the total monomers used will be no more than about 25 mol%, usually no more than about 15 mol%, more usually no more than about 5 mol%. The weight proportion of the other monomers will generally be no more than about 30%, usually no more than about 20%, more usually no more than about 10%.
[0039] The polymeric dispersant can be a styrene acrylic copolymer or a blend comprising two or more of said copolymers. In particular, where a strong acid residue is included in the polymeric dispersant, the dispersant can be a blend of a copolymer comprising the strong acid residue and a copolymer not comprising said residue. In said blend, it is generally desirable that the ratio of said copolymer is from 1:10 to 10:1, more typically from 5:1 to 1:5, by weight. In particular, the proportion of the copolymer comprising the strong acid residue is suitably at least 25%, more typically at least 40%, by weight of the polymeric dispersant.
[0040] Where strong acid residues are included in the polymeric dispersant, the total proportion of monomer residues comprising strong acid groups is suitably from 0.25 to 25 mol %, more typically from 0.5 to 20 mol % and suitably from 1 to 10 mol %.
[0041] Inclusion of monomers having strongly acidic substituents in the polymeric dispersant can provide improved dispersion of the solid granule form of the agrochemical formulation when dispersed in hard water, particularly water having a hardness above 500 ppm, such as up to 1,000 ppm, up to 2,000 ppm or even up to 5,000 ppm.
[0042] The polymer dispersant has a molecular weight of suitably 750 to 20,000, more suitably 1,000 to 10,000 and particularly 1,500 to 5,000. The polymer dispersant can be used as a free acid or as a salt. In practice, the form present in the formulation will depend on the acidity of the formulation. Suitably, the formulation will be close to neutral so that most of the acid groups will exist as salts. The cation in any of the salts can be an alkali metal, particularly sodium and / or potassium, ammonium or an amine, including alkanolamines such as ethanolamine, particularly triethanolamine. The polymer dispersant used in the present invention is suitably free of solvents that may interfere with the active ingredient or cause the particles to stick together. It is also useful if the polymer dispersant can be satisfactorily used in a variety of different granulation processes. It is also suitable that the polymer dispersant is heat-stable, can be easily dissolved in cold water from solid dispersible granules (a satisfactory polymer dispersant does not need to be easily dissolved in cold water from a bulk solid form) and does not gel.
[0043] The polymeric dispersants can be prepared by free-radical polymerization of the constituent monomers (for example with peroxides or redox initiators), in particular by solution polymerization, optionally also using chain transfer agents such as alkyl mercaptans (to control the molecular weight of the polymer). Suitable processes are described, for example, in EP 0697422 A.
[0044] The dispersant may be selected from copolymer dispersants comprising a copolymer of acrylic acid, a hydrophobic monomer, an alkyl acrylate of a monoalkyl polyethylene glycol and optionally a strong acid derivative of (meth)acrylic acid.
[0045] The acrylic monomer used to form the copolymer can be selected from (meth)acrylic acid or its salt, (meth)acrylamide, (meth)acrylonitrile, (meth)acrylic acid C 1-6 - alkyl esters such as ethyl (meth)acrylate, butyl (meth)acrylate or hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, substituted (meth)acrylate C 1-6- alkyl esters such as glycidyl methacrylate and acetoacetoxyethyl methacrylate, di(C)(meth)acrylate 1-4 -alkylamino) C 1-6 - alkyl esters such as dimethylaminoethyl acrylate or diethylaminoethyl acrylate, amides formed from: C 1-6 -Alkylamine, substituted C 1-6 - alkylamines such as 2-amino-2-methyl-1-propanesulfonic acid, ammonium salts, or di(C 1-4 -alkyl-amino) C 1-6 -alkylamine and (meth)acrylic acid and C 1-4 -Alkyl halide adducts.
[0046] Preferably, the acrylic acid monomer can be acrylic acid, methacrylic acid, crotonic acid, or a mixture thereof. More preferably, the monomer is acrylic acid.
[0047] The hydrophobic monomer may be selected from any monomer that is insoluble in water. In particular, the hydrophobic monomer may be selected from hydrophobic alkyl (meth)acrylates, styrenes, and vinyl compounds, and vinyl aromatic monomers.
[0048] Especially, vinyl aromatic monomers may be preferred.
[0049] The vinyl aromatic monomer can be and suitably is native styrene or a substituted styrene, particularly a hydrocarbyl (suitably alkyl) substituted styrene wherein the substituents are on the vinyl group or on the aromatic ring of the styrene, for example alpha-methylstyrene and vinyltoluene.
[0050] Suitable vinyl aromatic monomers may preferably contain 8 to 20 carbon atoms, most preferably 8 to 14 carbon atoms. Styrene and substituted styrenes are preferred, wherein the substituents, if present, are C 1 -C 6 alkyl.
[0051] Examples of vinyl aromatic monomers are styrene including substituted styrenes, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, tert-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, α-methylstyrene, and halogenated styrenes.
[0052] Preferably, the hydrophobic monomer may be styrene, α-methylstyrene, p-methylstyrene, tert-butylstyrene, or a combination thereof. More preferably, the hydrophobic monomer may be styrene.
[0053] Alkyl acrylates of monoalkyl polyethylene glycols may be preferred as nonionic hydrophilic monomers.
[0054] As part of the alkyl acrylate or monoalkyl, the alkyl group may be independently selected from C 1 -C 6 Alkyl, and especially C 1 -C 3 Alkyl. The alkyl group may preferably be selected from methyl, ethyl, n-butyl, or tert-butyl. Preferably, the alkyl group is methyl.
[0055] The number average molecular weight of the monoalkyl polyethylene glycol (ie, the alkyl acrylate of only the PEG chain and not the entire monoalkyl polyethylene glycol) may be at least 300 Daltons, preferably in the range of 350 to 900 Daltons, more preferably in the range of 400 to 600 Daltons.
[0056] Certain monoalkyl polyethylene glycols used as starting materials in the present invention are commercially available. Thus, methyl ethers of total molecular weights of 500 and 550, designated in the market as methoxy polyethylene glycol 550 and methoxy polyethylene glycol 750, respectively, are commercially available.
[0057] Preferably, the alkyl acrylate of monoalkyl polyethylene glycol is methoxy polyethylene glycol methacrylate (MPEGMA), and more particularly methoxy polyethylene glycol 500 methacrylate.
[0058] Strong acid derivatives of (meth)acrylic acid may include strong acids containing a sulfuric acid or sulfonic acid group (or a salt thereof). Examples of such monomers include acrylamidomethylpropylsulfonate (AMPS) and isethionate (meth)acrylate.
[0059] When present, the strong acid modified monomer typically constitutes from 1 to 30 mole %, more typically from 2 to 20 mole %, and suitably from 5 to 15 mole % of the acrylic acid monomers in the copolymer.
[0060] The polymer may be formed from hydrophobic monomers and may be a water-soluble polymer, the solubility occurring as a result of neutralization of the polymer.
[0061] It should be understood that the term "copolymer" as used herein includes polymers having two components as well as trimers and tetramers, and generally includes any polymer having two or more components. The copolymer may preferably be a random trimer or tetramer, optionally with a strong acid derivative of a (meth)acrylic acid monomer.
[0062] The copolymer may be formed by any suitable method and it may include free radical solution polymerisation or controlled living polymerisation.The monomers may be added simultaneously over a period of time in a controlled manner with a suitable initiator.
[0063] The amount of acrylic acid monomer present in the polymer can range from 10% to 90% by weight. Preferably, 15% to 60% by weight. More preferably, 20% to 50% by weight. Most preferably, 30% to 40% by weight.
[0064] The amount of vinyl aromatic monomer present in the polymer may range from 10% to 90% by weight. Preferably, 15% to 60% by weight. More preferably, 15% to 40% by weight. Most preferably, 20% to 30% by weight.
[0065] The amount of the alkyl acrylate monomer of polyethylene glycol present in the polymer can range from 10% to 90% by weight. Preferably, 15% to 60% by weight. More preferably, 20% to 50% by weight. Most preferably, 30% to 40% by weight.
[0066] When present, the strong acid modified monomers typically constitute from 1 to 30 wt %, more typically from 2 to 20 wt %, suitably from 5 to 15 wt %, and most preferably from 8 to 12 wt % of the acrylic acid monomers in the copolymer.
[0067] Other monomers can be included, such as acidic monomers such as itaconic acid or maleic acid or anhydride; strongly acidic monomers such as methallyl sulfonic acid (or salt); or non-acidic acrylic monomers such as acrylic acid esters, which may be alkyl esters, especially C 1 To C 6 Alkyl esters such as methyl methacrylate, butyl methacrylate or butyl acrylate, or hydroxyalkyl esters, especially C 1 To C 6 Hydroxyalkyl esters such as hydroxyethyl methacrylate or hydroxypropyl methacrylate; or vinyl monomers such as vinyl acetate. Generally, the proportion of the other monomers relative to the total monomers used will be no greater than about 10 mol%, usually no greater than about 7 mol%, and more usually no greater than about 5 mol%.
[0068] The polymer may have a molecular weight of less than 500,000 Daltons. Preferably, less than 100,000 Daltons. More preferably, less than 75,000 Daltons. The molecular weight may be in the range of 5,000 to 75,000 Daltons. More preferably, in the range of 10,000 to 60,000 Daltons. Still preferably, in the range of 15,000 to 50,000 Daltons. Most preferably, in the range of 20,000 to 40,000 Daltons.
[0069] The polymer can be used as a free acid or as a salt. In practice, the form present in the formulation will depend on the acidity of the formulation. Suitably, the formulation will be close to neutral so that most of the acid groups will exist as salts. The cation in any of the salts can be an alkali metal, particularly sodium and / or potassium, ammonium or an amine, including alkanolamines such as ethanolamine, particularly triethanolamine. In particular, the sodium or potassium salt form of the stabilized polymer is preferred.
[0070] The polymer or the monomers contained therein may be neutralized with at least 50% of the neutralizing agent. Preferably, it may be neutralized with at least 70% and preferably 75% to 85% of the neutralizing agent. Neutralization with sodium is preferred.
[0071] The pH of the polymer may range from 4.0 to 11.0. More preferably, it ranges from 5.0 to 10.0. Still more preferably, it ranges from 5.5 to 9.0. Most preferably, it ranges from 6.0 to 8.0.
[0072] The dispersant may be selected from nonionic graft copolymers of acrylates and alkylene oxides.
[0073] The acrylate may be a non-acidic acrylic monomer, such as an acrylate, which may be selected from alkyl esters, especially C 1 To C 6 Alkyl ester. Preferably, the alkyl ester can be selected from methyl methacrylate, butyl methacrylate or butyl acrylate. Methyl methacrylate is most preferred.
[0074] The number of acrylate monomer residues in the (poly)acrylate chain will preferably range from 2 to 50, more preferably from 5 to 40, and especially from 10 to 30.
[0075] The oxyalkylene group may be selected from the formula −(C y H 2y O)-
[0076] wherein y is an integer selected from 2, 3 or 4. Preferably, y is 2 or 3.
[0077] The oxyalkylene group may be selected from oxyethylene, oxypropylene, oxybutylene or oxytetramethylene. Preferably, the oxyalkylene group is selected from oxyethylene (EO) and / or oxypropylene (PO).
[0078] In the case where the oxyalkylene chain is homopolymeric, homopolymers of ethylene oxide or propylene oxide are preferred. More preferably, homopolymers of ethylene oxide are particularly preferred.
[0079] In the case where there are more than one oxyalkylene group (i.e. where n is 2 or more) and at least two are part of the same oxyalkylene chain, the oxyalkylene groups along the oxyalkylene chain may be the same or may be different. In this embodiment, the oxyalkylene chain may be a block or random copolymer of different oxyalkylene groups 5.
[0080] Typically, where a copolymer chain of oxyethylene and oxypropylene units is used, the molar proportion of oxyethylene units used will be at least 50% and more typically at least 70%.
[0081] The total number of alkylene oxide residues in the (poly)alkylene oxide chain will preferably be in the range of 2 to 50, more preferably 5 to 40, and especially 10 to 25.
[0082] The molecular weight of the nonionic graft copolymer of acrylate and alkylene oxide is generally 5,000 to 40,000, particularly 7,000 to 30,000, more particularly 8,000 to 25,000 and especially about 9,000 to 18,000.
[0083] Any nonionic graft copolymer of acrylate and alkylene oxide may be used. Preferably, the copolymer may be a nonionic polymethyl methacrylate-polyethylene oxide graft copolymer.
[0084] Other suitable dispersants may include naphthalene sulfonate blends, sodium N-methyloleyl taurate, or sodium dioctyl sulfosuccinate, or sodium lignin sulfonate.
[0085] The filler may be selected from mica particles coated with metal oxides, kaolin, calcium carbonate, or silicon dioxide. The particles have a particle size of 1 µm to 100 µm and a bulk density of 0.2 g / mL to 0.6 g / mL.
[0086] In some cases, the base material comprises mica coated with a layer of a metal oxide including, but not limited to, titanium dioxide, iron oxide, chromium oxide, or zirconium oxide.
[0087] In particular, preferred fillers include silicon dioxide, or titanium coated mica. Particularly preferably, the filler may be selected from mica particles coated with titanium dioxide in the anatase or rutile form or with a layer of iron oxide.
[0088] The bulk density of the filler may preferably be in the range of 0.20 to 0.60 mg / L, more preferably in the range of 0.25 to 0.55 mg / L, and still more preferably in the range of 0.30 to 0.53 mg / L.
[0089] It should be understood that, unless otherwise stated, the bulk density values described herein refer to the tapped bulk density, wherein the tapped density refers to the bulk density of the powder after a specified compaction process (usually involving container vibration). The bulk density to which the present invention relates is determined in accordance with CIPAC MT033 Content Handbook F "Tap Density".
[0090] The filler suitably has a median particle size in the range 0.1 to 50 μm, preferably 0.5 to 30 μm, more preferably 0.8 to 25 μm. Most preferably, 1 to 20 μm.
[0091] The particle size values are measured by a laser diffraction-based technique, which is used to determine the average particle size value. The filler sample is dispersed in an aqueous medium and homogenized, and the dispersion is analyzed by means of a device (e.g., Malvern Masterziser) that generates particle size distribution information by laser diffraction. The results are expressed as a size distribution curve calculated by the software as well as percentile values D10, D50, and D90 data (which are statistical parameters of the cumulative particle size distribution, which indicate the size below which 10%, 50%, or 90% of all particles are below).
[0092] The weight average molecular weight of the filler particle material may range from 1,000 to 5,000,000. Preferably, it ranges from 50,000 to 2,000,000. More preferably, it ranges from 100,000 to 1,000,000, and most preferably, from 150,000 to 300,000.
[0093] The filler particles may be homogeneous in that they consist of only one specific type of filler, for example all of the same composition and / or of equal molecular weight. In alternative embodiments, the filler particles may be heterogeneous in that they comprise a mixture, such as a mixture of different molecular weights.
[0094] Mineral-based fillers may preferably have a water absorption capacity greater than 50%, preferably greater than 60%. Water absorption refers to the ability of a substance to absorb water when immersed in water and is represented by the water absorption capacity, which is the ratio of the weight of water absorbed by the substance in a saturated state to the weight of dry matter.
[0095] The dispersant and filler are combined to provide a premix formulation suitable for forming a WP or WDG. The premix comprises the dispersant and the filler, may consist essentially of the dispersant and the filler, or may consist of the dispersant and the filler.
[0096] The amount of dispersant contained in the premix may be in the range of 2% to 20% by weight. More preferably, in the range of 4% to 15%. Still more preferably, in the range of 5% to 12%. Most preferably, in the range of 6% to 10%, as a percentage of the total premix.
[0097] The amount of filler contained in the premix may be in the range of 98% to 80% by weight. More preferably, in the range of 96% to 85%. Still more preferably, in the range of 95% to 88%. Most preferably, in the range of 94% to 90%, as a percentage of the total premix.
[0098] The weight ratio of dispersant to filler in the premix is preferably from about 0.05: 1 to about 0.2: 1. More preferably, from about 0.08: 1 to about 0.12: 1. This ratio range will generally be maintained for the premix, WP / WDG, and the diluted WP / WDG used in the spray formulation.
[0099] In the present application, microorganisms refer to fungi and bacteria which are in solid form and have relevant applications in agriculture as biological control, biological control agent, biopesticide and / or biological fertilizer or biofertilizer.
[0100] Biopesticides inherently attack other microorganisms and / or macroorganisms by several mechanisms and have therefore for many years been considered as a means of combating pests, particularly those in agriculture, etc. For example, bacteria that are toxic to insects have long been known and commercial insecticides based on such bacteria have been available for many years now.
[0101] Yet another important example is the use of fungi and / or bacteria which produce certain secondary metabolites (eg antibiotics, fungicides, bactericides, enzymes) for controlling plant diseases and / or insect pests.
[0102] Biological pesticides have clear and substantial advantages: being selective or highly specific for a particular target and generally being environmentally safe. As a result, interest and attention in them has increased in recent years.
[0103] Biopesticide actives may preferably be any microbiological organisms conventionally used for plant, seed or soil treatment. Biopesticides refer to biologically active substances, which in the context of the present invention are plant protection agents, more particularly microorganisms, which can kill and / or control different forms of organisms harmful to crops (such as pests and / or plant diseases) through different mechanisms.
[0104] Biopesticides may include biological fungicides, herbicides, insecticides (insecticides), algaecides, molluscicides, miticides, and rodenticides.
[0105] The biopesticide may be selected in particular from microorganisms that are spores and / or another structure of fungi, bacteria, yeasts and / or actinomycetes, but without limitation.
[0106] The characteristic of biofertilizer is the material containing living microorganisms, which can colonize in the rhizosphere or inside of cultivated crops and promote growth by increasing the supply or availability of major nutrients to host plants when applied to seeds, plant surfaces or soil. Biofertilizer can stimulate plant growth through natural processes such as nitrogen fixation, solvated phosphorus and / or through synthetic growth-promoting substances (such as precursors of plant growth hormones, gibberellins, ethylene) to provide nutrients to plants. Using biofertilizer can be expected to reduce the use of synthetic fertilizers and pesticides during the harvest season.
[0107] The biological fertilizer may be chosen in particular from microorganisms, which are spores and / or further structures of fungi, bacteria and / or yeasts.
[0108] Preferred bacterial strains for biofertilizers may be selected from the genera Rhizobium, Sinorhizobium, Mesorhizobium, Bradyrhizobium, Azorhizobium, and Allorhizobium.
[0109] The premix will be combined with microbial spores and / or another microbial structure to form a WP or WDG.
[0110] The amount of dispersant contained in the WP / WDG may be in the range of 1% to 20% by weight. More preferably, in the range of 2% to 15%. Still more preferably, in the range of 3% to 10%. Most preferably, in the range of 4% to 7%, as a percentage of the total WP / WDG.
[0111] The amount of filler contained in the WP / WDG may be in the range of 98% to 40% by weight. More preferably, in the range of 92% to 50%. Still more preferably, in the range of 90% to 60%. Most preferably, in the range of 87% to 62%, as a percentage of the total WP / WDG.
[0112] The amount of biopesticide or biofertilizer contained in WP / WDG may be in the range of 40% to 5% by weight, more preferably in the range of 35% to 7%, and still more preferably in the range of 32% to 8%, as a percentage of the total WP / WDG.
[0113] Both wettable powders (WP) and water dispersible granules (WDG) have been found to be particularly effective formulation forms for containing high amounts of biopesticide or biofertilizer spores and / or other microbial structures.
[0114] Wettable powders are to be understood as systems of spores and / or other microbial structures of biopesticides or biofertilizers, surfactants / dispersants and fillers, which form a suspension with water. WPs may contain wetting agents that promote suspension of the particles in water. WPs may be used in spray formulations and / or seed coating formulations.
[0115] Water dispersible granules are to be understood as granular formulations of the particle size of wettable powders, to be applied after disintegration and dispersion in water. WDGs are generally composed of the following: actives formulated as powders and processed into granules, wetting agents, dispersants and a mixture of fillers / diluents / disintegrants. WDGs may be particularly suitable for use in spray formulations.
[0116] The formulation containing the spores / microorganisms or other structures is placed in a spray tank to be sprayed onto the field or applied to seeds.
[0117] WP and WDG are designed to be diluted with water (or water-based liquids) to form corresponding end-use agronomic and agrochemical formulations, typically spray formulations.
[0118] For agronomic efficacy, active compounds require formulations that allow the active compound to be absorbed by the plant / target organism. Where concentrates (solid or liquid) are used as a source of active agrochemicals and / or adjuvants, the concentrates are generally diluted to form a final use formulation, generally a spray formulation.
[0119] Dilution may be performed with water in an amount of 1 to 10,000, especially 10 to 1,000 times the total weight of the concentrate to form a spray formulation.
[0120] The WP / WDG can be diluted for use to obtain a diluted composition that obtains a concentration of about 0.5% to about 5% by weight of the agrochemical active agent. In the diluted composition (e.g., a spray formulation, where the spray application rate can be 10 to 500 l.ha -1 ), the concentration of the biologically active agent may be from about 0.001% to about 2% by weight of the total formulation sprayed.
[0121] Spray formulations are aqueous agronomic formulations including all components that are desired to be applied to plants or their environment. Spray formulations can be prepared as follows: simple dilution of WP / WDG containing the desired components (except water), or a combination of diluting WP / WDG and adding other individual components or component mixtures. Generally speaking, this end-use mixing is carried out in the tank from which the spray formulation is sprayed, or alternatively in a storage tank for filling the spray tank. The mixing and mixtures are generally referred to as tank mixes and tank mixes.
[0122] Spray formulations generally have a pH ranging from mildly acidic (e.g., about 3) to mildly alkaline (e.g., about 10), and particularly a near-neutral pH (e.g., about 5 to 8). More concentrated formulations have similar acidity / alkalinity, but since they may be substantially non-aqueous, pH is not necessarily an appropriate measure thereof.
[0123] The agrochemical formulation may include a solvent (other than water) such as monopropylene glycol, an oil which may be a vegetable oil or a mineral oil such as a spray oil. The solvent may be included as a solvent for the surfactant adjuvant and / or as a humectant such as, in particular, propylene glycol. When used, the solvent is generally included in an amount of 5% to 500% by weight, suitably 10% to 100% by weight, of the weight of the surfactant adjuvant. The combination may also include a salt such as ammonium chloride and / or sodium benzoate and or urea, in particular as a gel inhibition adjuvant.
[0124] The diluted WP / WDG tank mix can be sprayed on the soil or used as a foliar spray.
[0125] The WP / WDG formulations described can also be used in seed treatments and seed coatings, for example in aqueous film coatings for seeds, such as film coating, encrusting or pelleting.
[0126] WP / WDG formulations can be applied to seeds in liquid form by diluting in water before application. Alternatively, they can be applied as part of a dry powder during the seed treatment process.
[0127] The WP / WDG formulations described herein can be applied during a film coating process, a shelling process, or a granulation process.
[0128] In particular, the present invention can be preferably used when treating seeds selected from corn, soybean, fodder and lettuce.
[0129] Premix, WP / WDG, seed coating formulation or diluted WP / WDG may also include other components as required. These other components may be selected from those including the following:
[0130] Binders, particularly those readily soluble in water to provide low viscosity solutions at high binder concentrations, such as polyvinyl pyrrolidone; polyvinyl alcohol; carboxymethyl cellulose; gum arabic; sugars such as sucrose or sorbitol; starch; ethylene-vinyl acetate copolymers, sucrose and alginates,
[0131] diluents, absorbents or carriers such as carbon black; talc; diatomaceous earth; kaolin; aluminum, calcium or magnesium stearate; sodium tripolyphosphate; sodium tetraborate; sodium sulfate; sodium silicate, aluminum silicate and mixed sodium-aluminum silicate salts; and sodium benzoate,
[0132] disintegrants, such as surfactants, substances that swell in water, for example, carboxymethylcellulose, collodion, polyvinylpyrrolidone and microcrystalline cellulose; swelling agents; salts such as sodium or potassium acetate, sodium carbonate, bicarbonate or sesquicarbonate, ammonium sulfate and dipotassium hydrogen phosphate;
[0133] Wetting agents such as alcohol ethoxylates and alcohol ethoxylate / propoxylate wetting agents;
[0134] dispersants such as sulfonated naphthaldehyde condensates and acrylic copolymers such as comb copolymers with end-capped polyethylene glycol side chains on a polyacrylic acid backbone;
[0135] Emulsifiers such as alcohol ethoxylates, ABA block copolymers, or castor oil ethoxylates;
[0136] Antifoaming agents such as silicone antifoaming agents, generally in amounts of 0.005% to 10% by weight of the formulation;
[0137] Viscosity modifiers such as commercially available water-soluble or miscible gums, for example xanthan gum, and / or cellulosic materials, for example carboxymethyl, ethyl or propyl cellulose; and / or
[0138] Preservatives and / or antimicrobials such as organic acids or their esters or salts such as ascorbic acid, for example ascorbyl palmitate, sorbic acid, for example potassium sorbate, benzoic acid, for example methyl and propyl benzoic acid and 4-hydroxybenzoate, propionic acid, for example sodium propionate, phenols, for example sodium 2-phenylphenol; 1,2-benzisothiazolin-3-one; or formaldehyde, either as such or as paraformaldehyde; or inorganic materials, for example sulphurous acid and its salts, are generally present in amounts of 0.01% to 1% by weight of the formulation.
[0139] The premix, WP / WDG, seed coating formulation, or diluted WP / WDG may also include agrochemical actives or nutrients as desired.
[0140] The agrochemical active agent may preferably be a solid-phase agrochemical active agent. Solid agrochemical active agent compounds are understood in the present invention to mean all substances conventionally used for plant or seed treatment with a melting point above 20° C. (standard pressure). Solid agrochemical active agents also include insoluble active ingredients, i.e. active ingredients whose solubility in water is such that after addition, a significant solid content is present in the concentrate.
[0141] Agrochemical active agents are biocides, which in the context of the present invention are plant protection agents, more particularly chemical substances which are used in various fields such as medicine, agriculture, forestry and mosquito control and which can kill and / or control different forms of living organisms. Also included in the class of biocides are so-called plant growth regulators.
[0142] Biocides used in the agrochemical formulations of the present invention are generally divided into two subclasses:
[0143] Pesticides, including fungicides, herbicides, insecticides (insecticides), algaecides, molluscicides, miticides and rodenticides; and
[0144] Antimicrobial agents, including bactericides, antibiotics, antibacterials, antivirals, antifungals, antiprotozoals and antiparasitics.
[0145] In particular, a biocide selected from pesticides (insecticides), fungicides or herbicides may be particularly preferred.
[0146] The term 'pesticide' is understood to mean any substance or mixture of substances which is intended for use in preventing, destroying, repelling or mitigating any pest or plant disease. Pesticides may be chemical substances or biological agents (such as viruses, fungi or bacteria) used to combat pests, including insects, plant pathogens, weeds, molluscs, birds, mammals, fish, nematodes (roundworms) and microorganisms that compete with humans for food, destroy goods, spread disease or become a nuisance. In the following examples, pesticides suitable for the agricultural chemical compositions of the present invention are provided.
[0147] Fungicides are chemical control agents for fungi. Fungicides are compounds used to prevent the spread of fungi in gardens and crops. Fungicides are also used to combat fungal infections. Fungicides can be contact or systemic. Contact fungicides kill fungi when sprayed onto their surfaces. Systemic fungicides must be absorbed by the plant to subsequently kill the fungi.
[0148] According to the present invention, examples of suitable fungicides include the following classes: (3-ethoxypropyl) mercuric bromide, 2-methoxyethyl mercuric chloride, 2-phenylphenol, 8-hydroxyquinoline, 8-phenylmercuric hydroxyquinoline, acibenzolar, acylamino acid fungicides, acypetacs, aldimorph, aliphatic nitrogen fungicides, allyl alcohol, amide fungicides, ampropylfos, dithiocarb, acylanilide fungicides, antibiotic fungicides, aromatic fungicides, aureofungin, oxepiconazole, azithiram, azoxystrobin, barium polysulfide, bensulfuron, bensulfuron, benomyl, quinone oxime hydrazone, bentaluron, benthiavalicarb, benzalkonium chloride, benzamacril, benzamide fungicides, benzamorf, benzanilide fungicides, benzimidazole fungicides, benzimidazole precursor fungicides, benzimidazolyl carbamate fungicides, benzohydroxamic acid, benzothiazole fungicides, bethoxazin, binachlor, biphenyl, triadimefon, thiochlorophenol, blasticidin, Bordeaux mixture, boscalid, bridged diphenyl fungicides, oxadiazole, pyrimidine sulfonate, Bordeaux mixture , butylthiocarb, butylamine, calcium polysulfide, captamidophthalide, captan, carbamate fungicides, morphine, phenylcarbamate / ester fungicides, carbendazim, carboxin, cyproconazole, carvone, Cheshunt mixture, mite-killing agent, chlobenthiazone, chloraniformethan, tetrachloroquinone, chlorfenazole, chlorodinitronaphthalene, chloroanisole, chloropicrin, thiophanate-methyl, tetrachloroquinoxaline, ethoxyconazole, ciclopirox, imidacloprid, clotrimazole, conazole fungicide, conazole fungicide fungicides (imidazoles), conazole fungicides (triazoles), copper (II) acetate, basic copper (II) carbonate, copper fungicides, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper (II) sulfate, basic copper sulfate, copper zinc chromate, cresol, cufraneb, cuprobam, cuprous oxide, cyazofamid, cyclamic acid amide, cyclic dithiocarbamate / ester fungicides, cycloheximide, cycloheximide, cymoxanil, cyanamide, cyproconazole, cyprodinil, dazomethanil, dibromochloropropane, imidacloprid, decafentin, dehydroacetic acid acid), dicarboximide fungicides, benzene flusulfamide, dichloronaphthoquinone, dichlorophen, dichlorophenyl, dicarboximide fungicides, sclerotin, benzyltriadol, dichlorocyanamide, pyrochloranil, chloranil, ethochlor, diethyl pyrocarbonate, fenpropimorph, fluazifop, dimethomorph,dimethomorph, diniconazole, dinitrophenol fungicide, chloranil, dinitrocrotonate, dinocton, dinopenton, dinosulphon, dinoterbon, diphenylamine, dipyrithione, disulfiram, dimethoate, dicyanoanthraquinone, dithiocarbamate fungicide, dinitrophenol, dodecanol, dodecyl morpholine, dodecyl morpholine, dodecyl morpholine, donatidine, DONATODINE, cyclohexanone, dichlorvos, fluopicolide, ethyl Cyproconazole, mancozeb, ethaboxam, ethoxyquin, 2,3-dihydroxypropylmercury ethylmercury, ethylmercury acetate, ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate, thiabendazole, famoxadone, imidacloprid, sodium sulfamethoxam, imidacloprid, chlorfenapyr, fenthiocarb, furamide, cyclamoxadone, seed coat ester, rice blastamide, fenpropathrin, fenpropidin, fenbutamide, triphenyltin, ferbam, pyrimidine, fluazinam, fludioxonil, fluoxamidopyram, fluclorac, trifloxystrobin, fluoxastrobin, fluquinconazole, flusilazole, sulfamethoxam, flutolanil, flutriafol , foltan, formaldehyde, phosphonic acid, wheat spike, furalaxyl, furazolidone, furamide fungicide, furanilide fungicide, dimethylfuran, furconazole, furconazole, furfural, seed dressing amine, furthiophanate-methyl, fruit green pyridine, griseofulvin, biguanide, quinoline acrylate, hexachlorobenzene, hexachlorobutadiene, toxic fungol, hexaconazole, hexylthiofos, mercury plus phenanthate, oxadiazine, imazalil, imidoazole, imidazole fungicide, biguanide, inorganic fungicide, inorganic mercury fungicide, iodomethane, imidoconazole, isopyruvate Bifungin, isoprodinil, valproic acid, pyraclostrobin, isovaledione, kasugamycin, kresoxim-methyl, lime sulfur, mancozeb, mancozeb, maneb, o-amide, mecarbinzid, pyraclostrobin, sulfamethoxam, mercuric chloride, mercuric oxide, mercurous chloride, mercuric fungicide, metalaxyl, metalaxyl-M, metam, metazoxolon, metconazole, sulfamethoxam, furazolidone, methyl bromide, methyl isothiocyanate, methyl mercuric benzoate, methyl mercury dicyandiamide dicyandiamide), pentachlorophenol methylmercuric salt, mesamiprole, metrafenone, metrafenone, mesamiprole, mesamiprole, morpholine fungicides, myclobutanil, meclofenoxate, N-(ethylmercury)-p-toluenesulfonylanilide, manson sodium, natamycin, nitrostyrene, phthalocyanine, flufenoxanol, OCH, octhilamide, furamide, organic mercury fungicides, organophosphorus fungicides, organotin fungicides, oxamoxadone, oxaloxane, oxathiapiprolin fungicides, oxazole fungicides, quinoline copper, oxpoconazole, oxycarboxin, pyralidone, penconazole, pencuron, pentachlorophenol,Penthiopyrad, phenylmercury urea, phenylmercury acetate, phenylmercury chloride, pyrocatechol phenylmercury derivatives, phenylmercury nitrate, phenylmercury salicylate, phenylsulfonamide fungicides, chlorpyrifos, tetrachlorophthalide, phthalimide fungicides, picoxystrobin, pyraclostrobin, mancozeb zinc, polymer dithiocarbamate fungicides, polyoxin, polyoxorim, polysulfide fungicides, potassium azide, potassium polysulfide, potassium thiocyanate, allylbenzazole, prochloraz Amine, Procymidone, Cyproconazole, Propiconazole, Propineb, Propoxyquin, Thiophanate, Prothioconazole, Pyraclostrobin, Pyraclostrobin, Pyrazole fungicides, Pyraclofos, Pyridine fungicides, Pyraclostrobin, Pyrimidine fungicides, Pyroxychlor, Pyroxypyralid, Pyrrole fungicides, Quinacetol, Quinazamid, Quinconazole, Quinoline fungicides, Quinones fungicides, quinoxaline fungicides, quinoxyfen, pentachloronitrobenzene, rabenzazole, salicylanilide, silthiopyrad, siloxane, sodium azide, sodium o-phenylphenol, sodium pentachlorophenol, sodium polysulfide, spiroxane, streptomycin, strobilurin fungicides, sulfonylanilide fungicides, sulfur, sultropen, TCMTB, tebuconazole, foliar thiophene fungicide, tetrachloronitrobenzene, tecoram, tetrafluconazole, thiabendazole, thiadifluor, thiazole fungicide, thiodimethoate, thiofluanid, thiocarbamate fungicide, thiochlorfenphim, thimerosal, thiophanate, methyl thiophanate, thiophene fungicide, cypermethrin, thiram, thiabendazole, tioxymid, tivedo, methyl tolclofos, tolnaftate, tolylfluanid, tolylmercury acetate acetate), triadimefon, triadimenol, cypermethrin, triarimol, oxadiazine, triazine fungicide, triazole fungicide, imidazobacter, tributyltin oxide, salicylate, tricyclazole, trifloxystrobin, triflumizole, triaminate, trichlorfon, unclassified fungicide, undecylenic acid, uniconazole, urea fungicide, validamycin, valinamide fungicide, vinclozolin, cyanamide, zinc cyclohexaneate, mancozeb, ziram, zoxamide and mixtures thereof.
[0149] Herbicides are pesticides used to kill unwanted plants. Selective herbicides kill specific targets, leaving the desired crop relatively unharmed. Some of them work by interfering with weed growth and are often based on plant hormones. Herbicides used to clear wasteland are non-selective and kill all plant matter they come into contact with. Herbicides are widely used in agriculture and in landscape turf management. They are used in total vegetation control (TVC) programs to maintain roads and railroads. Smaller amounts are used in forestry, pasture systems, and to manage areas where wildlife habitats are found.
[0150] Suitable herbicides may be selected from the group comprising aryloxycarboxylic acids such as 2-Methyl-4-chloro-4-pyridinium chloride, aryloxyphenoxypropionates such as clodinafop, cyclohexanedione oximes such as sethoxydim, dinitroanilines such as trifluralin, diphenyl ethers such as oxyfluorfen, hydroxybenzonitriles such as bromoxynil, sulfonylureas such as nicosulfuron, triazolopyrimidines such as penoxsulam, triketones such as mesotrione, or ureas such as diuron.
[0151] Particularly preferred herbicides may be selected from 2,4-dichlorophenoxyacetic acid (2,4-D), atrazine, dicamba as benzoic acid, glyphosate, imazapic as imidazolinone, isopropylamine as chloroacetamide, and amloprotinol, clopyralid, and triclopyrazone as pyridinecarboxylic acids or synthetic auxins.
[0152] Insecticides (insecticides) are pesticides used against all developmental forms of insects, and include ovicides and larvicides used against eggs and larvae of insects. Insecticides (insecticides) are used in agriculture, medicine, industry and in the home.
[0153] Suitable pesticides (insecticides) may include those selected from the group consisting of:
[0154] Chlorinated pesticides (insecticides) such as toxaphene, DDT, hexachlorocyclohexane, gamma-hexachlorocyclohexane, methoxychlor, pentachlorophenol, TDE, aldrin, chlordane, chlorphenone, dieldrin, endosulfan, endrin, heptachlor, mirex and mixtures thereof;
[0155] Organophosphorus compounds such as Acephate, Azinphos, Dimethoate, Chlorpyrifos, Chlorpyrifos-methyl, Diazinon, Dichlorvos (DDVP), Dicrotophos, Dimethoate, Dimethoate, Fenamiphos, Fenitrothion, Fenthion, Fenthiazate, Malathion, Methamidophos, Methidathion, Methyl-parathion, Mevinphos, Dibromophos, Oxymethoate, Sulfonate, Parathion, Phorate, Phosalone, Phosmet, Phostebupirim, Pirimiphos-methyl, Profenofos, Terbufos, Chlorpyrifos, Tribufos, Trichlorfon and mixtures thereof;
[0156] Carbamates such as aldicarb, carbofuran, carbaryl, methomyl, 2-(l-methylpropyl)phenylmethylcarbamate and mixtures thereof;
[0157] Pyrethroids such as allethrin, bifenthrin, deltamethrin, permethrin, resmethrin, sumithrin, tetramethrin, tralomethrin, transfluthrin and mixtures thereof;
[0158] Plant toxin-derived compounds such as Derris (rotenone), Pyrethrum, Neem (azadirachtin), Nicotine, Caffeine and mixtures thereof;
[0159] Neonicotinoids such as imidacloprid;
[0160] Avermectins, such as avermectin;
[0161] Oxadiazines such as indoxacarb;
[0162] Anthranilic acid diamides such as chlorantraniliprole (rynaxypyr).
[0163] Rodenticides are a class of pest control chemicals that are intended to kill rodents. Suitable rodenticides may include anticoagulants, metal phosphides, phosphides, and calciferol (vitamin D), and derivatives thereof.
[0164] Acaricides are pesticides that kill mites. Antibiotic acaricides, carbamate acaricides, formamidine acaricides, mite growth regulators, organochlorines, permethrins and organophosphate acaricides all belong to this category. Molluscicides are pesticides used to control mollusks such as moths, slugs and snails. These substances include metaldehyde, methiocarb and aluminum sulfate. Nematicides are a type of chemical pesticide used to kill parasitic nematodes (a phylum of worms).
[0165] In the following examples, antimicrobial agents suitable for the agrochemical compositions of the present invention are provided.
[0166] Disinfectants may include those selected from the group consisting of active chlorine, active oxygen, iodine, concentrated alcohols, phenolic substances, cationic surfactants, strong oxidants, heavy metals and their salts, and concentrated strong acids and bases at pH 1 to 13. Suitable antimicrobial agents (i.e., antiseptics that can be used on the human or animal body, skin, mucous membranes, wounds, etc.) may include dilute chlorine preparations, iodine preparations, peroxides, alcohols with or without antimicrobial additives, weak organic acids, phenolic compounds, and cation-active compounds.
[0167] Particularly preferred are active compounds from the following classes: azole fungicides (oxepiconazole, bifenthrin, oxadiazole, cyproconazole, benzyltriazole, difenoconazole, diniconazole, R-diniconazole, epoxiconazole, ethiconazole, clofenac, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furiconazole, furoconazole, hexaconazole, imazalil, imazalil sulfate, imidazole, imipenem, metconazole, myclobutanil, flufenac, oxpoconazole, paclobutrazol, penconazole, pyraclostrobin, prochloraz, propiconazole, prothioconazole, pyrimidine oxime, silyfenazole, tebuconazole, tetraconazole, triadone, triazole alcohol, flubamiprid, trifloxystrobin, trimethoprim, uniconazole, voriconazole, viniconazole), strobilurin fungicides (azoxystrobin, dimethomorph, fluoxastrobin, kresoxim-methyl, fenoxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin), SDH fungicides, chloronicotinyl insecticides (clothianidin, dinotefuran, imidacloprid, thiamethoxam, nithiazin, acetamiprid, nitenpyram, thiamethoxam), insecticides enols (spiroclofen, spiromesifen, spirotetramat), fiproles (fiprole, ethiprole) and butenolide, as well as pymetrozine, fluopyram, N-(3',4'-dichloro-5-fluoro-1,1'-biphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide and N-{2-[3-chloro-5-(trifluoromethyl)-2-pyridyl]ethyl}-2-(trifluoromethyl)benzamide. Herbicides, especially sulfonylureas, triketones and herbicide enols and safeners are also particularly preferred.
[0168] Nutrients may be present in addition to or in place of the agrochemical actives. In the formulations, the nutrients are generally in dry form.
[0169] The nutrients may preferably be solid-phase nutrients. Solid nutrients are understood in the present invention to mean substances with a melting point above 20° C. (at standard pressure). Solid nutrients also include insoluble nutrient ingredients, i.e. nutrient ingredients whose solubility in water is such that after addition there is a significant solid content in the concentrate.
[0170] Nutrients refer to chemical elements and compounds that are desirable or necessary to promote or improve plant growth. Suitable nutrients are generally described as macronutrients or micronutrients. Suitable nutrients for use in the concentrates according to the invention are all nutrient compounds.
[0171] Micronutrients generally refer to trace metals or trace elements, and are often administered in lower doses. Suitable micronutrients include trace elements selected from zinc, boron, chlorine, copper, iron, molybdenum and manganese. Micronutrients can be in soluble form or included as insoluble solids, and can be salts or chelated.
[0172] Macronutrients generally refer to those containing nitrogen, phosphorus and potassium, and include fertilizers such as ammonium sulfate, and water conditioners. Suitable macronutrients include fertilizers and other nitrogen, phosphorus, potassium, calcium, magnesium, sulfur compounds, and water conditioners.
[0173] Suitable fertilizers include inorganic fertilizers that provide nutrients such as nitrogen, phosphorus, potassium or sulfur. Fertilizers may be included in dilute formulations at relatively low concentrations or as more concentrated solutions, which at very high levels may include solid fertilizers as well as solutions.
[0174] It is contemplated that the inclusion of nutrients will depend on the specific nutrient: wherein micronutrients will generally be included in lower concentrations, and macronutrients will generally be included in higher concentrations.
[0175] The WP / WDG of the present invention provide improved spore / microorganism viability and thus better shelf life. They exhibit excellent efficacy combining a dispersion effect with an unexpected increase in fungal spore viability, thereby providing improved viability of the microorganisms.
[0176] At 25°C, within 180 days, the formulations according to the invention have a reduction in viability of the contained biopesticide of not more than 60% and preferably not more than 50%, wherein viability is as defined in the examples. It has been shown that the spore / microorganism reduction is reduced compared to without powder and dispersant.
[0177] The present invention also provides improved dispersibility capacity / capability in water and improved wettability in water.WP / WDGS are found to be self-dispersible, that is, they disperse directly, requiring limited or no agitation.
[0178] Additionally, the present invention provides improved mixing tank parameters - such as avoiding "lump formation" and nozzle clogging.
[0179] All features described herein may be combined with any of the above aspects in any combination. Example
[0180] In order that the present invention may be more readily understood, reference is now made to the following description, by way of example.
[0181] It should be understood that all tests and physical properties listed are determined at atmospheric pressure and room temperature (ie, 25°C) unless otherwise stated herein or unless otherwise indicated in the test methods and procedures described.
[0182] The following test method was used to determine the effectiveness of the adjuvant composition.
[0183] Sample preparation
[0184] Several liquid binder formulations were prepared according to Table 1 and using the materials listed below.
[0185] Mica granules, coated with TiO2 - particle size 10µm to 60µm, bulk density 0.343 g / mL
[0186] Kaolin - particle size 1µm to 20µm, bulk density 0.471 g / mL
[0187] Silica - particle size 15µm to 25µm, bulk density 0.166 g / mL
[0188] Metasperse 550S - Modified styrene acrylic polymer dispersant
[0189] Multiwet 8269 - Dioctyl sodium sulfosuccinate dispersant
[0190] Table 1. Composition (w / w) of wettable powder formulations used during the study.
[0192] All components were measured and blended until completely homogenized.After preparation, all samples were kept in a controlled environment at 20°C and 50% relative humidity throughout the evaluation period.
[0193] Test methods
[0194] The following test method was used.
[0195] Microbiological evaluation
[0196] All methods used to evaluate microbiological aspects followed the guidelines contained in IBR R&D WI 387 version 01. All evaluations were performed every 30 days up to 180 days after formulation, for a total of 7 evaluations.
[0197] Conidia viability assessment (direct viability)
[0198] To evaluate the viability of the conidia, it is necessary to carry out a dilution step for each formulation tested. To evaluate the viability, the dilution containing the conidia is pipetted into a Petri dish containing PDA (potato-dextrose-agar) medium. For each Petri dish, 10 drops of 15 µL are pipetted.
[0199] After adding the drop of conidia to the culture plates containing PDA medium, all culture plates were kept in a growth chamber protected from light at 25°C ± 1° for 15 hours. After the incubation period, 8 µL of lactophenol blue stain was used to paralyze conidia germination. Evaluation was performed after all the stain was absorbed by the culture medium. To evaluate the viability of conidia, 500 conidia were counted in each culture plate (a total of 5 evaluations per culture plate). Germinated and activated non-germinated conidia were considered viable)
[0200] The percentage of viable conidia was obtained for each drop using the following formula:
[0201] Viability (%) = (number of viable conidia / number of counted conidia) X 100
[0202] The final result was obtained by averaging the 5 drop evaluations.
[0203] Suspendability
[0204] Suspensibility was performed following the guidelines of CIPAC MT 184 (Suspensibility of a formulation diluted with water to form a suspension). The method involves weighing 2.5 g of the formulation in a standard cylindrical glass container containing water, adjusting the water volume to 250 mL, and leaving the system to stand in a 30°C water bath after homogenization. Finally, the percentage of solids remaining suspended in water after the standing time is calculated.
[0205] Survivability evaluation
[0206] The data were analysed for conidia viability evaluation and the results obtained are shown in Table 2. This shows the effect of different wettable powder formulations on the viability of Trichoderma asperellum conidia 180 days after formulation.
[0207] Table 2. Results obtained for the percentage of viable conidia 180 days after the formulation process. All results are expressed as percentage of viable conidia.
[0208] Regardless of the formulation composition, the addition of dispersants and fillers improved the percentage of viable conidia at 180 days after the formulation process compared to the control (pure conidia).
[0209] Even though all changes were not statistically different from each other, the 5% Metasperse 550S + 65% TiO 2 Formulations consisting of mica + 30% conidia, 5% Metasperse 550S + 65% kaolin + 30% conidia, 5% Metasperse 550S + 60% kaolin + 5% silica + 30% conidia, and 5% Metasperse 550S + 65% silica + 30% conidia showed higher cumulative conidia viability than other samples (except control) over the evaluation period, indicating the ability to be used as a biopesticide formulation.
[0210] Additionally, four of the six formulations with the highest cumulative viability over time contained dispersants and fillers; this indicates that the use of dispersants and fillers can mitigate the natural decrease in conidial viability observed in crude conidia of Trichoderma asperellum.
[0211] In terms of cumulative losses, the results are shown in Table 3 below:
[0212] Table 3. Absolute losses observed in conidia viability after 180 days of exposure to different wettable powder formulations.
[0213] All results were expressed as the cumulative percentage loss of conidia viability.
[0214] Taking into account the cumulative losses it can be observed that at 180 days after formulation the samples with dispersant and filler showed the lowest values concerning the loss of viability compared to the control.
[0215] Independently of the composition and based on the results obtained for the cumulative losses, it was observed that the inclusion of 5% of Atlox Metasperse 550S in the formulation reduced the loss of conidia viability up to 180 days after formulation.
[0216] The four formulations for which higher conidia viability values were detected were 5% Metasperse 550S + 65% coated with TiO 2 of mica + 30% conidia, 5% Metasperse 550S + 65% kaolin + 30% conidia, 5% Metasperse 550S + 60% kaolin + 5% silica + 30% conidia and 5% Metasperse 550S +65% silica + 30% conidia.
[0217] Suspendability evaluation
[0218] The suspensibility of WP formulated with spores was evaluated and the results are shown in Table 4 below.
[0219] Table 4. Suspensibility results
[0220] The suspendability results show that the choice of a particular filler can directly affect the suspension of solids.
[0221] In general and considering the results obtained for these four formulations, the results show that the use of dispersants and fillers can be advantageous, wherein the dispersants can attenuate the negative effects of fillers on conidia of Trichoderma asperellum.
[0222] It will be appreciated that the invention is not limited to the details of the above described embodiments, which are merely exemplary descriptions. Many variations are possible.
Claims
1. Wettable powder or water dispersible granules, comprising: (i) a dispersant selected from sulfonated naphthaldehyde condensates; acrylic copolymers having end-capped polyethylene glycol side chains on a polyacrylic acid backbone; copolymer dispersants comprising copolymers of acrylic acid, hydrophobic monomers, alkyl acrylates of monoalkyl polyethylene glycols and optionally strong acid derivatives of (meth)acrylic acid; nonionic graft copolymers of acrylates and alkylene oxides; or lignin sulfonates; (ii) Mineral-based fillers selected from: Mica particles coated with metal oxides; or Kaolin, silica, or calcium carbonate; Having a particle size of 1 µm to 100 µm and a bulk density of 0.2 g / mL to 0.6 g / mL; and (iii) at least one microorganism selected from fungal spores, or microorganisms having biopesticide or biofertilizer effects.
2. The wettable powder or water dispersible granules according to claim 1, wherein the dispersant is selected from water-dispersible styrene (meth) acrylic copolymers.
3. The wettable powder or water dispersible granules according to claim 1 or 2, wherein the polymer dispersant has a molecular weight of 750 to 20,000.
4. A wettable powder or water dispersible granules according to any preceding claim, wherein the metal oxide used for coating the mica particles is selected from titanium dioxide, iron oxide, chromium oxide, or zirconium oxide.
5. A wettable powder or water dispersible granules according to any preceding claim wherein the filler is selected from silica or titanium coated mica.
6. A wettable powder or water dispersible granules according to any preceding claim wherein the weight average molecular weight of the filler particle material is in the range of 50,000 to 2,000,000.
7. A wettable powder or water dispersible granules according to any preceding claim, wherein the mineral based filler has a water absorption capacity of greater than 50%.
8. Wettable powder or water dispersible granules comprising: (i) a dispersant selected from sulfonated naphthaldehyde condensates; acrylic copolymers having end-capped polyethylene glycol side chains on a polyacrylic acid backbone; copolymer dispersants comprising copolymers of acrylic acid, hydrophobic monomers, alkyl acrylates of monoalkyl polyethylene glycols and optionally strong acid derivatives of (meth)acrylic acid; nonionic graft copolymers of acrylates and alkylene oxides; or lignin sulfonates; (ii) a mineral-based filler selected from particles having a particle size of 1-60 µm, a bulk density of 0.2-0.6 g / ml and optionally a water absorption capacity greater than 50%; and (iii) at least one microorganism selected from fungal spores, or microorganisms having biopesticide or biofertilizer effects.
9. A wettable powder or water dispersible granule according to claim 8, wherein the mineral-based filler is selected from mica particles coated with metal oxides, or Kaolin, silica, or calcium carbonate.
10. A premix suitable for forming a wettable powder or water dispersible granules according to any one of claims 1 to 7, the premix comprising A dispersant selected from sulfonated naphthaldehyde condensates; acrylic copolymers having end-capped polyethylene glycol side chains on a polyacrylic acid backbone; copolymer dispersants comprising copolymers of acrylic acid, hydrophobic monomers, alkyl acrylates of monoalkyl polyethylene glycols and optionally strong acid derivatives of (meth)acrylic acid; nonionic graft copolymers of acrylates and alkylene oxides; or lignin sulfonates, and mineral-based fillers selected from: Mica particles coated with metal oxides; or Kaolin, silica, or calcium carbonate; With particle size ranging from 1µm to 100µm and bulk density ranging from 0.2 g / mL to 0.6 g / mL.
11. A premix according to claim 10, wherein the dispersant is selected from water dispersible styrene (meth) acrylic copolymers.
12. A premix according to claim 10 or claim 11 wherein the filler is selected from silica or titanium coated mica.
13. A process for preparing a wettable powder or water dispersible granules according to any one of claims 1 to 7, said process comprising mixing a premix according to claim 10 with at least one microorganism selected from microorganisms or fungal spores having a biopesticide or biofertilizer effect.
14. A formulation suitable for application to plants, comprising a dilute suspension of the wettable powder or water dispersible granules according to any one of claims 1 to 8.
15. A method for treating plants to control pests, the method comprising applying a diluted formulation according to any one of claims 1 to 8 to the plants or to the immediate vicinity of the plants.
16. A seed treatment formulation comprising the wettable powder or water dispersible granules according to any one of claims 1 to 8.
17. A method of treating seeds to control pests and diseases, the method comprising applying the formulation of claim 14 to the seeds.
18. A method for improving the viability of at least one beneficial microorganism on an agricultural target, comprising the step of combining on said agricultural target said beneficial microorganism selected from microorganisms or fungal spores having a biopesticide or biofertilizer effect with at least one dispersant as defined in any one of claims 1 to 8 and a mineral-based filler.