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WO1993005652A1 - A method of producing herbicidal granular products - Google Patents

A method of producing herbicidal granular products Download PDF

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Publication number
WO1993005652A1
WO1993005652A1 PCT/FI1992/000258 FI9200258W WO9305652A1 WO 1993005652 A1 WO1993005652 A1 WO 1993005652A1 FI 9200258 W FI9200258 W FI 9200258W WO 9305652 A1 WO9305652 A1 WO 9305652A1
Authority
WO
WIPO (PCT)
Prior art keywords
activator
solid
granules
ingredient
product
Prior art date
Application number
PCT/FI1992/000258
Other languages
French (fr)
Inventor
Pontus Harju-Jeanty
Ari Juppo
Original Assignee
Kemira Agro Oy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kemira Agro Oy filed Critical Kemira Agro Oy
Priority to EP92919886A priority Critical patent/EP0643555A1/en
Priority to PL92302907A priority patent/PL172504B1/en
Priority to JP5505554A priority patent/JPH06510767A/en
Priority to SK355-94A priority patent/SK35594A3/en
Publication of WO1993005652A1 publication Critical patent/WO1993005652A1/en
Priority to BG98679A priority patent/BG98679A/en
Priority to NO941121A priority patent/NO178681C/en

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Classifications

    • 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
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/22—O-Aryl or S-Aryl esters thereof

Definitions

  • the present invention relates to a method of producing herbi ⁇ cidal granular products which contain carbamoyloxyphenyl- carbamates and/or substituted benzofuranes, known per se, as active ingredients, surfactants, suspending agents, inert car riers, and possibly other auxiliary agents, such as stabi ⁇ lizers, defoamers, coloring agents, and preservatives.
  • active ingredients carbamoyloxyphenyl- carbamates and/or substituted benzofuranes, known per se
  • active ingredients such as active ingredients, surfactants, suspending agents, inert car riers, and possibly other auxiliary agents, such as stabi ⁇ lizers, defoamers, coloring agents, and preservatives.
  • the sa active ingredients are insoluble in water and in the main foliage-acting, and they are thus sprayed, as water dilutions, onto the plant stand. For this reason the granules are made water dispersible so that a homo
  • Carbamoyloxyphenylcarbamate and benzofurane herbicides have conventionally been formulated as emulsion concentrates in which the active ingredient is dissolved in organic solvents and can, with the help of solution emulsifiers, be caused to mix with water to form an emulsion.
  • These formulations have, however, the drawbacks of toxicity of the products, due to the organic solvents, inflammability of the products, as well as difficulty of obtaining a stable uncrystallizing emulsion of the product together with water. Crystallization is typical specifically of methyl-3-tol ⁇ lcarbamoyloxyphenylcarbamate.
  • Air-jet and suspension mills are used for the grinding to produce a maximally finely divided active ingredient, preferably in the order of magnitude of 1 - 5 microns, in order to achieve biologic efficacy and as stable a suspension as possible when the granule is dispersed into water.
  • the active ingredient may be present in a water dilutable formulation either as a liquid suspension concentrat or as a granular product dispersible in water.
  • the disadvan ⁇ tages of a liquid product form often include storage difficul ⁇ ties, handling problems due to high viscosity, and the residue remaining in incompletely emptying containers.
  • the last- mentioned disadvantage is becoming a significant environmental problem when the used containers are being disposed of.
  • solid granules dispersible in a li ⁇ quid are avoided with solid granules dispersible in a li ⁇ quid.
  • a granular product can be packaged in mate ⁇ rials, such as carton, which load the environment less, and thus the empty packages are easier to dispose of.
  • the basic properties of water-dispersible granules include, in addition to the chemical stability of the active ingredients, also a good ability to be dispersed into water, sufficient granule strength so that detrimental dust is not detached in connection with storage or handling, free flow of the granules, and an ability to remain uncaked during storage.
  • the granule may contain, in addition to a water-insoluble carrier, also dispersing, suspending, wetting, preserving, defoaming, and anti-caking agents.
  • carbamoyloxyphenylcarbamates the most notab of which are methyl-3-m-tolylcarbamoyloxyphenylcarbamate, gen ⁇ erally named phenmedipham, and ethyl-3-phenylcarbamoyloxy- phenylcarbamate, generally named desmedipham (BP 679,283),
  • These active ingredi ⁇ ents can be used separately or as mixtures together with each other and/or with other control agents, especially for weed control in sugar beet cultivation.
  • the granules, mixed together with granules containing the active ingredient can be packaged in one container, in one space within it, as a sufficiently evenly distributed granular mix to form one prod ⁇ uct, or can be used as a separately dispensed agent in a tank mixture.
  • a separate tablet can be dispensed together with a granular or tablet-form active ingredient to form a combined mixture for use.
  • inorgan ic substances which adsorb large amounts of oily substances an are of natural origin, such as silica-based substances, alumi ⁇ num oxide based substances, attapulgite, montmorillonite, mica based substances, diatomite, bentonite, talcum, kaolin, lime, gypsum, and water-insoluble or water-soluble salts.
  • porous organic substances of natural origin such as ground wood or corn cobs, ground coconut or almond shells, ground olive skins ground grain husks, cellulose, starch and alginates, or porous structures which are based on polymeric initial substances of natural origin which have been modified, such as lignin deriva tives, cellulose derivatives, starch derivatives, and cyclodex trins, or synthetic polymers such as polyacrylates, polyacryl- amides, polyvinyl derivatives, polymers of maleic acid, poly- urethanes, polylactides, and polymers of glycolic acid.
  • polymeric initial substances of natural origin which have been modified, such as lignin deriva tives, cellulose derivatives, starch derivatives, and cyclodex trins
  • synthetic polymers such as polyacrylates, polyacryl- amides, polyvinyl derivatives, polymers of maleic acid, poly- urethanes, polylactides, and polymers of glycolic acid.
  • the activator may be enclosed in the carrier material by coat ⁇ ing the impregnated particles with a polymer, such as polyviny alcohol, or with sugar based or sugar alcohol based substances, such as lactose, CMC and sorbitol. In this case the speed of release of the activator can also be regulated.
  • a polymer such as polyviny alcohol
  • sugar based or sugar alcohol based substances such as lactose, CMC and sorbitol
  • a liquid activator can also be enclosed in capsules, which can further be used in a granular product. Encapsulation methods are commonly known. The strength of the granules and their resistance to abrasion can also be affected by means of coatin materials. On the other hand, the flow of the product can be improved by them.
  • An activator which contains surfactants and/or oil is hot im ⁇ portant for the actual granulation; its main purpose is to enhance the biologic action of the product.
  • the proportion of activator may be in general 1 - 80 % of the weight of the granular product, preferably 0.5 - 5 times the amount of carbamoyloxyphenylcarbamate in the product.
  • the activator may be in a solid or a liquid state (at 20 °C) , in which case it can be impregnated into a carrier or be mixed with the mix to be granulated. Alternatively it may also be impregnated into or be attached to the product in some other manner after the granulation.
  • the activator may contain anionic, cationic, non-ionic or am- pholytic surfactants, or these together with a mineral oil, vegetable oil or animal oil.
  • the proportion of surfactants in the activator may be 2 - 100 %, preferably 50 - 100 %.
  • the pro portion of oil may respectively be 0 - 98 %, preferably 0 - 50 %.
  • the anionic surfactants may be alkyl sulfonates, alkylaryl sulfonates, sulfate ethers, fatty alcohol sulfates, sulfate ester sulfocarboxylic acids and their derivatives, alkyl- glycerolether sulfonates, sulfoesters, sulfonamides and phos ⁇ phoric acid mono- and diesters, bile acids and their salts.
  • the cationic surfactants may be alkylamines or alkylarylamines, alkyl or alkylaryl imidazolines, and alkylaminoamides.
  • the non-ionic surfactants may be fatty alcohol ethoxylates, fatty acid ethoxylates, alkylaryl ethoxylates, alkyl sugar ethoxylates or alkyl sugar alcohol ethoxylates, alkylamine or alkylarylamine polyglycol ethers, fatty acid amide derivatives, diethanolamides or polydiethanolamides of fatty acids, deriva ⁇ tives of mono-, di-, and triglycerides, acetylene diols, and silicon-based surfactants.
  • ampholytic surfactants may be alkyl and alkylaryl betaine derivatives, alkyl and alkylaryl (poly)glycine derivatives, alkylamide and alkylarylamide carboxylates, and alkylamine and alkylarylamine sulfonates. Surfactants which contain fluorine may also be used.
  • the oily substance may be a mineral oil, preferably having a low viscosity so that it can easily become impregnated into the carrier. On the other hand, the oil must not significantly impede the crop plant. It is most advantageous to use low- aromatic paraffin oil, e.g. Neutral solvent 150, Exxon.
  • the oily substance may be a vegetable oil or its hydrolysis prod- uct, such as soy oil or a fatty acid mixture of soy oil.
  • the oil may also contain phospholipids and sterols.
  • the oily substance may be of animal origin, in which case it preferable if the oil contains a large amount of unsaturated fatty acids and their glycerides.
  • the material can be comminuted, for example, while dry in an air jet mill or as a suspension in a pearl mill. It is essen ⁇ tial that the particle size of the solid is on average approx 10 ⁇ m and that of the active ingredient preferably in the ord of 5 p (measured by a Coulter apparatus), in order for the biologic efficacy to be achieved.
  • auxiliary agents can be used which promot granule formation, re-wetting of the granules, "and rapid deco position and dispersion of the granules at the time the solu ⁇ tion for use is being prepared, as well as agents which inhib the foaming of the solution for use.
  • active in ⁇ gredient may decompose in a basic solution for use
  • inorganic or organic pH control agents may be used in the mixture, such as phosphoric acid or its acid salts and citric acid, so that the pH of the solution for use will be below 7, preferably 3. - 5.5.
  • Auxiliary granulation agents may be used in granules in which the active ingredient and the activator are in the same granu or in separate active-ingredient granules and activator gran ⁇ ules.
  • Agents promoting the decomposition of the granule which may polymers such as polyvinyl pyrrolidone and starch and its mod fied forms, or salts such as ammonium sulfate, or organic water-soluble compounds such as urea, or substances capable of liberating gas, such as carbonates.
  • dispersants such as phenyl sulfonates, alkylnaphthalene sulfonates and polymerized naph ⁇ thalene sulfonates, polyacrylic acids and their salts, poly- acrylamides, polyalkoxydiamine derivatives, polyethylene oxides, polypropylene oxide, polybutylene oxide, taurine deriv atives and their mixtures, and sulfonated lignin derivatives.
  • Dispersants can be used at 0.1 - 50 %, preferably 5 - 20 % of the granular product.
  • Similar products may also be used as agents promoting granula ⁇ tion, such as polyethylene glycol, in which case it is advan ⁇ tageous to add the activator-containing component at a propor ⁇ tion of 1 - 20 % to the completed granule which contains the active ingredient.
  • the foaming of a mixture to be prepared for spraying can be controlled with defoamers such as silica-based agents. It is preferable to use such agents at 0 - 0.5 I of the amount of the granular product.
  • Prior-known methods can be used for the granulation, such as disc granulation, spray drying (e.g. Niro) , fluid-bed granula ⁇ tion (e.g. Glatt and Schugi), stir granulation using a vertical mixer (e.g. Fielder) or a blade mixer (e.g. Forberg), extruder granulation (e.g. Nica) or compacting granulation (e.g. Bepex apparatus) or centrifugal granulation (e.g. CF-granulator, Freund Industrial Co) , or spray-bed granulation.
  • spray drying e.g. Niro
  • fluid-bed granula ⁇ tion e.g. Glatt and Schugi
  • stir granulation using a vertical mixer (e.g. Fielder) or a blade mixer (e.g. Forberg), extruder granulation (e.g. Nica) or compacting granulation (e.g. Bepex apparatus) or centrifugal granulation
  • the activator may be compressed into a water-dispersible tab- let, in which case its size may vary depending on the matrix.
  • Conventional tablet presses include rotation (Mansty) and ec centric tablet presses (Diaf) .
  • the granule sur ⁇ face can be hardened mechanically by rounding the granule, for example, by using a Spheronizer apparatus (Nica) or by coating the granules with materials suitable for the purpose, as mentioned above.
  • the pro ⁇ duct may be dried either in the apparatus used for the granu ⁇ lation or in a separate apparatus intended for drying (e.g. a fluid-bed drier) . It is advantageous if the moisture content of the granular product is below 5 %, preferably below 1 %.
  • the granule size of the final product may vary, depending on the granulation method, on average up to 3 mm or considerably higher, in the case of tablets dispersible in water.
  • control agents can be mixed together with carbamoyloxyphenylcarbamates (such as phenmedipham and desmedipham) to form a granular product.
  • the control agents may be herbicides, agents for plant-disease control, and insecticides, as well as growth control agents.
  • herbicides used particularly in the cultivation of sugar beet such as ethofumesate, methamitron, chlorodazone, lenasil, pyridate, metholachlorine, trichloro- acetic acid, EPTC, quinmerac, cycloate, chlopyralide, flur- oxipyr, isocarbimide, propham, trifluraline, alloxydime so ⁇ dium, cetoxydime, diallate, fluazifop-butyl, triallate, dala- pon or propaqizafob.
  • herbicides used particularly in the cultivation of sugar beet such as ethofumesate, methamitron, chlorodazone, lenasil, pyridate, metholachlorine, trichloro- acetic acid, EPTC, quinmerac, cycloate, chlopyralide, flur- oxipyr, isocarbimide, propham, tri
  • the products of the invention can be used after the emergence of seedlings of the crop plant, preferably in several rounds application during the growing season.
  • a suitable amount of active ingredient per one spraying is 0.1 - 1 kg per hectare, depending on the number of rounds of application.
  • a separate granular phenmedipham product can be prepared from raw-material mixture which contains: phenmedipham 80 % lignin sulfonates 7.4 % phenyl sulfonates 7.0 % diatomite 2.0 % kaolin 3.6 %
  • the raw materials used for the preparation are pre-ground with an air-jet mill (Alpine) for granulation.
  • the granulation can be carried out by extrusion (Nica) , in which case water is mixed with the dry mix at 10 % of the mix.
  • the diameter of the openings in the matrix is 1 mm.
  • the extruded mix is cut into granules of approx. 2 mm in length, which can be further round ed in a Sp eronizer apparatus.
  • the product is dried in a fluid bed drier.
  • the product obtained by the method disperses excel ⁇ lently into water.
  • the suspension can be verified with an experiment in which 1 g of product is dispensed into a 100 ml narrow-tipped graduated test tube containing 100 ml of distilled water (+25 °C) . After the wetting of the granules has been noted, the tube is turned 30 times through 180 degrees. Sediment formation is observed for 1 min, 5 min, and 10 min.
  • the amount of sediment separated at 1 min after mixing is 0.05 ml, at 5 min after mixing 0.05 ml, and at 10 min after mixing 0.05 ml.
  • the average particle size in the suspension was approx. 2 ⁇ m.
  • a separate granular phenmedipham product can be prepared from pre-ground raw material mixture which contains: phenmedipham 89 • 5 lignin sulfonate derivatives 7.2 phenyl sulfonates 3.6 %
  • the mixture can be granulated by spray drying from a 50 % aqueous suspension of the mixture (Niro) .
  • the average size of the granules depends on the size of the apparatus.
  • the granul are round in shape. Determined by the method described above, the suspension results are: 1 min) 0.15 ml; 5 min) 0.9 ml; 10 min) 1.2 ml.
  • the average particle size in the suspension i 3 urn.
  • a separate granular phenmedipham product can be prepared from the raw materials mentioned in Example 1 by using disc granul ation, in which case the mix to be granulated is wetted using water at 10 % by weight, calculated from the dry matter.
  • the suspension results are: 1 min) 0.02 ml; 5 min) 0.15 ml; 10 mi 0.25 ml.
  • the average particle size in the suspension is appro 3 um.
  • Separate granules containing an activator can be prepared by making from a pre-ground carrier mixture by disc granulation granules which contain: silicic acid (precipitated, e.g. Zeolthix 265) 85 % ammonium sulfate 2 % sodium chloride 6 % lignin sulfonates 2 phenyl sulfonates 5
  • an activator solution which contains: alkyl-sorbitol ethoxylate 42 % fatty alcohol ethoxylate 21 % ethoxylated fatty acid esters 8 % ethoxylated fatty acid phosphate esters 5 % alkylaryl sulfonic acid 5 % alkylamine ethoxylate 4 % paraffin oil 15 a, o
  • Separate granules containing an activator may also be mixed to form a single granule mixture with the above-mentioned granule formulations which contain active ingredients, or it can be dispensed separately to form a tank mixture with them.
  • the granules disperse moderately into water.
  • a granular product containing phenmedipham and an activator ca be prepared from a raw-material mixture which contains: phenmedipham 16.0 % lignin sulfonates 2.6 % phenyl sulfonates 5.5 % urea 7.0 % kaolin 5.5 % diatomite 5.0 % mixture B 50.4 % polyethylene glycol 8.0 %
  • Mixture B contains: silicic acid (precipitated) 37.5 % bentonite 2.5 % fatty alcohol ethoxylates 16.0 % polyoxyethylene sorbitols 33.8 % paraffin oil 5.1 % alkylamine ethoxylates 5.1 %
  • the mixture is granulated in a disc in which the mix is heate to +70 °C, and the formed granular product is cooled back to room temperature.
  • the suspension properties of the product ar moderate.
  • a layered granular product containing phenmedipham and an act vator can be prepared from a mixture which contains: phenmedipham 16.0 % lignin sulfonates 2.7 % phenyl sulfonates 5.3 % kaolin 15.5 % diatomite 5.0 a - polyethylene glycol 5.0 % mixture B 50.4 % (as in Example 5)
  • Mixture B is applied as a coating with the help of polyethyle glycol to a granule prepared from the other raw materials, at +70 °C in a disc granulator.
  • the suspension properties of the granular product are moderate.
  • a granular product containing phenmedipham and an activator ca be prepared by the extrusion technique from a raw-material mixture which contains: phenmedipham 32.0 % lignin sulfonates phenyl sulfonates kaolin diatomite naphthene sulfonates mixture C
  • Mixture C contains: silicic acid (precipitated) phenyl sulfonates ammonium sulfate sodium chloride lignin sulfonates naphthene sulfonates mixture A
  • the suspension properties are: 1 min) 0.15 ml; 5 min) 0.3 ml; 10 min) 0.4 ml.
  • a granular product containing phenmedipham and desmedipham can be prepared from a mixture which contains: phenmedipham 60.0 % desmedipham 20.0 % lignin sulfonates 5.9 % phenyl sulfonates 5.6 % kaolin 4.0 % diatomite 2.0 %
  • the suspension properties of the granular product are: 1 min) 0.01 ml; 5 min) 0.02 ml; 10 min) 0.03 ml.
  • a granular product containing phenmedipham and ethofumesate can be prepared by the disc granulation technique from a mixture which contains: phenmedipham 32.0 % ethofumesate 40.0 % lignin sulfonates 6.0 % phenyl sulfonates 5.0 % naphthene sulfonates 9.0 % bentonite 0.2 % urea 7.8 %
  • the suspension properties of the granular product are: 1 min) 0.01 ml; 5 min) 0.03 ml; 10 min) 0.04 ml.
  • Granules containing phenmedipham and ethofumesate can be pre ⁇ pared by disc granulation from a mixture which contains: phenmedipham 35.0 % ethofumesate 34.7 % lignin sulfonates 5.9 % phenyl sulfonates 5.6 % diatomite 2.0 % kaolin 16.8 %
  • the suspension properties were: 1 min) 0.15 ml; 5 min) 0.5 ml; 10 min) 0.8 ml.
  • a ' granular product containing phenmedipham and methamitron ca be prepared by disc granulation from a mixture which contains: phenmedipham 16.0 % methamitron 64.0 % lignin sulfonates 5.9 % phenyl sulfonates 5.6 % diatomite 2.0 % kaolin 6.5 %
  • the suspension properties of the granular product are: 1 min) 0.01 ml; 5 min) 0.02 ml; 10 min) 0.03 ml.
  • a granular product containing phenmedipham and chlorodazone c be prepared by disc granulation from a mixture which contains: phenmedipham 25.0 % chlorodazone 50.0 % lignin sulfonates 5.9 o phenyl sulfonates 5.6 diatomite 1.1 Q. kaolin 12.4
  • the suspension capacity of the granules is: 1 min) 0.03 ml; 5 min) 0.10 ml; 10 min) 0.15 ml.
  • a granular product containing phenmedipham and chlorodazone ca be prepared by disc granulation from a mixture which contains: phenmedipham 20.0 % chlorodazone 60.0 % lignin sulfonates 5.9 % phenyl sulfonates 5.6 % diatomite 1.1 % kaolin 7.4 %
  • the suspension properties of the product are: 1 min) 0.03 ml; 5 min) 0.10 ml; 10 min) 0.15 ml.
  • a granular product containing phenmedipham, desmedipham and chlorodazone can be prepared by disc granulation from a mixtur which contains: phenmedipham 12.0 % desmedipham 3.0 % chlorodazone 45.0 % lignin sulfonates 5.9 % phenyl sulfonates 7.0 % fluorinated surfactant 2.0 % alkylaryl betaine 5.0 % diatomite 1.0 % kaolin 19.1 %
  • the suspension capacity of the granules is: 1 min) 0.1 ml; 5 min) 0.35 ml; 10 min) 0.45 ml.
  • a tablet containing phenmedipham and an activator can be pre- pared by compression using a pressure of 300 kg/cm from a mixture which contains:
  • the tablet can be made in a mold having a diameter of 50 mm, which case 30 g of mixture is used.
  • the suspension properties of the tablet are moderate when the dispersion of the tablet in a 500 ml decanter containing 300 of water is observed visually.
  • the activities of the formulations produced were tested in action against weeds commonly encountered in sugar beet cul ⁇ tivation, such as amaranth (Amaranthus retroflexus) , rape (Brassica napus) , goosefoot (Chenopodium album) , and common chickweed (Stellaria media) .
  • weeds commonly encountered in sugar beet cul ⁇ tivation such as amaranth (Amaranthus retroflexus) , rape (Brassica napus) , goosefoot (Chenopodium album) , and common chickweed (Stellaria media) .
  • Four pots per weed species per test specimen were used in the experiments.
  • the efficacies we evaluated in accordance with typical evaluation principles on scale of 0 - 10, the complete destruction of the plant being described by 10. The mean of four pots was reported.
  • the sensitivity to injury of the sugar beet (Beta vulgaris) wa determined on the same scale.
  • the biologic efficacy of a mixture of granular phenmedipham (a in Example 1) and a granular activator (as in Example 4) was compared with a phenmedipham-containing emulsion concentrate preparation (Kemifam) available on the market.
  • the amounts of active ingredient in the test specimens were the same, 640 g o active ingredient per hectare.
  • the efficacies were inspected 7 days after the spraying.
  • Example 1 0.8 kg 7.3 8.2 8.7 7.2 1.0 + Example 4 3.0 kg
  • Example 8 0.8 kg 8.3 5.3 9.0 22.6 1.0 + Example 4 3.8 kg
  • Example 10 1.5 kg 7.0 9.0 9.5 0 + Example 4 1.1 kg
  • Methamitron which works both soil-applied and foliage-applie does not require activators in the same way as does phen ⁇ medipham; the relatively high efficacy of granular product 10 is an indication of this. However, even in this case a signif icant improvement of action on rape is achieved with an addi ⁇ tion of activator. Overall, using a granular product of phen ⁇ medipham + methamitron + activator, an excellent selective biologic action is achieved without any symptoms of injury in the sugar beet.
  • the purpose of the experiment was to compare the biologic ac ⁇ tion of granular products containing phenmedipham to the action of emulsion and suspension concentrate products already avail ⁇ able commercially.
  • the efficacy of the granular product containing an active in ⁇ gredient, used together with a granular activator, the total amount of the material used being 1.75 kg/ha, is as good as th efficacy of the suspension product when used at 3 1/ha.
  • a granular product containing more activator was used,. in which case the total amount of material used is 2.75 kg/ha, a sig ⁇ nificantly better efficacy is obtained with the granular prod ⁇ uct than with the suspension product.
  • a liquid activator in the con ⁇ ventional manner as a tank mixture, as in test specimen 5.
  • the activator granules of Example 4 contain mixture A 60 %, in which case test specimens 4 and 5 contain equal amounts of the liquid ingredient.
  • the solid carrier material of the granular product in ⁇ creases the effect of the activator granules on the efficacy o the active ingredient by up to 10 %. It is also noteworthy tha this granular product is more than 10 % more effective than th commercial suspension concentrate product and up to 20 % more effective than the commercial emulsion concentrate product.
  • Kemiron is an emulsion concentrate containing ethofumesate 200 g per liter, and granular ethofumesate (EFU granule) is a water dispersible granular product containing effective in ⁇ gredient 65 %.
  • EFU granule granular ethofumesate

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  • Life Sciences & Earth Sciences (AREA)
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  • Health & Medical Sciences (AREA)
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  • Plant Pathology (AREA)
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Abstract

The invention relates to a method of producing granular mixtures which contain herbicides known per se, the activator used being a solid composition in which the activator ingredients are either impregnated into and/or mixed with a carrier material.

Description

A method of producing herbicidal granular products
The present invention relates to a method of producing herbi¬ cidal granular products which contain carbamoyloxyphenyl- carbamates and/or substituted benzofuranes, known per se, as active ingredients, surfactants, suspending agents, inert car riers, and possibly other auxiliary agents, such as stabi¬ lizers, defoamers, coloring agents, and preservatives. The sa active ingredients are insoluble in water and in the main foliage-acting, and they are thus sprayed, as water dilutions, onto the plant stand. For this reason the granules are made water dispersible so that a homogenous suspension which will not clog the sprayer will be obtained when the product is di¬ luted with water.
Carbamoyloxyphenylcarbamate and benzofurane herbicides have conventionally been formulated as emulsion concentrates in which the active ingredient is dissolved in organic solvents and can, with the help of solution emulsifiers, be caused to mix with water to form an emulsion. These formulations have, however, the drawbacks of toxicity of the products, due to the organic solvents, inflammability of the products, as well as difficulty of obtaining a stable uncrystallizing emulsion of the product together with water. Crystallization is typical specifically of methyl-3-tolγlcarbamoyloxyphenylcarbamate.
Product forms in which the active ingredients are not in a dis solved form are as such advantageous, since then the problems of toxicity, inflammability, packaging material, and storage are usually avoided, since especially in the case of foliage- acting herbicides, penetration and translocation abilities are required in order to achieve sufficient biologic efficacy. Hydrolytic decomposition is often also a disadvantage. An ac¬ tive ingredient in molecular form is, in a true liquid, capabl of penetrating through the wax and cuticle layers much more effectively than is a solid particle. For this reason, in- soluble particles of the active ingredient must be as finely ground as possible, and their penetration and translocation abilities must be improved with oils, organic solvent addi¬ tions, and surfactants. In the case of carbamoyloxyphenylcarb mates in particular, it is indispensable to add exceptionally large amounts of these auxiliary agents in order to achieve a sufficient biologic efficacy. Air-jet and suspension mills are used for the grinding to produce a maximally finely divided active ingredient, preferably in the order of magnitude of 1 - 5 microns, in order to achieve biologic efficacy and as stable a suspension as possible when the granule is dispersed into water.
In solid form, the active ingredient may be present in a water dilutable formulation either as a liquid suspension concentrat or as a granular product dispersible in water. The disadvan¬ tages of a liquid product form often include storage difficul¬ ties, handling problems due to high viscosity, and the residue remaining in incompletely emptying containers. The last- mentioned disadvantage is becoming a significant environmental problem when the used containers are being disposed of. These problems are avoided with solid granules dispersible in a li¬ quid. In addition, a granular product can be packaged in mate¬ rials, such as carton, which load the environment less, and thus the empty packages are easier to dispose of.
The basic properties of water-dispersible granules include, in addition to the chemical stability of the active ingredients, also a good ability to be dispersed into water, sufficient granule strength so that detrimental dust is not detached in connection with storage or handling, free flow of the granules, and an ability to remain uncaked during storage. In order to achieve these properties, the granule may contain, in addition to a water-insoluble carrier, also dispersing, suspending, wetting, preserving, defoaming, and anti-caking agents. It is known that carbamoyloxyphenylcarbamates, the most notab of which are methyl-3-m-tolylcarbamoyloxyphenylcarbamate, gen¬ erally named phenmedipham, and ethyl-3-phenylcarbamoyloxy- phenylcarbamate, generally named desmedipham (BP 679,283),
Figure imgf000005_0001
where Rl and R2 = CH3 or Rl = H and R2 = CH2CH, are selective and good by their her.bicidal properties. These active ingredi¬ ents can be used separately or as mixtures together with each other and/or with other control agents, especially for weed control in sugar beet cultivation.
Conventionally the above active ingredients have been formu¬ lated as emulsion concentrates. But since the aim is to avoid organic solvents, and since phenmedipham tends to crystallize when these formulation forms are diluted with water, the objec has now been to produce water-dispersible granules of these active ingredients. It is previously known to prepare water- dispersible granules from herbicides (US 3.920.442), as also dispersible triazine herbicidal granules, which contain a sur¬ factant which improves the crystallization properties (US 4,197,112), or granules the physical properties of which are improved by surfactants (EP 201,417). The obstacle to the com¬ mercialization of dispersible carbamoyloxyphenylcarbamates has been the difficulty of incorporating sufficient biologic ef¬ ficacy into the product, since the amount of liquid oil and/or surfactants is very high in ratio to the amounts of the active ingredients (approx. 1:1) and uneconomical to implement techni cally.
It is known that a good biologic efficacy can be achieved with water dispersible granules made of certain active ingredients of herbicides. However, with carbamoyloxyphenylcarbamates, sufficient efficacy cannot be reached by these methods.
Now it has been observed surprisingly that, with water disper ible granular products which contain carbamoyloxyphenylcarba- mate, it is possible not only to achieve the above properties of a granular product but also to enhance them significantly preparing a granular or tablet-form product in which an acti¬ vator is impregnated into a carrier, which for its part is added, evenly distributed or as a layer on the surface of the granule or the tablet or as a core inside the granule or the tablet. On the other hand, a separate granule or tablet can be made of a liquid activator and the carrier. The granules, mixed together with granules containing the active ingredient, can be packaged in one container, in one space within it, as a sufficiently evenly distributed granular mix to form one prod¬ uct, or can be used as a separately dispensed agent in a tank mixture. A separate tablet can be dispensed together with a granular or tablet-form active ingredient to form a combined mixture for use.
By using an activator impregnated into a carrier, the enhancin of the biologic efficacy of solid carbamoyloxyphenylcarbamate has even been increased as compared with unimpregnated acti¬ vator; this has been observed in both greenhouse and field tests.
As the carrier for the activator it is possible to use inorgan ic substances which adsorb large amounts of oily substances an are of natural origin, such as silica-based substances, alumi¬ num oxide based substances, attapulgite, montmorillonite, mica based substances, diatomite, bentonite, talcum, kaolin, lime, gypsum, and water-insoluble or water-soluble salts.
On the other hand, it is possible to use as the carrier porous organic substances of natural origin, such as ground wood or corn cobs, ground coconut or almond shells, ground olive skins ground grain husks, cellulose, starch and alginates, or porous structures which are based on polymeric initial substances of natural origin which have been modified, such as lignin deriva tives, cellulose derivatives, starch derivatives, and cyclodex trins, or synthetic polymers such as polyacrylates, polyacryl- amides, polyvinyl derivatives, polymers of maleic acid, poly- urethanes, polylactides, and polymers of glycolic acid.
The activator may be enclosed in the carrier material by coat¬ ing the impregnated particles with a polymer, such as polyviny alcohol, or with sugar based or sugar alcohol based substances, such as lactose, CMC and sorbitol. In this case the speed of release of the activator can also be regulated.
A liquid activator can also be enclosed in capsules, which can further be used in a granular product. Encapsulation methods are commonly known. The strength of the granules and their resistance to abrasion can also be affected by means of coatin materials. On the other hand, the flow of the product can be improved by them.
An activator which contains surfactants and/or oil is hot im¬ portant for the actual granulation; its main purpose is to enhance the biologic action of the product.
The proportion of activator may be in general 1 - 80 % of the weight of the granular product, preferably 0.5 - 5 times the amount of carbamoyloxyphenylcarbamate in the product.
The activator may be in a solid or a liquid state (at 20 °C) , in which case it can be impregnated into a carrier or be mixed with the mix to be granulated. Alternatively it may also be impregnated into or be attached to the product in some other manner after the granulation. The activator may contain anionic, cationic, non-ionic or am- pholytic surfactants, or these together with a mineral oil, vegetable oil or animal oil. The proportion of surfactants in the activator may be 2 - 100 %, preferably 50 - 100 %. The pro portion of oil may respectively be 0 - 98 %, preferably 0 - 50 %.
The anionic surfactants may be alkyl sulfonates, alkylaryl sulfonates, sulfate ethers, fatty alcohol sulfates, sulfate ester sulfocarboxylic acids and their derivatives, alkyl- glycerolether sulfonates, sulfoesters, sulfonamides and phos¬ phoric acid mono- and diesters, bile acids and their salts.
The cationic surfactants may be alkylamines or alkylarylamines, alkyl or alkylaryl imidazolines, and alkylaminoamides.
The non-ionic surfactants may be fatty alcohol ethoxylates, fatty acid ethoxylates, alkylaryl ethoxylates, alkyl sugar ethoxylates or alkyl sugar alcohol ethoxylates, alkylamine or alkylarylamine polyglycol ethers, fatty acid amide derivatives, diethanolamides or polydiethanolamides of fatty acids, deriva¬ tives of mono-, di-, and triglycerides, acetylene diols, and silicon-based surfactants.
The ampholytic surfactants may be alkyl and alkylaryl betaine derivatives, alkyl and alkylaryl (poly)glycine derivatives, alkylamide and alkylarylamide carboxylates, and alkylamine and alkylarylamine sulfonates. Surfactants which contain fluorine may also be used.
The oily substance may be a mineral oil, preferably having a low viscosity so that it can easily become impregnated into the carrier. On the other hand, the oil must not significantly impede the crop plant. It is most advantageous to use low- aromatic paraffin oil, e.g. Neutral solvent 150, Exxon. The oily substance may be a vegetable oil or its hydrolysis prod- uct, such as soy oil or a fatty acid mixture of soy oil. The oil may also contain phospholipids and sterols.
The oily substance may be of animal origin, in which case it preferable if the oil contains a large amount of unsaturated fatty acids and their glycerides.
It is a prerequisite for the granulation of the active in¬ gredient, or of the active ingredient and its carrier which contains an activator, or for the granulation of the carrier the active ingredient or the activator, that the material to granulated is finely divided.
The material can be comminuted, for example, while dry in an air jet mill or as a suspension in a pearl mill. It is essen¬ tial that the particle size of the solid is on average approx 10 μm and that of the active ingredient preferably in the ord of 5 p (measured by a Coulter apparatus), in order for the biologic efficacy to be achieved.
In the granulation, auxiliary agents can be used which promot granule formation, re-wetting of the granules, "and rapid deco position and dispersion of the granules at the time the solu¬ tion for use is being prepared, as well as agents which inhib the foaming of the solution for use. Since the active in¬ gredient may decompose in a basic solution for use, inorganic or organic pH control agents may be used in the mixture, such as phosphoric acid or its acid salts and citric acid, so that the pH of the solution for use will be below 7, preferably 3. - 5.5.
Auxiliary granulation agents may be used in granules in which the active ingredient and the activator are in the same granu or in separate active-ingredient granules and activator gran¬ ules. Agents promoting the decomposition of the granule, which may polymers such as polyvinyl pyrrolidone and starch and its mod fied forms, or salts such as ammonium sulfate, or organic water-soluble compounds such as urea, or substances capable of liberating gas, such as carbonates.
As agents improving the suspension of the granules it is pos¬ sible to use, as is commonly known, dispersants such as phenyl sulfonates, alkylnaphthalene sulfonates and polymerized naph¬ thalene sulfonates, polyacrylic acids and their salts, poly- acrylamides, polyalkoxydiamine derivatives, polyethylene oxides, polypropylene oxide, polybutylene oxide, taurine deriv atives and their mixtures, and sulfonated lignin derivatives. Dispersants can be used at 0.1 - 50 %, preferably 5 - 20 % of the granular product.
Similar products may also be used as agents promoting granula¬ tion, such as polyethylene glycol, in which case it is advan¬ tageous to add the activator-containing component at a propor¬ tion of 1 - 20 % to the completed granule which contains the active ingredient.
The foaming of a mixture to be prepared for spraying can be controlled with defoamers such as silica-based agents. It is preferable to use such agents at 0 - 0.5 I of the amount of the granular product.
Prior-known methods can be used for the granulation, such as disc granulation, spray drying (e.g. Niro) , fluid-bed granula¬ tion (e.g. Glatt and Schugi), stir granulation using a vertical mixer (e.g. Fielder) or a blade mixer (e.g. Forberg), extruder granulation (e.g. Nica) or compacting granulation (e.g. Bepex apparatus) or centrifugal granulation (e.g. CF-granulator, Freund Industrial Co) , or spray-bed granulation.
The activator may be compressed into a water-dispersible tab- let, in which case its size may vary depending on the matrix. Conventional tablet presses include rotation (Mansty) and ec centric tablet presses (Diaf) .
It is also possible to use for the granulation and tablettin two or more of the above methods in series. The granule sur¬ face can be hardened mechanically by rounding the granule, for example, by using a Spheronizer apparatus (Nica) or by coating the granules with materials suitable for the purpose, as mentioned above.
It is important that the granular product is dried. The pro¬ duct may be dried either in the apparatus used for the granu¬ lation or in a separate apparatus intended for drying (e.g. a fluid-bed drier) . It is advantageous if the moisture content of the granular product is below 5 %, preferably below 1 %.
The granule size of the final product may vary, depending on the granulation method, on average up to 3 mm or considerably higher, in the case of tablets dispersible in water.
It is self-evident that also other control agents can be mixed together with carbamoyloxyphenylcarbamates (such as phenmedipham and desmedipham) to form a granular product. The control agents may be herbicides, agents for plant-disease control, and insecticides, as well as growth control agents.
It is advantageous to use herbicides used particularly in the cultivation of sugar beet, such as ethofumesate, methamitron, chlorodazone, lenasil, pyridate, metholachlorine, trichloro- acetic acid, EPTC, quinmerac, cycloate, chlopyralide, flur- oxipyr, isocarbimide, propham, trifluraline, alloxydime so¬ dium, cetoxydime, diallate, fluazifop-butyl, triallate, dala- pon or propaqizafob.
The products of the invention can be used after the emergence of seedlings of the crop plant, preferably in several rounds application during the growing season. A suitable amount of active ingredient per one spraying is 0.1 - 1 kg per hectare, depending on the number of rounds of application.
The invention is described below in greater detail with the help of examples.
Example 1
A separate granular phenmedipham product can be prepared from raw-material mixture which contains: phenmedipham 80 % lignin sulfonates 7.4 % phenyl sulfonates 7.0 % diatomite 2.0 % kaolin 3.6 %
The raw materials used for the preparation are pre-ground with an air-jet mill (Alpine) for granulation. The granulation can be carried out by extrusion (Nica) , in which case water is mixed with the dry mix at 10 % of the mix. The diameter of the openings in the matrix is 1 mm. The extruded mix is cut into granules of approx. 2 mm in length, which can be further round ed in a Sp eronizer apparatus. The product is dried in a fluid bed drier. The product obtained by the method disperses excel¬ lently into water.
The suspension can be verified with an experiment in which 1 g of product is dispensed into a 100 ml narrow-tipped graduated test tube containing 100 ml of distilled water (+25 °C) . After the wetting of the granules has been noted, the tube is turned 30 times through 180 degrees. Sediment formation is observed for 1 min, 5 min, and 10 min.
In the case of the above-mentioned granules, the amount of sediment separated at 1 min after mixing is 0.05 ml, at 5 min after mixing 0.05 ml, and at 10 min after mixing 0.05 ml.
The average particle size in the suspension, determined using Coulter LS 130 apparatus, was approx. 2 μm.
For comparison purposes, a determination of the suspension pr perties was performed on a commercial product called Goltix. The values obtained were: 1 min) 0.01 ml; 5 min) 0.1 ml; and min) 0.18 ml.
Example 2
A separate granular phenmedipham product can be prepared from pre-ground raw material mixture which contains: phenmedipham 89 •5 lignin sulfonate derivatives 7.2 phenyl sulfonates 3.6 %
The mixture can be granulated by spray drying from a 50 % aqueous suspension of the mixture (Niro) . The average size of the granules depends on the size of the apparatus. The granul are round in shape. Determined by the method described above, the suspension results are: 1 min) 0.15 ml; 5 min) 0.9 ml; 10 min) 1.2 ml. The average particle size in the suspension i 3 urn.
Example 3
A separate granular phenmedipham product can be prepared from the raw materials mentioned in Example 1 by using disc granul ation, in which case the mix to be granulated is wetted using water at 10 % by weight, calculated from the dry matter. The suspension results are: 1 min) 0.02 ml; 5 min) 0.15 ml; 10 mi 0.25 ml. The average particle size in the suspension is appro 3 um.
Example 4
Separate granules containing an activator can be prepared by making from a pre-ground carrier mixture by disc granulation granules which contain: silicic acid (precipitated, e.g. Zeolthix 265) 85 % ammonium sulfate 2 % sodium chloride 6 % lignin sulfonates 2 phenyl sulfonates 5
and by impregnating into it an activator solution (mixture A) which contains: alkyl-sorbitol ethoxylate 42 % fatty alcohol ethoxylate 21 % ethoxylated fatty acid esters 8 % ethoxylated fatty acid phosphate esters 5 % alkylaryl sulfonic acid 5 % alkylamine ethoxylate 4 % paraffin oil 15 a, o
at the ratio 1 : 1.5
Separate granules containing an activator may also be mixed to form a single granule mixture with the above-mentioned granule formulations which contain active ingredients, or it can be dispensed separately to form a tank mixture with them. The granules disperse moderately into water.
Example 5
A granular product containing phenmedipham and an activator ca be prepared from a raw-material mixture which contains: phenmedipham 16.0 % lignin sulfonates 2.6 % phenyl sulfonates 5.5 % urea 7.0 % kaolin 5.5 % diatomite 5.0 % mixture B 50.4 % polyethylene glycol 8.0 %
Mixture B contains: silicic acid (precipitated) 37.5 % bentonite 2.5 % fatty alcohol ethoxylates 16.0 % polyoxyethylene sorbitols 33.8 % paraffin oil 5.1 % alkylamine ethoxylates 5.1 %
The mixture is granulated in a disc in which the mix is heate to +70 °C, and the formed granular product is cooled back to room temperature. The suspension properties of the product ar moderate.
Example 6
A layered granular product containing phenmedipham and an act vator can be prepared from a mixture which contains: phenmedipham 16.0 % lignin sulfonates 2.7 % phenyl sulfonates 5.3 % kaolin 15.5 % diatomite 5.0 a - polyethylene glycol 5.0 % mixture B 50.4 % (as in Example 5)
Mixture B is applied as a coating with the help of polyethyle glycol to a granule prepared from the other raw materials, at +70 °C in a disc granulator. The suspension properties of the granular product are moderate.
Example 7
A granular product containing phenmedipham and an activator ca be prepared by the extrusion technique from a raw-material mixture which contains: phenmedipham 32.0 % lignin sulfonates phenyl sulfonates kaolin diatomite naphthene sulfonates mixture C
Figure imgf000016_0001
Mixture C contains: silicic acid (precipitated) phenyl sulfonates ammonium sulfate sodium chloride lignin sulfonates naphthene sulfonates mixture A
Figure imgf000016_0002
The suspension properties are: 1 min) 0.15 ml; 5 min) 0.3 ml; 10 min) 0.4 ml.
Example 8
A granular product containing phenmedipham and desmedipham can be prepared from a mixture which contains: phenmedipham 60.0 % desmedipham 20.0 % lignin sulfonates 5.9 % phenyl sulfonates 5.6 % kaolin 4.0 % diatomite 2.0 %
The suspension properties of the granular product are: 1 min) 0.01 ml; 5 min) 0.02 ml; 10 min) 0.03 ml.
Example 9
A granular product containing phenmedipham and ethofumesate can be prepared by the disc granulation technique from a mixture which contains: phenmedipham 32.0 % ethofumesate 40.0 % lignin sulfonates 6.0 % phenyl sulfonates 5.0 % naphthene sulfonates 9.0 % bentonite 0.2 % urea 7.8 %
The suspension properties of the granular product are: 1 min) 0.01 ml; 5 min) 0.03 ml; 10 min) 0.04 ml.
Example 9 b
Granules containing phenmedipham and ethofumesate can be pre¬ pared by disc granulation from a mixture which contains: phenmedipham 35.0 % ethofumesate 34.7 % lignin sulfonates 5.9 % phenyl sulfonates 5.6 % diatomite 2.0 % kaolin 16.8 %
The suspension properties were: 1 min) 0.15 ml; 5 min) 0.5 ml; 10 min) 0.8 ml.
Example 10
A'granular product containing phenmedipham and methamitron ca be prepared by disc granulation from a mixture which contains: phenmedipham 16.0 % methamitron 64.0 % lignin sulfonates 5.9 % phenyl sulfonates 5.6 % diatomite 2.0 % kaolin 6.5 %
The suspension properties of the granular product are: 1 min) 0.01 ml; 5 min) 0.02 ml; 10 min) 0.03 ml. Example 11
A granular product containing phenmedipham and chlorodazone c be prepared by disc granulation from a mixture which contains: phenmedipham 25.0 % chlorodazone 50.0 % lignin sulfonates 5.9 o phenyl sulfonates 5.6 diatomite 1.1 Q. kaolin 12.4
The suspension capacity of the granules is: 1 min) 0.03 ml; 5 min) 0.10 ml; 10 min) 0.15 ml.
Example 11 b
A granular product containing phenmedipham and chlorodazone ca be prepared by disc granulation from a mixture which contains: phenmedipham 20.0 % chlorodazone 60.0 % lignin sulfonates 5.9 % phenyl sulfonates 5.6 % diatomite 1.1 % kaolin 7.4 %
The suspension properties of the product are: 1 min) 0.03 ml; 5 min) 0.10 ml; 10 min) 0.15 ml.
Example 12
A granular product containing phenmedipham, desmedipham and chlorodazone can be prepared by disc granulation from a mixtur which contains: phenmedipham 12.0 % desmedipham 3.0 % chlorodazone 45.0 % lignin sulfonates 5.9 % phenyl sulfonates 7.0 % fluorinated surfactant 2.0 % alkylaryl betaine 5.0 % diatomite 1.0 % kaolin 19.1 %
The suspension capacity of the granules is: 1 min) 0.1 ml; 5 min) 0.35 ml; 10 min) 0.45 ml.
Example 13
A tablet containing phenmedipham and an activator can be pre- pared by compression using a pressure of 300 kg/cm from a mixture which contains:
Figure imgf000019_0001
The tablet can be made in a mold having a diameter of 50 mm, which case 30 g of mixture is used.
The suspension properties of the tablet are moderate when the dispersion of the tablet in a 500 ml decanter containing 300 of water is observed visually.
Biologic experiments:
The activities of the formulations produced were tested in action against weeds commonly encountered in sugar beet cul¬ tivation, such as amaranth (Amaranthus retroflexus) , rape (Brassica napus) , goosefoot (Chenopodium album) , and common chickweed (Stellaria media) . Four pots per weed species per test specimen were used in the experiments. The efficacies we evaluated in accordance with typical evaluation principles on scale of 0 - 10, the complete destruction of the plant being described by 10. The mean of four pots was reported.
The sensitivity to injury of the sugar beet (Beta vulgaris) wa determined on the same scale.
Experiment 1
The biologic efficacy of a mixture of granular phenmedipham (a in Example 1) and a granular activator (as in Example 4) was compared with a phenmedipham-containing emulsion concentrate preparation (Kemifam) available on the market. The amounts of active ingredient in the test specimens were the same, 640 g o active ingredient per hectare. The efficacies were inspected 7 days after the spraying.
Figure imgf000020_0001
+ Example 4 1.5 kg
Example 1 0.8 kg 7.3 8.2 8.7 7.2 1.0 + Example 4 3.0 kg
The result shows that a granular phenmedipham product without an activator is not biologically effective. On the other hand, by means of the granular activator the granular phenmedipham product can be activated so that with the same amount of the product (3.8 kg as compared with 4 1) its action on amaranth, rape and common chickweed is better than that of the reference, and injury to the sugar beet is very little.
Experiment 2
In the experiment, the efficacies of granular products contain- ing phenmedipham and an activator were compared with that of a emulsion concentrate product (Kemifam) available on the market and of a suspension concentrate product (Betaflow) available o the market. The amount of active ingredient per hectare was 64 g/ha in all the experiments. The evaluation was carried out 14 days after the spraying.
Test product Efficacy ama- rape chick- sugar ranth weed beet
Kemifam 4 4 4 1
Betaflow 4 4 3 1
Example 5 3 3 4 1
Example 6 4 3 3 1
The results show that the granular formulations of phenmedipha have biologic efficacies equal to those of both of the emulsio and suspension concentrate references. The injury to the crop plant is also the same.
Experiment 3
In the experiment, the efficacy of a mixture of a granular product (such as Example 8) containing phenmedipham (69 %) and desmedipham (20 %) and a granular product (such as Example 4) containing an activator was compared with a commercially avail able emulsion concentrate preparation containing phenmedipham (129 g/1) and desmedipham (34 g/1). The amounts of active in¬ gredient per hectare were 652 g for Betanal Compact and 640 g for Example 8 + Example 4. The efficacies were determined 14 days after the spraying.
Figure imgf000021_0001
Example 8 0.8 kg 8.3 5.3 9.0 22.6 1.0 + Example 4 3.8 kg
The experiment also shows that a mixture of phenmedipham and desmedipham works even better than the corresponding emulsion concentrate product which served as a reference. The injury to sugar beet was the same with both products.
Experiment 4
In the experiment, the efficacy of granules (such as Example 9 containing phenmedipham and ethofumesate and of granules (such as Example 4) containing an activator was compared with that o a commercially available emulsion concentrate product, Betaron which contains phenmedipham 80 g/1 and ethofumesate 100 g/1. The efficacies were determined 14 days after the spraying. The total amount of active ingredients per experiment was 640 g/ha
Figure imgf000022_0001
+ Example 4 0.67 kg
The experiment shows that a granular mixture of phenmedipham and ethofumesate also requires the addition of an activator, whereby a biologically at least equally good result is achieved as with the reference. Injuries caused are identical.
Experiment 5
In the experiment, the efficacies of a granular product con¬ taining phenmedipham and methamitron (such as Example 10) and of that product and a granular activator (such as Example 4) were compared with the efficacy of a tank mixture which con¬ sisted of a phenmedipham suspension concentrate product which contained active ingredient 160 g/1 and of a granular methamitron product (Goltix) having a concentration of 700 g/kg. The amounts of active ingredients per hectare were the same for all the test specimens. The efficacies were determin 14 days after the spraying.
Test product Efficacy product/ ama- rape chick- sugar hectare ranth weed beet phenmedipham 1.5 1 9.5 9.5 10 0 SC Goltix 1.37 kg
Example 10 1.5 kg 7.0 7.0 9.0 0
Example 10 1.5 kg 7.0 9.0 9.5 0 + Example 4 1.1 kg
Methamitron, which works both soil-applied and foliage-applie does not require activators in the same way as does phen¬ medipham; the relatively high efficacy of granular product 10 is an indication of this. However, even in this case a signif icant improvement of action on rape is achieved with an addi¬ tion of activator. Overall, using a granular product of phen¬ medipham + methamitron + activator, an excellent selective biologic action is achieved without any symptoms of injury in the sugar beet.
Experiment 6
In the experiment, a comparison was made among the efficacies of a granular product containing phenmedipham and chlorodazon such as Example 11 b, in which the concentrations were 20 and 60 % respectively, and it and a granular activator, such as E ample 4, and a suspension concentrate containing effective phenmedipham and chlorodazone, the concentrations being 100 a 300 g/1. On the other hand, the significance of the granular activator in a triple-mixture granular product which containe phenmedipham, desmedipham and chlorodazone was investigated. The amounts of active ingredient per hectare are the same for all the test specimens. The efficacies were determined 14 days after the spraying
Figure imgf000024_0001
+ Example 4 2.3 kg
The experiment shows clearly how the increase in efficacy is important also in the mixture formulation of foliage-acting phenmedipham and soil-acting chlorodazone. The same applies to the triple mixture which contains foliage-acting desmedipham in addition to the two former.
Field experiments
Field experiment 1
The purpose of the experiment was to compare the biologic ac¬ tion of granular products containing phenmedipham to the action of emulsion and suspension concentrate products already avail¬ able commercially.
The experiments were conducted in accordance with conventional field experiment practices. There were three rounds of applica¬ tion, all performed after the emergence of seedlings of sugar beet. The efficacy was examined visually and evaluated in rela¬ tion to an untreated plant stand, the value for which was 0. Value 100 describes complete control capacity. The amount of phenmedipham used in each round of spraying was 480 g/ha.
Q.
6 7
Figure imgf000025_0001
The efficacy of the granular product containing an active in¬ gredient, used together with a granular activator, the total amount of the material used being 1.75 kg/ha, is as good as th efficacy of the suspension product when used at 3 1/ha. When a granular product containing more activator was used,. in which case the total amount of material used is 2.75 kg/ha, a sig¬ nificantly better efficacy is obtained with the granular prod¬ uct than with the suspension product. In the experiment, the granules containing activator were dispensed separately for reasons of test-performing techniques, but it is clear that a granular mix containing an active ingredient and an activator can be mixed in advance to form a single homogenous mix to be dispensed as one.
Together with a granular product which contains active in¬ gredient it is possible to use a liquid activator in the con¬ ventional manner as a tank mixture, as in test specimen 5. The activator granules of Example 4 contain mixture A 60 %, in which case test specimens 4 and 5 contain equal amounts of the liquid ingredient. However, it can be observed surprisingly that the solid carrier material of the granular product in¬ creases the effect of the activator granules on the efficacy o the active ingredient by up to 10 %. It is also noteworthy tha this granular product is more than 10 % more effective than th commercial suspension concentrate product and up to 20 % more effective than the commercial emulsion concentrate product.
Field experiment 2
In the experiment, the biologic efficacy of a granular product containing phenmedipham and ethofumesate (Example 9 a) and an activator (Example 4) was compared with the efficacy of an emulsion concentrate product (Betaron) available on the market. The overall test arrangements were as in field experiment 1. The amount of active ingredient used was 540 g per ha per spraying round.
Figure imgf000026_0001
With a total amount of 1.33 kg of the granular product, almost the same efficacy was obtained as with 3 1 of the emulsion concentrate. The handling of the product containing an active ingredient and an activator in connection with the spraying did not cause difficulties.
Field experiment 3
In the experiment, the efficacies of a conventional spraying program used in the cultivation of sugar beet and a spraying program based on granules were compared. In practice, phen¬ medipham, methamitron or ethofumesate is not generally used alone, but tank mixtures of these are used, in which the mixin ratios may vary, depending on the weeds.
Kemiron is an emulsion concentrate containing ethofumesate 200 g per liter, and granular ethofumesate (EFU granule) is a water dispersible granular product containing effective in¬ gredient 65 %. The amounts of active ingredient per hectare were the same with both the test specimens.
Conventional program:
1st spraying 1.5 1 Kemifam + 1 kg Goltix + 0.5 1 Kemiron
2nd spraying 1.5 1 Kemifam + 1 kg Goltix + 1.0 1 Kemiron
3rd spraying 1.5 1 Kemifam + 0.5 kg Goltix + 1.0 1 Kemiron
Program based on granules:
1st spraying 0.2 kg Example 1 + 1 kg Goltix + 1.15 kg EFU- granules
2nd spraying 0.2 kg Example 1 + 1 kg Goltix + 0.3 kg EFU- granules
3rd spraying 0.2 kg Example 1 + 0.5 kg Goltix + 0.3 kg EFU- granules each spraying containing 1.15 kg Example 4
Efficacies: conventional program 90 % granule-based program 89 %
The results show that the program based on granular products has worked as well as has the program in which phenmedipham an ethofumesate are in liquid form as emulsion-emulsion concen¬ trates.

Claims

Claims
1. A method for enhancing the efficacy of granular or tablet-form herbicidal products, such as methyl-3-m-tolyl- carbamoyloxyphenylcarbamate, ethyl-3-phenyl-carbamoyloxyphenyl carbamate, 2-ethoxy-2,3-dihydro-3,3-dimethylbenzofurane-5-yl- methane sulfonate, 5-amino-4-chloro-2-phenylpyridazine~3(24)- one and 4-amino-4,5-dihydro-3-methyl-6-phenyl-l,2,4-triazine-5 one, by using activators known per se, characterized in that the activator substances and activator constituents are impreg¬ nated into and/or mixed with a solid carrier material which possibly contains auxiliary agents known per se, whereby a solid activator composition is obtained, and the obtained solid activator composition is contacted with the herbicidal product either a) by forming a layer it on the granule or tablet surface or b) by incorporating it as a core inside the granule or tablet or c) by mixing the solid components together.
2. A method according to Claim 1, characterized in that the carrier is inorganic or organic by structure or is a mixture of such substances.
3. A method according to Claim 2, characterized in that the carrier is of natural origin.
4. A method according to Claim 2 , characterized in that the carrier is of synthetic origin.
5. A method according to any of the above claims, charac¬ terized in that the activator ingredient is made up of prior- known surfactants and/or oils.
6. A method according to Claim 5, characterized in that the surfactants are anionic, cationic, amphoteric or non-ionic surfactants or their mixtures. 7. A method according to Claim 5, characterized in that t oils are mineral oils, vegetable oils, animal oils, their hy drolysis products, or their mixtures.
8. A method according to Claim 5 or 6, characterized in that the proportion of surfactants is approx. 50 - 100 % of activator ingredient.
9. A method according to Claim 5 or 7, characterized in that the proportion of oil is at maximum approx. 50 % of the activator ingredient.
10. A method according to Claim 1, characterized in that th proportion of the activator ingredient is approx. 10 - 70 %, preferably 30 - 90 %, of the solid activator composition.
11. A method according to Claim 1, characterized in that th auxiliary agents are agents required for the dispersing, wet¬ ting, granulating, stabilizing, pH control, or defoaming of t activator.
12. A method according to Claim 1, characterized in that th herbicidal products and the solid activator composition are granulated or tabletted together or separately.
13. A method according to Claim 1, characterized in that other plant protection agents, preferably chlorodazone and methamitron, are used in the same granule or as a separate granule together with carbamoyloxyphenylcarbamate, preferably phenmedipham, desmedipham and/or ethofumesate. AMENDED CLAIMS
[received by the International Bureau on 23 February 1993 (23.02.93); original claims 1-13 replaced by amended claims 1-12 (2 pages)] 1. A method for the preparation of a herbicidal product in granular form, said product comprising methyl-3- -tolyl-car¬ bamoyloxyphenylcarbamate or ethyl-3-phenyl-carbamoylo¬ xyphenylcarbamate as a herbicidally effective compound and surfactants and/or oils as an activator ingredient, characte rized in that the activator ingredient is combined with a solid carrier material to form a solid activator composition and the composition as obtained is combined with the herbici dally effective compound to form a herbicidal product in which said composition and said compound are comprised in tw separate solid phases, the product being formed a) by forming granules comprising the herbicidally effecti¬ ve compound and by covering the granules with a layer of the solid activator composition, or b) by forming granules consisting of the solid activator composition and by covering the granules with a solid layer comprising the herbicidally effective compound, or c) by forming first granules comprising the herbicidally effective compound and second granules consisting of the solid activator composition and by mixing said first and second granules together.
2. A method according to Claim 1, characterized in that the activator ingredient is a liquid, which is impregnated into the solid carrier material.
3. A method according to Claim 2, characterized in that the activator ingredient is a solid which is mixed with the solid carrier material.
4. A method according to Claim 1, characterized in that the carrier material is of natural origin.
5. A method according to Claim 1, characterized in that the carrier is a synthetic material
6. A method according to Claim 1, characterized in that the activator ingredient comprises anionic, cationic, aiπphoteric or non-ionic surfactants or thir mixtures.
7. A method according to Claim l, characterized in that the activator ingredient comprises mineral oils, vegetable oils, animal oils, their hydrolysis products or their mixtures.
8. A method according to Claim 1, characterized in that the proportion of surfactants is approx. 50 - 100 % of the acti¬ vator ingredient.
9. A method according to Claim 1, characterized in that the proportion of oil is at maximum approx. 50 % of the activato ingredient.
10. A method according to Claim 1, characterized in that the proportion of the activator ingredient is approx. 10 - 70 %, of the solid activator composition.
11. A method according to Claim 1, characterized in that auxiliary agents are included in the solid activator composi¬ tion for dispersing, wetting, granulating, stabilizing, pH control, or defoaming of the activator composition.
12. A method according to Claim 1, characterized in that in addition to said herbicidally effective compounds, other plant protection agents, such as chlorodazone, methamitron o ethofumesate are incorporated in the product in the same granules as said herbicidally effective compounds or as sepa¬ rate granules.
PCT/FI1992/000258 1991-09-27 1992-09-25 A method of producing herbicidal granular products WO1993005652A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP92919886A EP0643555A1 (en) 1991-09-27 1992-09-25 A method of producing herbicidal granular products
PL92302907A PL172504B1 (en) 1991-09-27 1992-09-25 Method for the production of granular herbicidal product PL PL PL
JP5505554A JPH06510767A (en) 1991-09-27 1992-09-25 Method for manufacturing herbicide granular products
SK355-94A SK35594A3 (en) 1991-09-27 1992-09-25 Method of preparing of herbicidal granular products
BG98679A BG98679A (en) 1991-09-27 1994-03-24 Method for the preparation of herbicide granulated products
NO941121A NO178681C (en) 1991-09-27 1994-03-25 Process for the preparation of herbicidal granular products

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI914545A FI93416C (en) 1991-09-27 1991-09-27 Process for the preparation of a herbicide product in granular or tablet form
FI914545 1991-09-27
LVP-92-491A LV10147B (en) 1991-09-27 1992-12-24 Process for preparing of granulated herbicides

Publications (1)

Publication Number Publication Date
WO1993005652A1 true WO1993005652A1 (en) 1993-04-01

Family

ID=30116977

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI1992/000258 WO1993005652A1 (en) 1991-09-27 1992-09-25 A method of producing herbicidal granular products

Country Status (14)

Country Link
EP (1) EP0643555A1 (en)
JP (1) JPH06510767A (en)
BG (1) BG98679A (en)
CA (1) CA2119753A1 (en)
CZ (1) CZ69394A3 (en)
EE (1) EE9400054A (en)
FI (1) FI93416C (en)
HU (1) HU213638B (en)
LT (1) LT3420B (en)
LV (1) LV10147B (en)
NO (1) NO178681C (en)
PL (1) PL172504B1 (en)
SK (1) SK35594A3 (en)
WO (1) WO1993005652A1 (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2704387A1 (en) * 1993-04-28 1994-11-04 Rhone Poulenc Agrochimie Concentrated compositions of active ingredients in agriculture.
EP0968649A1 (en) * 1998-07-02 2000-01-05 E.I. Du Pont De Nemours And Company Adjuvants for novel dry herbicide formulations
US6093680A (en) * 1996-10-25 2000-07-25 Monsanto Company Composition and method for treating plants with exogenous chemicals
US6130186A (en) * 1996-10-25 2000-10-10 Monsanto Company Composition and method for treating plants with exogenous chemicals
WO2007048851A1 (en) 2005-10-28 2007-05-03 Basf Se Solid crop protection agents containing polyalkoxylate, method for their production and use thereof
WO2007048850A1 (en) 2005-10-28 2007-05-03 Basf Se Solid formulations containing polyalkoxylate, method for their production and use thereof
EP2046123A4 (en) * 2006-07-24 2012-08-22 Syngenta Participations Ag Controlled release granules
WO2013149898A1 (en) * 2012-04-02 2013-10-10 Basf Se Granules obtainable by milling pesticide and silica, addition of adjuvant, and fluidized bed granulation
US9750251B2 (en) 2008-02-14 2017-09-05 Bayer Intellectual Property Gmbh Liquid herbicidal preparations
CN112221424A (en) * 2020-10-14 2021-01-15 浙江新安化工集团股份有限公司 System and method for continuously producing ammonium glyphosate granules
WO2025046264A1 (en) 2023-08-29 2025-03-06 Quimicos E Solucoes Sustentaveis Do Brasil S.A. Solid composition comprising particles of silicate and diutan gum

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6726447B2 (en) * 2015-06-25 2020-07-22 第一工業製薬株式会社 Aqueous pesticide composition

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH630508A5 (en) * 1976-11-03 1982-06-30 Schering Ag SELECTIVE HERBICIDAL AGENT AND METHOD FOR THE PRODUCTION THEREOF.
US4386101A (en) * 1980-11-20 1983-05-31 Ciba-Geigy Corporation Unsymmetrical bis-carbamates and their use for combating pests
EP0107107A1 (en) * 1982-10-04 1984-05-02 O.M.Scott + Sons Company Granulated plant protection agent and process for its preparation
DE1567164C2 (en) * 1966-09-10 1985-03-07 Schering AG, 1000 Berlin und 4709 Bergkamen Herbicidal agents based on N-carbamoyloxyphenyl carbamates
US4557751A (en) * 1981-03-10 1985-12-10 Minnesota Mining And Manufacturing Company Compositions containing surfactant and broadleaf foliar herbicide
EP0201417A1 (en) * 1985-05-06 1986-11-12 Rhone-Poulenc Chimie Surfactant composition, process for its preparation and its use
EP0224845A1 (en) * 1985-11-30 1987-06-10 Hoechst Aktiengesellschaft Water-dispersible granules
EP0257686A1 (en) * 1986-08-20 1988-03-02 Akzo N.V. Herbicides and fungicides containing activity promoting additives
DE4024436A1 (en) * 1989-08-02 1991-02-07 Sumitomo Chemical Co WATER DISPERSIBLE GRANULATE AND METHOD FOR THE PRODUCTION THEREOF
EP0413267A1 (en) * 1989-08-14 1991-02-20 Hoechst Schering AgrEvo GmbH Water-dispersible granules
WO1991013546A1 (en) * 1990-03-12 1991-09-19 E.I. Du Pont De Nemours And Company Water-dispersible or water-soluble pesticide granules from heat-activated binders
EP0465899A1 (en) * 1990-07-06 1992-01-15 Bayer Ag Herbicidal agent based on a combination of metamitron/ethofumesat/phenmedipham/desmedipham
EP0473003A2 (en) * 1990-08-24 1992-03-04 Bayer Ag Solidformulations
EP0476555A2 (en) * 1990-09-15 1992-03-25 Hoechst Schering AgrEvo GmbH Synergistic herbicidal agents

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3920442A (en) 1972-09-18 1975-11-18 Du Pont Water-dispersible pesticide aggregates
US4197112A (en) 1977-10-12 1980-04-08 E. I. Du Pont De Nemours And Company Water-dispersible herbicide compositions

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1567164C2 (en) * 1966-09-10 1985-03-07 Schering AG, 1000 Berlin und 4709 Bergkamen Herbicidal agents based on N-carbamoyloxyphenyl carbamates
CH630508A5 (en) * 1976-11-03 1982-06-30 Schering Ag SELECTIVE HERBICIDAL AGENT AND METHOD FOR THE PRODUCTION THEREOF.
US4386101A (en) * 1980-11-20 1983-05-31 Ciba-Geigy Corporation Unsymmetrical bis-carbamates and their use for combating pests
US4557751A (en) * 1981-03-10 1985-12-10 Minnesota Mining And Manufacturing Company Compositions containing surfactant and broadleaf foliar herbicide
EP0107107A1 (en) * 1982-10-04 1984-05-02 O.M.Scott + Sons Company Granulated plant protection agent and process for its preparation
EP0201417A1 (en) * 1985-05-06 1986-11-12 Rhone-Poulenc Chimie Surfactant composition, process for its preparation and its use
EP0224845A1 (en) * 1985-11-30 1987-06-10 Hoechst Aktiengesellschaft Water-dispersible granules
EP0257686A1 (en) * 1986-08-20 1988-03-02 Akzo N.V. Herbicides and fungicides containing activity promoting additives
DE4024436A1 (en) * 1989-08-02 1991-02-07 Sumitomo Chemical Co WATER DISPERSIBLE GRANULATE AND METHOD FOR THE PRODUCTION THEREOF
EP0413267A1 (en) * 1989-08-14 1991-02-20 Hoechst Schering AgrEvo GmbH Water-dispersible granules
WO1991013546A1 (en) * 1990-03-12 1991-09-19 E.I. Du Pont De Nemours And Company Water-dispersible or water-soluble pesticide granules from heat-activated binders
EP0465899A1 (en) * 1990-07-06 1992-01-15 Bayer Ag Herbicidal agent based on a combination of metamitron/ethofumesat/phenmedipham/desmedipham
EP0473003A2 (en) * 1990-08-24 1992-03-04 Bayer Ag Solidformulations
EP0476555A2 (en) * 1990-09-15 1992-03-25 Hoechst Schering AgrEvo GmbH Synergistic herbicidal agents

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2704387A1 (en) * 1993-04-28 1994-11-04 Rhone Poulenc Agrochimie Concentrated compositions of active ingredients in agriculture.
WO1994024861A1 (en) * 1993-04-28 1994-11-10 Rhone Poulenc Agrochimie Concentrated compositions of active substances used in agriculture
AU694116B2 (en) * 1993-04-28 1998-07-16 Merial Ltd Concentrated compositions of active substances used in agriculture
US6255254B1 (en) 1993-04-28 2001-07-03 Aventis Cropscience Sa Concentrated compositions containing agriculturally-active material
US6093680A (en) * 1996-10-25 2000-07-25 Monsanto Company Composition and method for treating plants with exogenous chemicals
US6130186A (en) * 1996-10-25 2000-10-10 Monsanto Company Composition and method for treating plants with exogenous chemicals
US6479434B1 (en) 1996-10-25 2002-11-12 Monsanto Technology Llc Composition and method for treating plants with exogenous chemicals
EP0968649A1 (en) * 1998-07-02 2000-01-05 E.I. Du Pont De Nemours And Company Adjuvants for novel dry herbicide formulations
WO2007048851A1 (en) 2005-10-28 2007-05-03 Basf Se Solid crop protection agents containing polyalkoxylate, method for their production and use thereof
WO2007048850A1 (en) 2005-10-28 2007-05-03 Basf Se Solid formulations containing polyalkoxylate, method for their production and use thereof
CN101351120A (en) * 2005-10-28 2009-01-21 巴斯夫欧洲公司 Solid crop protection agents containing polyalkoxylate, method for their production and use thereof
US20090131260A1 (en) * 2005-10-28 2009-05-21 Basf Aktiengesellschaft Solid Formulations Containing Polyalkoxylate, Method for their Production and use thereof
US8497230B2 (en) 2005-10-28 2013-07-30 Basf Aktiengesellschaft Solid crop protection agents containing polyalkoxylate, method for their production and use thereof
EP2046123A4 (en) * 2006-07-24 2012-08-22 Syngenta Participations Ag Controlled release granules
US9750251B2 (en) 2008-02-14 2017-09-05 Bayer Intellectual Property Gmbh Liquid herbicidal preparations
WO2013149898A1 (en) * 2012-04-02 2013-10-10 Basf Se Granules obtainable by milling pesticide and silica, addition of adjuvant, and fluidized bed granulation
US9980481B2 (en) 2012-04-02 2018-05-29 Basf Se Granules obtainable by milling pesticide and silica, addition of adjuvant, and fluidized bed granulation
CN112221424A (en) * 2020-10-14 2021-01-15 浙江新安化工集团股份有限公司 System and method for continuously producing ammonium glyphosate granules
WO2025046264A1 (en) 2023-08-29 2025-03-06 Quimicos E Solucoes Sustentaveis Do Brasil S.A. Solid composition comprising particles of silicate and diutan gum

Also Published As

Publication number Publication date
LTIP436A (en) 1994-10-25
LV10147B (en) 1995-08-20
PL172504B1 (en) 1997-10-31
CA2119753A1 (en) 1993-04-01
FI914545A0 (en) 1991-09-27
NO941121D0 (en) 1994-03-25
NO941121L (en) 1994-03-25
FI914545L (en) 1993-03-28
HU9400866D0 (en) 1994-06-28
HUT70887A (en) 1995-11-28
JPH06510767A (en) 1994-12-01
LT3420B (en) 1995-09-25
HU213638B (en) 1997-08-28
SK35594A3 (en) 1995-02-08
EP0643555A1 (en) 1995-03-22
FI93416B (en) 1994-12-30
NO178681C (en) 1996-05-15
FI93416C (en) 1995-04-10
LV10147A (en) 1994-10-20
CZ69394A3 (en) 1994-11-16
NO178681B (en) 1996-02-05
BG98679A (en) 1995-05-31
EE9400054A (en) 1995-12-15

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