US20070072775A1 - Granular controlled release agrochemical compositions and process for the preparation thereof - Google Patents

Granular controlled release agrochemical compositions and process for the preparation thereof Download PDF

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Publication number
US20070072775A1
US20070072775A1 US11/238,376 US23837605A US2007072775A1 US 20070072775 A1 US20070072775 A1 US 20070072775A1 US 23837605 A US23837605 A US 23837605A US 2007072775 A1 US2007072775 A1 US 2007072775A1
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United States
Prior art keywords
composition
granular
core material
active ingredient
coating layer
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Abandoned
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US11/238,376
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English (en)
Inventor
Lonneke van Boxtel-Verhoeven
Johannes Gijsbertus Antonius Terlingen
Petra Leonarda Lunde-Vannuys
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Everris International BV
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OMS Investments Inc
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Publication date
Application filed by OMS Investments Inc filed Critical OMS Investments Inc
Priority to US11/238,376 priority Critical patent/US20070072775A1/en
Assigned to OMS INVESTMENTS, INC. reassignment OMS INVESTMENTS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LUNDE-VANNUYS, PETRA LEONARDA HENDRICA, TERLINGEN, JOHANNES GIJSBERTUS ANTONIUS, VAN BOXTEL-VERHOEVEN, Lonneke Jacoba
Priority to EP20060815700 priority patent/EP1928231B1/en
Priority to PL06815700T priority patent/PL1928231T3/pl
Priority to ES06815700T priority patent/ES2462542T3/es
Priority to AU2006297275A priority patent/AU2006297275B2/en
Priority to CA 2623740 priority patent/CA2623740C/en
Priority to CN201410577764.7A priority patent/CN104387157B/zh
Priority to BRPI0616469A priority patent/BRPI0616469B8/pt
Priority to CNA2006800447625A priority patent/CN101500410A/zh
Priority to PCT/US2006/037893 priority patent/WO2007041234A2/en
Priority to EP20120177258 priority patent/EP2545775A3/en
Publication of US20070072775A1 publication Critical patent/US20070072775A1/en
Priority to US13/008,771 priority patent/US8497229B2/en
Assigned to SCOTTS INTERNATIONAL B.V. reassignment SCOTTS INTERNATIONAL B.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OMS INVESTMENTS, INC.
Assigned to EVERRIS INTERNATIONAL B.V. reassignment EVERRIS INTERNATIONAL B.V. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: SCOTTS INTERNATIONAL B.V.
Priority to US13/952,187 priority patent/US9012363B2/en
Abandoned legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • A01N25/14—Powders or granules wettable
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B1/00—Superphosphates, i.e. fertilisers produced by reacting rock or bone phosphates with sulfuric or phosphoric acid in such amounts and concentrations as to yield solid products directly
    • C05B1/02—Superphosphates
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/30—Layered or coated, e.g. dust-preventing coatings
    • C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer

Definitions

  • the present invention relates to granular agrochemical compositions and to processes for producing such compositions. More particularly, it relates to controlled release agrochemical compositions having a first coating layer comprising a wax composition with a biologically active ingredient incorporated therein applied on the surface of a core material and having a second coating layer comprising a polymeric composition applied on the surface of the first coating layer and to processes for preparing such compositions.
  • Agrochemicals as referred to herein include biologically active ingredients/plant protection products such as insecticides, herbicides, fertilizers, growth regulators, pheromones, biostimulants, acaricides, miticides, nematocides, fungicides and the like.
  • biologically active ingredients/plant protection products such as insecticides, herbicides, fertilizers, growth regulators, pheromones, biostimulants, acaricides, miticides, nematocides, fungicides and the like.
  • Such agrochemicals are well known and are in common usage for controlling pests and diseases and for promoting plant growth in agriculture. In practice, it is important to make a sufficient amount of such agrochemical or active ingredient available to the biological system in order to control pests or disease or to promote growth. Too much active ingredient, however, is inefficient and not desired because of environmental and economic concerns. Furthermore, higher amounts of active ingredient lead to increased risks of leaching to ground water or surface water. Higher amounts can also lead to
  • the risk of exposure to the active ingredient is more limited.
  • the active ingredient is released to the soil under the influence of water.
  • the release rate varies depending on the formulation of the granule.
  • the granules can be divided into two categories. The first category releases the active ingredient quickly and has to be applied several times during the season.
  • the second category releases the active ingredient over a period of time and provides control of pests during an extended period up to a whole season.
  • the concentration of active ingredient must be above the minimal effective level during the whole period.
  • the rate of degradation and leaching depends on the active ingredient and the amount that is lost, is directly related to the concentration of the active ingredient in the soil. Thus high concentrations result in relatively more degradation and leaching.
  • EP Patent 079668 discloses an encapsulated pesticide product wherein a granular core is coated with a pesticide and then a plurality of layers of a membrane like coating are applied over the pesticidal coat to enable controlled release of such pesticide over a period of time upon contact with water.
  • EP Patent 079668 are structurally distinct from the products of the present invention and, accordingly, disadvantageously fail to exhibit a controlled rate of release of the pesticide over a period greater than about 30 days from the date of initial exposure of the product to moisture in a manner such that essentially all of the pesticide coated on the core is released from the granular composition before the water soluble portion of the core material is released from the product as is achieved with the compositions of the present invention.
  • U.S. Pat. No. 6,682,751 discloses a granular pesticide comprising a core material coated with an inner polymer membrane formed in-situ on the core material with a pesticide applied to the inner polymer membrane and an outer controlled release polymer membrane formed in situ on the pesticide to permit controlled release.
  • the pesticide may be incorporated in several “sandwich” layers.
  • 6,682,751 are structurally different from the products of the present invention and fail to exhibit a controlled rate of release of the pesticide over a period greater than about 30 days from the date of initial exposure of the product to moisture in a manner such that essentially all of the pesticide coated on the core is released from the granular composition before the water soluble portion of the core material is released from the product.
  • U.S. Pat. No. 6,080,221 discloses the coating of porous surfaces of fertilizer particles with tenacious pesticide-resin solids to form attrition resistant fertilizer-pesticide combination particles.
  • the pesticide is dispersed in a resinoid matrix, which is subsequently bonded onto and into the fertilizer surface.
  • U.S. Pat. No. 4,971,796 describes another slow release granular product in which the pesticide is matrixed into the coating.
  • the granule comprises one layer of proteinacious material or more layers of proteinacious material with intermediate spacing layers.
  • the active ingredient is in the proteinacious layer and is released when this layer degrades. The release rate is changed by varying the cross linking or the thickness of the layer.
  • No. 6,080,221 and U.S. Pat. No. 4,971,796 fail to exhibit a controlled rate of release of the pesticide over a period greater than about 30 days from the date of initial exposure of the product to moisture in a manner such that essentially all of the pesticide coated on the core is released from the granular composition before the core material is released from the product.
  • U.S. Pat. No. 6,187,074 and U.S. Pat. No. 6,309,439 disclose a fertilizer coated with a carboxyl-carrying ethylene copolymer, the carboxyl-carrying ethylene copolymer being composed of 75%-90% by weight ethylene and from 10%-25% by weight of an alpha-olefinically unsaturated C3-C8 carboxylic acid.
  • the coated fertilizer particles specifically do not contain any crop protection chemicals.
  • the products disclosed in these patents fail to exhibit a controlled rate of release of the pesticide over a period greater than about 30 days from the date of initial exposure of the product to moisture in a manner such that essentially all of the pesticide coated on the core is released from the granular composition before the core material is released from the product.
  • U.S. Pat. No. 6,693,063 discloses products that are structurally distinct from the present compositions teaching wax microcapsules and wax dispersion of pesticides in the absence of a water soluble core material.
  • Other encapsulated pesticides which do not include water soluble core materials are disclosed in Japanese Examined Patent Publication JP-B 5002/1989, JP-A 9304/1994 and JP-A 72805/1994.
  • EP Patent 0755370 discloses other matrix release products which are mixtures of a nitromethylene or related substances with fertilizers and glue.
  • EP Patent 1063215 describes briquettes that slowly release active ingredients. The slow release is obtained via absorption or adsorption of the active ingredient onto solids with high surface area.
  • the matrix systems all demonstrate release mechanisms wherein the release of active ingredients from the matrix systems is via desorption from an absorped state or by diffusion and not by an osmotic (pump) release mechanism as employed herein.
  • the release rate of such matrix systems depends on the concentration of the active ingredient in the system.
  • the release rate of such granules decreases over time resulting in initial fast release of active ingredients which provides high amounts of active ingredient in the soil at the start, and a slow release at the end.
  • biodegradable systems such as those disclosed in U.S. Pat. No. 4,062,855 wherein active ingredients are incorporated into a polymer that are released via biodegradation.
  • U.S. Pat. No. 4,267,280 describes a product that has a biodegradable polymer system that contains the pesticide. It releases the pesticide depending on environmental conditions via hydrolyses or depolymerization.
  • a disadvantage of these biodegradable products is that the release of active ingredient depends on the speed of degradation of the polymer and this degradation depends on the activity of ambient microorganisms.
  • the activity of the microorganisms can vary greatly depending on the soil type and local environmental conditions, types of microbes, pH, temperature, moisture the like.
  • the release rate of active ingredients varies and it is difficult to match the release precisely with the minimal required active ingredient concentrations.
  • coated granular pesticidal compositions are disclosed in International Patent Publication WO 02/05641 wherein a pesticidal composition is disclosed that can slowly release an active ingredient. That publication discloses the preparation of several granular materials with different numbers of coating layers or properties of the coating layers. Each of the granular materials has its own release profile. By blending the different granules they can obtain the desired release pattern of the product. The variation of release is purely based on coating properties and not on solubility of components in the formulation.
  • EP Patent 0966882 discloses a controlled release granular product wherein only single granules exhibit a delay of release after which the pesticide is released. Thus, after a period of time, a particular granule breaks open and delivers a portion of active ingredient to the environment. The release over a period of time is established by combining multiple ‘delayed release’ granules, which all have different delay times. The granules themselves do not exhibit controlled release properties, only a delayed release.
  • EP Patent 1148107 discloses a coating procedure for granules with a low content of volatile substances. This coating procedure ensures that the release function of the granules does not change in two weeks time.
  • formulations of this general type is disclosed in International Patent Publication WO 99/07654 comprising encapsulated fertilizers with a polymeric envelope that contains a hormone (e.g. an auxin or cytokinine).
  • the hormone is mixed with a monomer that form a polymeric envelope.
  • the products disclosed in this reference do not exhibit a controlled rate of release of the pesticide over a period greater than about 30 days from the date of initial exposure of the product to moisture in a manner such that essentially all of the pesticide coated on the core is released from the granular composition before the core material is released from the product.
  • agrochemical compositions that provide controlled release of active ingredients including efficiency and economy of use of the active ingredients, the reduced environmental impact achieved, the ability to employ a single application of the composition for extended control of pests and diseases, reduction in user exposure to the compositions, it is clear that new, more technically advanced agrochemical products would be highly desirable.
  • a desired objective is to provide agrochemical compositions that provide extended useful life with essentially complete release of an active ingredient occurring over a periods of greater than about 30 days from the date of initial exposure to moisture.
  • compositions which functionally demonstrate a controlled rate of release of the active ingredient over a period of time greater than about 30 days from the date of initial exposure of the compositions to moisture in a manner such that essentially all of the active ingredient coated on the core is released from the granular composition before the core material is released from the product.
  • the present invention relates to granular agrochemical compositions which exhibit functionality wherein essentially complete release of the active ingredients occurs over a period of time greater than about 30 days.
  • These granular compositions comprise a granular core material which, preferably, is at least partially water soluble, coated with a first coating layer comprising a wax material having a biologically active plant protection product or active ingredient incorporated therein and having a second coating layer comprising a polymeric composition applied on the surface of the first coating layer.
  • the present invention involves the development of a new system for release of active ingredients, such as herbicides, growth regulators, pheromones, bactericides, insecticides, acaricides and fungicides and the like, over a defined period of time with high efficiency.
  • active ingredients such as herbicides, growth regulators, pheromones, bactericides, insecticides, acaricides and fungicides and the like
  • the granular agrochemical composition of the present invention exhibit a controlled rate of release of the biologically active ingredient therefrom over a period greater than about 30 days from the date of initial exposure of the granular composition to moisture whereby essentially all of the biologically active ingredient incorporated in the wax material of the first coating layer is released from the granular composition while at least a residual amount of the core material remains in the granular composition.
  • the release rate of the compositions can be influenced by changing the coating properties, the solubility of the core-material and by adjusting various others of the product constituents.
  • FIG. 1 illustrates the release rate of a granular agrochemical composition of the present invention.
  • FIG. 2 illustrates the release rate of another embodiment of the granular agrochemical compositions of the present invention.
  • FIG. 3 illustrates the release rate of a another embodiment of the granular agrochemical compositions of the present invention.
  • FIG. 4 illustrates the release rate of another embodiment of the granular agrochemical compositions of the present invention.
  • FIG. 5 illustrates the release rate of another embodiment of the granular agrochemical compositions of the present invention.
  • the products of the present invention comprise granular agrochemical compositions including a granular core material having a first coating layer applied on the surface of the core material and a second coating layer applied over the surface of the first coating layer.
  • the first coating layer comprises a wax material having a plant protection product incorporated therein and the second coating layer comprising a polymeric composition.
  • the granular composition of this invention exhibit a controlled rate of release of a plant protection product therefrom over a period greater than about 30 days from the date of initial exposure of the granular composition to moisture, preferably up to about 104 weeks after initial exposure to moisture, whereby essentially all of the plant protection product incorporated in the wax material of the first layer is released from the granular composition while at least a residual amount of the water soluble core material remains in the granular composition and methods to make such a granular agrochemical composition.
  • the present compositions enable lower application rates for the same period of control because the plant protection products is essentially completely released at a control rate over a period of greater than 30 days, preferably up to about 104 weeks, from the date of initial exposure to water.
  • the products of this invention have a high efficiency. This means that essentially all of the active ingredient, preferably greater than 90% of the initial weight of the active ingredient in the wax coating layer is released to the environment before the water soluble content of the core material is completely depleted.
  • the process for preparing the granular compositions of the present invention which exhibit essentially complete release of the active ingredient over a period greater than about 30 days, preferably comprises coating a core material with a first coating layer comprising a wax material having a biologically active ingredient incorporated therein and applying a second coating layer comprising a polymeric composition applied over the surface of the first coating layer.
  • the core material is at least partially water soluble ensuring transport of water to the granule through the first and second coating layers via osmosis.
  • the “osmotic” transport of the ingredients occurs as a result of the pumping of water into and a solution out of the granule and continues until all core material has been released. Accordingly, once dissolved, the water dissolvable core material as well as the biologically active ingredient in the first coating layer are transported out of the granule.
  • Suitable core materials for use herein are fertilizers such as ammonium sulfate, potassium nitrate, potassium sulfate, urea, ammonium nitrate, monopotassium sulfate, ammonium phosphate, super-phosphate, calcium phosphates, potassium phosphate, potassium chloride, magnesium oxide, magnesium sulfate, dolomite and the like or any fertilizers obtained from compounding a mixture of these fertilizers.
  • non-active materials such as sugar and other granular materials may be employed as the core material herein, if desired.
  • the core materials comprise at least one secondary nutrient and/or micronutrient.
  • Suitable secondary nutrients include calcium, magnesium, sulfur and mixtures thereof.
  • Suitable micronutrients, in chelated or non-chelated form, include iron copper, zinc, manganese, boron, cobalt, chlorine, sodium, molybdenum and mixtures thereof.
  • the wax composition to be employed to form the first coating layer in a most preferred embodiment of this invention, should be water soluble to facilitate an even better dissolution of the active ingredient in the coating layer.
  • the granular agrochemical composition of the present invention exhibits a controlled rate of release of a plant protection product (active ingredient) therefrom over a period greater than about 30 days from the date of initial exposure of the granular composition to moisture whereby essentially all of the plant protection product incorporated in the wax material of the first layer is released from the granular composition while at least a residual amount of the water soluble core material remains in the granular composition.
  • suitable biologically active ingredients for use herein are pesticides, insecticides, herbicides, fungicides, fertilizers, growth regulators, pheromones, biostimulants, acaricides, miticides, nematocides and mixtures thereof.
  • Suitable insecticides include one or more of the following: dimethyl acetylphosphoramidothioate; ethanimidamide, N- ⁇ (6-chloro-3-pyridinyl)methyl ⁇ -N′-cyano-N-methyl-, (E)-(9Cl)(CA Index name); hydrazinecarboxylic acid, 2-(4-methoxy ⁇ 1 , 1 ′-biphenyl ⁇ -3-YL)-, 1-methylethyl ester (9Cl) (CA Index Name); methyl ⁇ 1 , 1 ′-biphenyl ⁇ -3-YL)methyl 3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, ⁇ 1.alpha.,3.alpha.(Z) ⁇ -(.+ ⁇ .)-; naphthyl-n-methylcarbamate; pyrrole-3-carbonitrile, 4-bromo-2-(4-ch
  • Suitable fungicides for use in the present invention include tetrachloroisophthalonitrile; ethoxy-3-(trichloromethyl)-1,2,4-thiadiazole; dichlorophenyl)-4-propyl-1,3-dioxolan-2-YL)methyl)-1H-1,2,4-triazole; carbamic acid, 2-1-(4-chlorophenyl)-1H-pyrazol-3-ylyoxyymethylyphenylymethoxy-methyl ester (CAS name); dimethyl((1,2-phenylene)bis(iminocarbonothioyl))bis(carbamate) and the like.
  • Suitable plant growth regulators for use in the present invention include RS,3RS)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-YL)pentan-3-OL; cyclohexanecarboxylic acid, 4-(cyclopropylhydroxymethylene)-3,5-dioxo-,ethyl ester.
  • biologically active ingredients which may be employed in preparing the granular compositions of this invention include (z)-11-tetradecenyl acetate; 1,2-benzisothiazolin-3-on; 1,2-Dibromoethane; 1,3-dichloro-5,5-dimethylhydantoine; 1,3-dichloro-5-ethyl-5-methylhydantoine; 1-bromo-3-chloro-5,5-dimethylhydantoine; 1-Chloro-2,3-epoxyethane; 1-methylcyclopropene;1-naftylacetamide; 1-naftylacetic acid; 2-(thiocyanomethylthio)benzothiazole; 2,2 dibromo-3-nitrilopropionamide; 2,2′-Bipyridyl; 2,2-dithiobisbenzamide; 2,4,5-T, 2,4-D, 2,4-DB; 2,4-Dichloroanisole; 2,4-
  • the core material should release slower than the active ingredient. Otherwise, residues of active ingredient would remain in the controlled release system after complete release of the core material.
  • the granular core material employed for preparing the compositions is at least partially water soluble and may comprise any of a variety of well known, standard NPK or other such fertilizer granules such as those described in European Community Regulation (EC) No. 2003/2003.
  • the core material may be a water-soluble salt or other such material, e.g. sodium-salts or calcium-salts.
  • non-ionic materials may be suitable for use in forming the core of the present compositions, particularly, those which can provide osmotic pressure when dissolved.
  • examples, of such materials are sugar and urea granules.
  • the materials for use in forming the core for the compositions of this invention should have a solubility of about 2 to about 800 g/l, preferably, about 120-450 g/l.
  • the core material should be shaped as a granule having a diameter of about 0.35 to about 6 mm, preferably, about 0.72-4 mm for better distribution of the product.
  • the wax material to be employed for use in preparing the first coating layer should have a melting point between about 50° C. and the degradation temperature of the active ingredient or core material, preferably above about 80° C.
  • the wax can be hydrophobic or hydrophillic.
  • waxes for use herein are higher alkenes; stearamides; polyolefines such as polyethylene, oxidized polyethylenes, polypropylene, polyisobutylene, styrene-based polymers; (block) copolymers of polyolefines; polyesters; (block) copolymers of polyesters; polyethers, e.g.
  • the biologically active ingredient or plant protection product for incorporation in the wax to form the first coating layer should be selected from the group consisting of insecticides, herbicides, fertilizers, growth regulators, pheromones, biostimulants, acaricides, miticides, nematocides, fungicides and mixtures thereof and the like.
  • the controlled release systems of this invention enable economical application of a total amount of active ingredient necessary for season long control without increased risk of leaching, phytotoxicity for crops and is safe for users.
  • the active ingredient is applied without the use of a solvent.
  • low-solubility active ingredients can be used.
  • the system is efficient. At most, only very limited amounts, preferably less than about 10% by weight and, most preferably, less than about 1% by weight, of the active ingredient should be left inside the system.
  • the water-solubility of the core material is adjusted to correspond to the water-solubility of the active ingredient.
  • the core material-solubility is too high compared to the active ingredient-solubility, all of the core-material may be released before the release of all the active ingredient. This results in residue of active ingredient in the granules which is not desirable from an environmental and commercial point of view. If the solubility of the core material is too low compared to the solubility of the active ingredient, too much of the core material may be left in the composition after the release of the active. This results in an inefficient use of the core material.
  • the solubility of the active ingredient and core material may be influenced by additives, such as ionic or non-ionic surfactants, water-soluble polymers or complexing agents. Not all active ingredients demonstrate good water-solubility. Increasing the solubility of an active ingredient, for example, by using a non-ionic surfactant for the active ingredient application renders the actives more soluble and may make the compositions of this invention more widely applicable. Not only the solubility of the core material but, also, the dissolving rate of the core material versus the active ingredient should be considered in formulating the compositions of this invention. Typically, the ratio of core material to active ingredient should be about 1000 to about 0.1 and, preferably, about 200-10.
  • the coating thickness employed should be matched with the solubility of the core material and the active ingredient.
  • the longevity of release of the active ingredients of the present compositions can be modified by varying the amount of polymeric coating employed.
  • the water-permeability of the polymer coating can be changed.
  • the polymer coating layer can be formed from any (semi-)water-permeable polymeric material, including copolymers, known in the art such as known thermosetting resins, thermoplastic resins and other polymeric materials or latex polymers and mixtures thereof.
  • the polymer coating enables slow release of the active ingredient over a period of about 6 to about 104 weeks, preferably, about 3-6 months.
  • thermoplastic coating materials such as vinyl resins such as poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), poly(vinyl pyrrolidone), poly(vinyl acetal), poly(vinyl methylacetamide); polyolefines such as polyethylene, polypropylene, polyisobutylene; styrene-based polymers; acrylic polymers; polyesters such as poly(alkylene terephthalate), poly(caprolactone); poly(oxy alkylene)s, such as poly(ethylene oxide), poly(propylene oxide); cellulose derivatives, such as celluloseacetate; polyamides; polyamines; polycarbonates; polyimides; polysulfones; polysulfides; polysaccharides and the like.
  • vinyl resins such as poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), poly(viny
  • thermosetting polymeric coating materials for use herein include polyesters such as alkyds or modified alkyds; epoxy resins; urethane resins; and aminoplastics.
  • the polymeric composition for use in forming the second coating layer comprises a dicyclopentadiene (“DCPD”) polymeric product (containing either linseed oil or an alkyd resin based on a soybean oil) such the polymer coatings employed to produce such fertilizers as those sold by the Scotts Company under the trademark Osmocote® as disclosed in U.S. Pat. No. 3,223,518 and U.S. Pat. No. 4,657,576.
  • DCPD dicyclopentadiene
  • the active ingredient is applied onto the granular core material with a wax.
  • the active ingredient/wax combination is a solid at room temperature and it is applied onto the granular core material as a liquid.
  • the active ingredient can be mixed with a (molten) wax and applied drop wise or sprayed onto the granular material.
  • the active ingredient does not need to dissolve.
  • the mixture of active ingredient and wax can be applied as a dispersion.
  • functional additives such as surfactants, which are used to modify the water solubility, can be applied with the active ingredients.
  • ionic or non-ionic surfactants enables use of active ingredients in the present compositions that have a low solubility in water, thus, broadening their applicability.
  • waxes that are non-ionic surfactants can be used herein.
  • the present invention encompasses both granular controlled release agrochemical compositions and processes for the preparation thereof and addresses the problems encountered with regard to functionality of prior compositions in terms of active ingredient release over an extended period of time.
  • compositions and processes of the present invention are further illustrated by the examples below.
  • the examples serve only to illustrate the invention and should not be interpreted as limiting since further modifications of the disclosed invention will be apparent to those skilled in the art. All such modifications are deemed to be within the scope of the invention as defined in the claims.
  • a sample of the granular agrochemical compositions of the present invention was prepared employing an 0-2-40 fertilizer granule obtained from The Scotts Company (Howden, UK) as the granular core material. This granular core was predominantly composed of potassium sulfate.
  • the sample composition was prepared by initially heating 50 g of the 0-2-40 fertilizer granules (1.7-2.0 mm) in a rotating drum to 110° C.
  • a non-ionic surfactant wax (a polyethyleneglycol-block-polyethylene, cas nr.: [251553-55-6], hydroxyl number 52.00 mg KOH/g, containing 20% (by weight) polyethylene glycol, obtained from Sigma-Aldrich), was melted and 0.25 g of a biologically active ingredient (imidacloprid, obtained from Sigma-Aldrich) was mixed into in the molten wax.
  • a non-ionic surfactant wax a polyethyleneglycol-block-polyethylene, cas nr.: [251553-55-6], hydroxyl number 52.00 mg KOH/g, containing 20% (by weight) polyethylene glycol, obtained from Sigma-Aldrich
  • the resulting mixture of imidacloprid and wax was added to the warm fertilizer (potassium sulfate) granules to form a coating layer on the granular core.
  • the granules with the imidacloprid and wax coating thereon were allowed to cool to room temperature.
  • a second coating layer was applied over the imidacloprid and wax coating layer according to the following procedure.
  • the active-impregnated granules were heated 15 minutes in a rotating flask in an oil-bath at 95° C.
  • the solid content of the added resin was 40%.
  • White spirit was used as a solvent and a drier was used to enhance the curing.
  • air was purged through the system to evaporate the solvent from the resin. After coating 5.5 pph (parts per hundred by weight) on the granular composition having the first coating layer thereon, the resulting composition was cooled to room temperature and was ready for testing.
  • the imidacloprid concentration in this composition was 0.30% by weight as determined by standard High Performance Liquid Chromatography chemical analytical analysis techniques.
  • the test sample of this Example 1 was subjected to release testing wherein the release of the active ingredient from the coated granular composition was evaluated in water in a so-called waterleach test.
  • waterleach test 200 ml of water was added to 10 g of the coated granular composition. Then the sample was stored at 21° C. and the water was replaced completely with fresh water after 1 day and at weekly intervals thereafter.
  • the removed water was analyzed on active ingredient content with standard analytical methods.
  • the release profile was calculated from the initial active ingredient concentration in the granule.
  • the core dissolution was calculated from the measured conductivity.
  • the measured conductivity can be translated into a total amount of nutrients released using the appropriate calibration constants. These calibration constants are specific for a particular type of fertilizer and are determined experimentally.
  • the compositions of this invention provided a release of about 95% (by weight) of the active ingredient over a period of 287 days from the date of initial exposure to moisture while about only about 50% (by weight) of the core material was released over that same time period so that about 50% (by weight) of the water soluble portion of the granular core material remained within the granular composition over the 287 day duration.
  • composition produced in accordance with this Example 2 is distinguishable from the compositions produced in accordance with Example 1 in regard to the wax material employed in forming the first coating layer of test sample of the granular agrochemical composition of the present invention.
  • the procedure used to produce the test sample of this Example 2 was in accordance with the process of Example 1.
  • an 0-2-40 fertilizer granule obtained from The Scotts Company which was predominantly composed of potassium sulfate was employed as the granular core material for the sample composition which was prepared by initially heating 50 g of the 0-2-40 fertilizer granules (1.7-2.0 mm) in a rotating drum to 110° C. Then, 0.75 g of a polyethyleneglycol-block-polyethylene, cas nr.: [97953-22-5], hydroxyl number 55.00 mg KOH/g, containing 50% (by weight) polyethylene glycol, obtained from Sigma-Aldrich) was melted and 0.25 g of a biologically active ingredient (imidacloprid, obtained from Sigma-Aldrich) was mixed into the molten wax.
  • This wax differed from the wax employed in Example 1 but possessed similarly suitable surfactant characteristics for the imidacloprid biologically active ingredient which was incorporated by mixing into in the molten wax as described in Example 1.
  • Example 2 The imidacloprid concentration in the composition of this Example 2 was 0.22% (by weight) as determined by standard High Performance Liquid Chromatography chemical analytical analysis techniques.
  • Example 2 The composition of this Example 2 was subjected to the release testing procedure as described in Example 1 and the results of this testing is illustrated in FIG. 2 .
  • this granular composition having the biologically active imidacloprid ingredient incorporated into the wax provided an effective and efficient system for release of the active ingredient over a period of greater than 30 days.
  • the results shown in FIG. 2 are shown in FIG. 2 .
  • the composition of this invention provided a release of about 96% (by weight) of the active ingredient over a period of 287 days from the date of initial exposure to moisture while only about 65% (by weight) of the core material was released over that same time period so that about 35% (by weight) of the water soluble portion of the granular core material remained within the granular composition over the 287 day duration.
  • composition produced in accordance with this Example 3 is distinguishable from the compositions produced in accordance with Example 2 in regard to the amount of the active ingredient which was incorporated into the wax material in forming the first coating layer of test sample of the granular agrochemical composition of the present invention.
  • Example 3 The procedure used to produce the test sample of this Example 3 was in accordance with the process of Example 1. Specifically, an 0-2-40 fertilizer granule obtained from The Scotts Company which was predominantly composed of potassium sulfate was employed as the granular core material for the sample composition which was prepared by initially heating 50 g of the 0-2-40 fertilizer granules (1.7-2.0 mm) in a rotating drum to 110° C.
  • Example 3 The imidacloprid concentration in the composition of this Example 3 was 0.95% by weight as determined by standard High Performance Liquid Chromatography chemical analytical analysis techniques.
  • Example 3 The composition of this Example 3 was subjected to the release testing procedure as described in Example 1 and the results of this testing is illustrated in FIG. 3 .
  • this granular composition having the biologically active imidacloprid ingredient incorporated into the wax provided an effective and efficient system for release of the active ingredient over a period of greater than 30 days.
  • the results shown in FIG. 3 are shown in FIG. 3 .
  • the composition of this invention provided a release of about 86% (by weight) of the active ingredient over a period of 175 days from the date of initial exposure to moisture while only about 67% (by weight) of the core material was released over that same time period so that about 33% (by weight) of the water soluble portion of the granular core material remained within the granular composition over the 175 day duration.
  • composition produced in accordance with this Example 4 is distinguishable from the compositions produced in accordance with Example 1 in regard to the active ingredient which was incorporated into the wax material in forming the first coating layer of test sample of the granular agrochemical composition of the present invention and in regard to polymer composition which was employed in forming the second coating layer on the compositions.
  • the procedure used to produce the test sample of this Example 4 was in accordance with the process of Example 1.
  • an 0-2-40 fertilizer granule obtained from The Scotts Company which was predominantly composed of potassium sulfate was employed as the granular core material for the sample composition which was prepared by initially heating 50 g of the 0-2-40 fertilizer granules (1.7-2.0 mm) in a rotating drum to 110° C.
  • Example 1 a polyethyleneglycol-block-polyethylene, cas nr.: [251553-55-6], hydroxyl number 52.00 mg KOH/g, containing 20% by weight polyethyleneglycol, obtained from Sigma-Aldrich), was melted and 3.5 g of a Fosetyl-Aluminum biologically active ingredient obtained from Bayer CropSciences was incorporated by mixing into the molten wax by the same procedure described in Example 1.
  • the resulting mixture of Fosetyl-Aluminum and wax was added to the warm fertilizer (potassium sulfate) granules to form a coating layer on the granular core.
  • the granules with the Fosetyl-Aluminum and wax coating thereon were allowed to cool to room temperature.
  • a polymeric second coating layer was applied over the Fosetyl-Aluminum and wax by the process described in Example 1 to produce the granular composition for testing.
  • the polymer employed as the second coating layer was a modified unsaturated oil copolymer based alkyd resin sold under the trade name Necolin 4071 by Ashland-Sudchemie-Kernfest GmbH, Germany.
  • the Fosetyl-Aluminum concentration in the composition of this Example 4 was 4.75% (by weight) as determined by standard High Performance Liquid Chromatography chemical analytical analysis techniques.
  • Example 4 The composition of this Example 4 was subjected to the release testing procedure as described in Example 1 except that the Fosetyl-Aluminium release was analyzed with ion-chromatography column: Phenomenex starion A300:1050 ⁇ 4.6 mm, eluens 5% acetone in water, with 1 mM HNO3 and 3 mM NaNO 3 and the results of this testing is illustrated in FIG. 4 .
  • this granular composition having the biologically active Fosetyl-Aluminum ingredient incorporated into the wax provided an effective and efficient system for release of the active ingredient over a period of greater than 30 days.
  • the composition of this invention provided release of 99% (by weight) of the active ingredient over a period of about 267 days from the date of initial exposure to moisture while only about 50% (by weight) of the core material was released over that same time period.
  • test sample compositions in accordance with this invention was produced utilizing a hydrophobic wax material in forming the first coating layer.
  • the procedure used to produce the test sample of this Example 5 was in accordance with the process of Example 1.
  • an 0-2-40 fertilizer granule obtained from The Scotts Company which was predominantly composed of potassium sulfate was employed as the granular core material for the sample composition which was prepared by initially heating 50 g of the 0-2-40 fertilizer granules (1.7-2.0 mm) in a rotating drum to 110° C. Then, 2.5 g of a hydrophobic wax (Novoflow 02102 obtained from Holland Novochem BV, Nieuwegein, the Netherlands)—was melted and 2.5 g of a Fosetyl-Aluminum biologically active ingredient obtained from Bayer CropSciences was incorporated by mixing into the molten wax by the same procedure described in Example 1.
  • a hydrophobic wax Novoflow 02102 obtained from Holland Novochem BV, Nieuwegein, the Netherlands
  • the resulting mixture of Fosetyl-Aluminum and wax was added to the warm fertilizer (potassium sulfate) granules to form a coating layer on the granular core.
  • the granules with the Fosetyl-Aluminum and wax coating thereon were allowed to cool to room temperature.
  • a polymeric second coating layer was applied over the Fosetyl-Aluminum and wax by the process described in Example 1 to produce the granular composition for testing.
  • the polymer employed as the second coating layer was a modified unsaturated oil copolymer based alkyd resin sold under the trade name Necolin 4071 by Ashland-Sudchemie-Kernfest GmbH, Germany.
  • the Fosetyl-Aluminum concentration in the composition of this Example 5 was 3.5% by weight as determined by standard High Performance Liquid Chromatography chemical analytical analysis techniques.
  • Example 5 The composition of this Example 5 was subjected to the release testing procedure as described in Example 1 as modified in Example 4 and the results of this testing is illustrated in FIG. 5 .
  • this granular composition having the biologically active Fosetyl-Aluminum ingredient incorporated into the hydrophobic wax provided an effective and efficient system for release of the active ingredient over a period of greater than 30 days.
  • the results shown in FIG. 5 are shown in FIG. 5 .
  • the composition of this invention provided release of about 80% (by weight) of the active ingredient over a period of about 266 days from the date of initial exposure to moisture while only about 36% (by weight) of the core material was released over that same time period so that about 64% (by weight) of the water soluble portion of the granular core material remained within the granular composition over the approximately 266 day duration.
  • This result demonstrates the benefits derived from employing a hydrophobic wax resulting in a slower releasing product which is desirable when a highly soluble active ingredient is incorporated therein.

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US11/238,376 US20070072775A1 (en) 2005-09-29 2005-09-29 Granular controlled release agrochemical compositions and process for the preparation thereof
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CN201410577764.7A CN104387157B (zh) 2005-09-29 2006-09-27 颗粒控释农用化学品组合物及其制备方法
CNA2006800447625A CN101500410A (zh) 2005-09-29 2006-09-27 颗粒控释农用化学品组合物及其制备方法
ES06815700T ES2462542T3 (es) 2005-09-29 2006-09-27 Composiciones agroquímicas granuladas de liberación controlada y procedimiento para la preparación de las mismas
AU2006297275A AU2006297275B2 (en) 2005-09-29 2006-09-27 Granular controlled release agrochemical compositions and process for the preparation thereof
CA 2623740 CA2623740C (en) 2005-09-29 2006-09-27 Granular controlled release agrochemical compositions and process for the preparation thereof
EP20060815700 EP1928231B1 (en) 2005-09-29 2006-09-27 Granular controlled release agrochemical compositions and process for the preparation thereof
BRPI0616469A BRPI0616469B8 (pt) 2005-09-29 2006-09-27 Composição agroquímica granular, e, processo para preparar a mesma
PL06815700T PL1928231T3 (pl) 2005-09-29 2006-09-27 Granulowane kompozycje agrochemiczne do kontrolowanego uwalniania i sposób ich wytwarzania
PCT/US2006/037893 WO2007041234A2 (en) 2005-09-29 2006-09-27 Granular controlled release agrochemical compositions and process for the preparation thereof
US13/008,771 US8497229B2 (en) 2005-09-29 2011-01-18 Granular controlled release agrochemical compositions and process for the preparation thereof
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Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060089259A1 (en) * 2004-10-12 2006-04-27 Oms Investments, Inc. Shaped plant growth nutrient products and processes for the production thereof
US20080103048A1 (en) * 2006-10-26 2008-05-01 Radabaugh Robert M A Methods for the production of granular composite pesticidal compositions and the compositions produced thereby
WO2012143679A2 (en) * 2011-04-20 2012-10-26 Exosect Limited Coating compositions for pathogen control in cotton
WO2012143676A3 (en) * 2011-04-20 2013-02-21 Exosect Limited Coating compositions for pathogen control in ornamentals
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US20140221208A1 (en) * 2011-01-25 2014-08-07 Agrium Advanced Technologies Controlled release copper sulfate for phytoplankton control
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WO2015119514A1 (en) * 2014-02-10 2015-08-13 Dow Agrosciences Llc Stable solid herbicide delivery systems
US20160235685A1 (en) * 2013-09-27 2016-08-18 L'oreal Photosensitive capsules and cosmetic and pharmaceutical use thereof
DE102015012380A1 (de) * 2015-09-21 2017-03-23 Ask Chemicals Gmbh Beschichtetes Kernteilchen und Verfahren zur Herstellung desselben
WO2018111685A1 (en) * 2016-12-15 2018-06-21 Wellmark International Extended release formulation
US10015965B2 (en) 2014-02-10 2018-07-10 Dow Agrosciences Llc Methods for using stable solid herbicide delivery systems
EP3298094A4 (en) * 2015-05-22 2019-01-16 Honeywell International Inc. WAX-BASED FERTILIZER COATINGS COMPRISING POLYETHYLENE OR POLYPROPYLENE POLYMERS
WO2019046349A1 (en) * 2017-08-30 2019-03-07 Nutrient Encapsulation Technologies FERTILIZER COATED WITH POLYMER
US11377395B2 (en) * 2017-09-13 2022-07-05 Lg Chem, Ltd. Controlled-release type fertilizer with decreased floating property comprising polyoxyethylene alky(-aryl) ether and method for preparing the same

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US20070072775A1 (en) * 2005-09-29 2007-03-29 Oms Investments, Inc. Granular controlled release agrochemical compositions and process for the preparation thereof
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RU2676734C2 (ru) 2013-08-19 2019-01-10 Дзе Мозаик Компани Система и способы введения эффективных сельскохозяйственных, биологических и/или препятствующих пылеобразованию добавок в гранулированные удобрения
AU2015212412B2 (en) 2014-01-31 2019-07-11 SABIC Agri-Nutrients Company Fertilizer capsule comprising one or more cores and method of making same
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WO2016107548A1 (en) * 2014-12-31 2016-07-07 Dow Agrosciences Llc Nitrification inhibitor compositions and methods for preparing the same
WO2016186526A1 (en) * 2015-05-20 2016-11-24 Ballance Agri-Nutrients Limited Fertiliser composition
US11104618B2 (en) 2015-07-20 2021-08-31 Sabic Global Technologies B.V. Fertilizer composition and methods of making and using same
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MX2018001759A (es) 2015-08-12 2018-07-06 Mosaic Co Tratamiento acido para fertilizantes para incrementar al solubilidad y disponibilidad del zinc.
WO2017087265A1 (en) 2015-11-16 2017-05-26 Sabic Global Technologies B.V. Methods of manufacture for coated granular fertilizers
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EP3414214A1 (en) 2016-02-08 2018-12-19 SABIC Global Technologies B.V. Method of making a fertilizer seed core
CN106386883B (zh) * 2016-12-01 2019-07-12 福建省罗源创鲜农业科技有限公司 一种食用菌熏虫颗粒及其制备方法
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Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4062855A (en) * 1971-09-27 1977-12-13 University Of Washington Synthetic polymers furnishing controlled release of a biologically active component during degradation
US4267280A (en) * 1977-02-07 1981-05-12 Mccormick Charles L Controlled release pesticides and method of preparation
US4435383A (en) * 1980-09-05 1984-03-06 E. I. Du Pont De Nemours And Company Slow release pesticide formulations
US4880455A (en) * 1987-03-24 1989-11-14 Haifa Chemicals Limited Method for the manufacture of slow-release fertilizers
US4946686A (en) * 1987-09-24 1990-08-07 Merck & Co., Inc. Solubility modulated drug delivery system
US4971796A (en) * 1988-10-05 1990-11-20 Sjogren Robert D Slow release pest control granule composition
US5516520A (en) * 1992-07-31 1996-05-14 Industrial Technology Research Institute Controlled-release pesticides and methods for preparation and use thereof
US5652196A (en) * 1991-07-22 1997-07-29 Oms Investments, Inc. Timed release of water-soluble plant nutrients
US5917110A (en) * 1996-10-18 1999-06-29 Tetra Technologies, Inc. Moisture-resistant calcium containing particles
US5938813A (en) * 1997-01-27 1999-08-17 Sqm Nitratos, S.A. Granular coated particles containing urea and metal nitrate, and process for making the same
US6080221A (en) * 1999-09-17 2000-06-27 Agri-Nutrients Technology Group, Inc. Vacuum coated particulate fertilizers
US6187074B1 (en) * 1995-06-13 2001-02-13 K + S Aktiengesellschaft Coated fertilizer granules
US6248278B1 (en) * 1997-11-15 2001-06-19 Trisport Limited Compression moulding method
US6284278B1 (en) * 1997-06-13 2001-09-04 Contrix Ltd. Controlled release chemicals
US20030215657A1 (en) * 2002-05-15 2003-11-20 Oms Investments, Inc. Triggered start products and processes for the production and use thereof
US20040015877A1 (en) * 1998-09-29 2004-01-22 Arrouye Yan J. Method and apparatus for "just-in-time" dynamic loading and unloading of computer software libraries
US6682751B1 (en) * 2001-09-12 2004-01-27 Rlc Technologies, L.L.C. Controlled-release pesticidal composition and method of making
US6693063B2 (en) * 2000-12-20 2004-02-17 Aventis Cropscience Gmbh Herbicidal composition

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3223518A (en) 1961-08-18 1965-12-14 Archer Daniels Midland Granular fertilizer having a plurality of coatings and the process of making
JPS543479B2 (pt) 1973-06-28 1979-02-23
JPS57126402A (en) 1981-01-29 1982-08-06 Asahi Chem Ind Co Ltd Granular prolonged release type agricultural chemical
WO1983000799A1 (en) 1981-08-31 1983-03-17 Sierra Chem Slow release pesticide and composite granules and method for making the same
NL8403505A (nl) 1984-11-16 1986-06-16 Sierra Chemical Europ Kunstmestsamenstelling in korrelvorm met een geregelde afgifte van meststoffen en werkwijze voor het bereiden hiervan.
US4891223A (en) * 1987-09-03 1990-01-02 Air Products And Chemicals, Inc. Controlled release delivery coating formulation for bioactive substances
JPH01192669A (ja) * 1988-01-27 1989-08-02 Komori Printing Mach Co Ltd 輪転印刷機の折機
JPH0745353B2 (ja) * 1989-07-27 1995-05-17 旭化成工業株式会社 農材被覆粒状肥料
JPH069304A (ja) 1992-06-26 1994-01-18 Ube Ind Ltd 被覆粒状農薬
JPH0672805A (ja) 1992-07-10 1994-03-15 Ube Ind Ltd 被覆粒状農薬
DE4412833A1 (de) 1994-04-14 1995-10-19 Bayer Ag Insektizide Düngemischungen
WO1995034200A1 (en) * 1994-06-10 1995-12-21 Fernz Corporation Limited Biodegradable sustained release composition
JP3456604B2 (ja) * 1994-09-26 2003-10-14 セントラル硝子株式会社 多層被覆粒状肥料
AU726550B2 (en) 1997-01-20 2000-11-09 Jnc Corporation Timed-release control-type coated granular pesticide
IL121496A (en) 1997-08-07 2001-06-14 Univ Ben Gurion Fertilizers wrapped for controlled release
DE69924023T2 (de) 1998-12-14 2006-04-13 Chisso Corp. Beschichtete biologisch aktive körner
JP2001005002A (ja) 1999-06-18 2001-01-12 Canon Inc 液晶素子及び液晶表示装置
US6225258B1 (en) 1999-06-25 2001-05-01 Lesco Technologies Llc Controlled release pesticide and fertilizer briquettes
GB0017277D0 (en) 2000-07-13 2000-08-30 Novartis Ag Organic compounds
CN1280242C (zh) * 2003-03-28 2006-10-18 中国科学院沈阳应用生态研究所 一种具有框架结构的缓释复合肥
CN1657512A (zh) * 2005-02-05 2005-08-24 方连明 包膜控释肥料及其组合以及制备方法
US20070072775A1 (en) * 2005-09-29 2007-03-29 Oms Investments, Inc. Granular controlled release agrochemical compositions and process for the preparation thereof

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4062855A (en) * 1971-09-27 1977-12-13 University Of Washington Synthetic polymers furnishing controlled release of a biologically active component during degradation
US4267280A (en) * 1977-02-07 1981-05-12 Mccormick Charles L Controlled release pesticides and method of preparation
US4435383A (en) * 1980-09-05 1984-03-06 E. I. Du Pont De Nemours And Company Slow release pesticide formulations
US4880455A (en) * 1987-03-24 1989-11-14 Haifa Chemicals Limited Method for the manufacture of slow-release fertilizers
US4946686A (en) * 1987-09-24 1990-08-07 Merck & Co., Inc. Solubility modulated drug delivery system
US4971796A (en) * 1988-10-05 1990-11-20 Sjogren Robert D Slow release pest control granule composition
US5652196A (en) * 1991-07-22 1997-07-29 Oms Investments, Inc. Timed release of water-soluble plant nutrients
US5516520A (en) * 1992-07-31 1996-05-14 Industrial Technology Research Institute Controlled-release pesticides and methods for preparation and use thereof
US6187074B1 (en) * 1995-06-13 2001-02-13 K + S Aktiengesellschaft Coated fertilizer granules
US6309439B1 (en) * 1995-06-13 2001-10-30 K + S Aktiengesellschaft Coated fertilizer granules
US5917110A (en) * 1996-10-18 1999-06-29 Tetra Technologies, Inc. Moisture-resistant calcium containing particles
US5938813A (en) * 1997-01-27 1999-08-17 Sqm Nitratos, S.A. Granular coated particles containing urea and metal nitrate, and process for making the same
US6284278B1 (en) * 1997-06-13 2001-09-04 Contrix Ltd. Controlled release chemicals
US6248278B1 (en) * 1997-11-15 2001-06-19 Trisport Limited Compression moulding method
US20040015877A1 (en) * 1998-09-29 2004-01-22 Arrouye Yan J. Method and apparatus for "just-in-time" dynamic loading and unloading of computer software libraries
US6080221A (en) * 1999-09-17 2000-06-27 Agri-Nutrients Technology Group, Inc. Vacuum coated particulate fertilizers
US6693063B2 (en) * 2000-12-20 2004-02-17 Aventis Cropscience Gmbh Herbicidal composition
US6682751B1 (en) * 2001-09-12 2004-01-27 Rlc Technologies, L.L.C. Controlled-release pesticidal composition and method of making
US20030215657A1 (en) * 2002-05-15 2003-11-20 Oms Investments, Inc. Triggered start products and processes for the production and use thereof
US6787234B2 (en) * 2002-05-15 2004-09-07 Oms Investments, Inc. Triggered start products and processes for the production and use thereof

Cited By (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8399020B2 (en) * 2004-10-12 2013-03-19 Everris International B.V. Shaped plant growth nutrient products and processes for the production thereof
US20060089259A1 (en) * 2004-10-12 2006-04-27 Oms Investments, Inc. Shaped plant growth nutrient products and processes for the production thereof
US20080103048A1 (en) * 2006-10-26 2008-05-01 Radabaugh Robert M A Methods for the production of granular composite pesticidal compositions and the compositions produced thereby
US9155306B2 (en) * 2006-10-26 2015-10-13 Oms Investments, Inc. Methods for the production of granular composite pesticidal compositions and the compositions produced thereby
US20140221208A1 (en) * 2011-01-25 2014-08-07 Agrium Advanced Technologies Controlled release copper sulfate for phytoplankton control
US9113627B2 (en) 2011-04-20 2015-08-25 Exosect Limited Coating compositions for pathogen control in oilseeds
US11033025B2 (en) * 2011-04-20 2021-06-15 Terramera Exco Holdings Ltd. Coating compositions for pathogen control in monocotyledonous plants
WO2012143678A3 (en) * 2011-04-20 2013-03-07 Exosect Limited Coating compositions for pathogen control in vegetables
WO2012143674A3 (en) * 2011-04-20 2013-02-21 Exosect Limited Coating compositions for pathogen control in monocotyledonous plants
WO2012143679A3 (en) * 2011-04-20 2013-05-30 Exosect Limited Coating composition for pathogen control in cotton
WO2012143683A3 (en) * 2011-04-20 2013-06-06 Exosect Limited Compositions for growth and vigour in ornamentals
WO2012143680A3 (en) * 2011-04-20 2013-06-06 Exosect Limited Coating composition for plant structures
WO2012143684A3 (en) * 2011-04-20 2013-06-13 Exosect Limited Compositions for growth and vigour from oilseeds
WO2012143685A3 (en) * 2011-04-20 2013-06-13 Exosect Limited Composition for seed growth and vigour in monocots
WO2012143681A3 (en) * 2011-04-20 2013-06-13 Exosect Limited Compositions for growth and vigour in vegetables
WO2012143682A3 (en) * 2011-04-20 2013-06-13 Exosect Limited Compositions for growth and vigour in soybean
WO2012143686A3 (en) * 2011-04-20 2013-06-27 Exosect Limited Compositions for growth and vigour in cotton
US20140056956A1 (en) * 2011-04-20 2014-02-27 Exosect Limited Coating compositions for pathogen control in monocotyledonous plants
CN103619166A (zh) * 2011-04-20 2014-03-05 埃克索塞克特有限公司 用于单子叶植物中的病原体控制的包衣组合物
CN103635084A (zh) * 2011-04-20 2014-03-12 埃克索塞克特有限公司 用于蔬菜中的病原体控制的包衣组合物
WO2012143675A3 (en) * 2011-04-20 2013-02-21 Exosect Limited Coating compositions for pathogen control in soybean
GB2490248B (en) * 2011-04-20 2015-12-02 Exosect Ltd Use of compositions for growth and vigour from oilseeds
GB2490239B (en) * 2011-04-20 2015-12-02 Exosect Ltd Use of a coating composition for pathogen control in cotton
WO2012143676A3 (en) * 2011-04-20 2013-02-21 Exosect Limited Coating compositions for pathogen control in ornamentals
WO2012143679A2 (en) * 2011-04-20 2012-10-26 Exosect Limited Coating compositions for pathogen control in cotton
GB2490241B (en) * 2011-04-20 2015-12-02 Exosect Ltd Use of a coating composition for pathogen control in soybean
GB2490238B (en) * 2011-04-20 2015-12-02 Exosect Ltd Use of a coating composition for pathogen control in vegetables
GB2490243B (en) * 2011-04-20 2015-12-02 Exosect Ltd Use of a coating compositions for pathogen control in ornamentals
WO2012143677A3 (en) * 2011-04-20 2013-02-28 Exosect Limited Coating compositions for pathogen control in oilseeds
US10029952B2 (en) 2011-04-20 2018-07-24 Exosect Limited Compositions for growth and vigour in soybean
GB2490242B (en) * 2011-04-20 2015-12-02 Exosect Ltd Use of a coating composition for pathogen control in monocotyledonous plants
GB2490237B (en) * 2011-04-20 2015-12-02 Exosect Ltd Use of coating compositions for pathogen control in oilseeds
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US9961894B2 (en) 2011-04-20 2018-05-08 Exosect Limited Coating compositions for pathogen control in cotton
US9955685B2 (en) 2011-04-20 2018-05-01 Exosect Limited Coating composition for pathogen control in soybean
US9732006B2 (en) 2011-04-20 2017-08-15 Exosect Limited Composition for seed growth and vigour in monocots
US9955684B2 (en) 2011-04-20 2018-05-01 Exosect Limited Coating composition for pathogen control in vegetables
US20160235685A1 (en) * 2013-09-27 2016-08-18 L'oreal Photosensitive capsules and cosmetic and pharmaceutical use thereof
US10945963B2 (en) * 2013-09-27 2021-03-16 L'oreal Photosensitive capsules and cosmetic and pharmaceutical use thereof
WO2015119514A1 (en) * 2014-02-10 2015-08-13 Dow Agrosciences Llc Stable solid herbicide delivery systems
US10015965B2 (en) 2014-02-10 2018-07-10 Dow Agrosciences Llc Methods for using stable solid herbicide delivery systems
US10098342B2 (en) 2014-02-10 2018-10-16 Dow Agrosciences Llc Stable solid herbicide delivery systems
CN104086283A (zh) * 2014-06-11 2014-10-08 句容谷歌庄园现代农业科技发展有限公司 一种茶叶专用脲醛缓释肥料及其制备方法
EP3298094A4 (en) * 2015-05-22 2019-01-16 Honeywell International Inc. WAX-BASED FERTILIZER COATINGS COMPRISING POLYETHYLENE OR POLYPROPYLENE POLYMERS
DE102015012380A1 (de) * 2015-09-21 2017-03-23 Ask Chemicals Gmbh Beschichtetes Kernteilchen und Verfahren zur Herstellung desselben
US10645931B2 (en) 2016-12-15 2020-05-12 Wellmark International Extended release formulation
US10645932B2 (en) 2016-12-15 2020-05-12 Wellmark International Extended release formulation
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US10562827B1 (en) * 2017-08-30 2020-02-18 Nutrient Encapsulation Technologies Polymer coated fertilizer
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US11377395B2 (en) * 2017-09-13 2022-07-05 Lg Chem, Ltd. Controlled-release type fertilizer with decreased floating property comprising polyoxyethylene alky(-aryl) ether and method for preparing the same

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