SK35594A3 - Method of preparing of herbicidal granular products - Google Patents

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

Technical field

The present invention relates to a process for the preparation of herbicidal granular products containing carbamoyloxyphenylcarbamates and / or substituted benzofurans, known per se, as active ingredients, other surfactants, suspending agents, inert carriers and other possible auxiliary agents such as stabilizers, antifoams, dyes and preservatives, stabilizers. Said active ingredients are insoluble in water and in the main means used to act on the foliage, and which are sprayed on the plant sites in the form of dilute aqueous solutions. For this reason, water dispersible granules are prepared from which, after dilution with water, a homogeneous suspension is obtained which does not clog the nebulizer.

BACKGROUND OF THE INVENTION

Carbamoyloxyphenylcarbamate and benzofuran herbicides have been conventionally formulated as ein emulsion concentrates in which the active ingredient is dissolved in organic solvents, and emulsifier solutions can be used, allowing mixing with water to form an emulsion. However, these formulations have the disadvantage of toxicity of the products with respect to organic solvents, of the flammability of the products and of the difficulty of obtaining a stable emulsion of the product together with water, in which no crystal formation would occur. Crystallization is particularly typical of methyl 3-tolylcarbamoylphenylcarbamate.

Product forms in which the active ingredients are not in dissolved form are preferred, since in such cases, problems concerning toxicity, flammability, packaging materials and further storage can be avoided, since in particular in the case of foliage herbicides it is desirable the ability to penetrate and translocate in order to achieve the desired biological effect. Often a disadvantage is also the hydrolysis decomposition. The active ingredient in molecular form is, in ideal quaternary, able to penetrate through layers of wax and cuticles much more

k lf

I more effective than in the form of solid particles. Therefore, insoluble particles of the active ingredient should be finely divided as far as possible and their penetration and trenslocation capability must be improved with oils, organic co-solvents and surfactants. Particularly in the case of carbamoyloxyphenylcarbamates, it is necessary to add an exceptionally large amount of these adjuvants in order to achieve the desired biological effect. Jet mills and suspension mills are used for grinding to finely grind the active ingredient, preferably from one to five microns in size to achieve the desired biological effect and, as far as possible, a stable suspension when these granules are dispersed in the granules. water.

If the active ingredient is in solid form, it may be present in a water-dilutable formulation either as a liquid suspension concentrate or as a water-dispersible granular product. Common disadvantages of the product in liquid form include storage difficulties, handling problems due to the high viscosity, and residues remaining when the containers are not completely emptied. The latter disadvantage proves to be a significant environmental problem when used containers are disposed of. These problems can be avoided by using solid liquid dispersible granules. In addition, the granular product can be packaged in materials such as cardboard paper boxes, cartons that are less environmentally friendly, and also empty cartons are easier to dispose of.

In addition to the chemical stability of the active ingredients, the basic properties of water dispersible granules include good water dispersibility, the treatment of the granules to avoid the formation of undesirable dust in conjunction with storage or handling, granular flowability and non-caking during storage. To achieve these properties, the granules may contain, in addition to the water-insoluble carrier, agents dispersing, suspending, wetting, preserving, antifoaming and anti-caking agents.

It is known that carbamoyloxyphenylcarbamates, most notably methyl 3-m-tolylcarbemoyloxyphenylcarbamate, commonly referred to as phenmedipham, and ethyl 3-phenylcarbamoyloxyphenylcarbamate, commonly referred to as desmedipham (BP 679,283)

- 3 with the general formula:

W

NHC90R ^ť

R 1 where R ¹ and R ² are CH 1 or R ¹ is H and R ² is CH ₂ CH are selective and have good herbicidal properties. These active ingredients can be used separately or as mixtures with one another and / or with other pesticides in the mixtures, in particular not to control growth in sugar beet cultivation.

Conventionally, the aforementioned active ingredients have been formulated as emulsion concentrates. However, while attempts are made to avoid organic solvents, and since phenmedipham tends to crystallize when this formulation is diluted with water, there is now an interest in producing water dispersible granules from these active ingredients. The preparation of water dispersible granules from herbicides (US patent 3,920,442) has also been known, as well as dispersible triazine herbicidal granules containing a surfactant which acts to improve crystallization properties (US patent 4,197,112) or granules with poor physical properties by surface coating. (EP patent 207,417) · An obstacle to the commercial use of dispersible carbamoyloxyphenylcarbamates has been the difficulty of imparting the desired desired biological effect to a given product, since the amount of liquid oil and / or surfactants is large in scale to the amounts of active ingredients (approximately 1: 1). ) and uneconomical due to technical implementation.

It is known that a good biological effect of water-dispersible granules can be obtained from herbicides with certain active ingredients. However, the use of carbamoyloxyphenylcarbamates did not produce the desired effect desired by these methods.

SUMMARY OF THE INVENTION

Surprisingly, it has now been found that by using granular products containing carbamoyloxyphenylcarbamates, not only the abovementioned properties of the granular products can be achieved, but that they can be significantly improved in the preparation of a granular product or a tablet product where the activator is impregnated into a carrier added to this portion that is uniformly distributed or in a layer on the surface of the granule or tablet or as a core within the granule or tablet. Of course, the granules or tablets may be prepared from a liquid ectator and a carrier. The granules mixed with the granules containing the active ingredient may be in the same compartment in the same compartment, which granules may be distributed either as a mixture or as a single product from the container. The discrete tablets may also be distributed together with a granular or terbined form of the active ingredient, forming a combined mixture for use.

By using an activator impregnated in a carrier, the biological effect of the solid carbocoyloxyphenylcarbamate obtained is so increased that it is comparable to an unimpregnated activator; these results were obtained in both greenhouse and field tests.

As carrier for the activator, it is possible to use inorganic substances which absorb large amounts of oily substances and are of natural origin, such as those based on silicon dioxide, still based on alumina, atapulgite, montomorilonitone, mica, but also diatomite, bentonite, talc , kaolin, calcium oxide, gypsum, and water-soluble salts or non-water-soluble salts.

It is. can be used as carrier porous organic substances of natural origin, such as wood sawdust or ground corn cobs, ground coconut or almond shells, ground grain husks, ground olive husks, cellulose, starch and elginates, or porous structures which are superimposed on poly starting substances of natural origin which can be modified, such as lignin derivatives, cellulose derivatives, starch derivatives and cyclodextrins, or synthetic polymers such as polyacrylates, polyacrylamides, polyvinyl derivatives, polymers of maleic acid, polyurethanes, polylactides and polymers of glycolic acid.

The activator may be incorporated into the carrier material by depositing impregnated particles with a polymer, such as polyvinyl alcohol or with a sugar-based substance or based on an alcoholic sugar, such as lactose, CMC and sorbitol. In this case, the release rate of the actuator can also be controlled.

The liquid activator can also be encapsulated in capsules, capsules which can be further used in the granular product. Methods of encapsulation are generally known. Methods of depositing materials can also be influenced by the strength of the granules and their resistance to abrasion. However, the flowability of the product can thereby be improved.

An activator which contains surfactants and / or events is not important for the actual formulation; its main effect is to increase the biological effect of the product.

The proportion of activator can generally be in the range of 1 to 80% by weight of the granular product, preferably 0.5 to 5 times more than the amount of carbamoyloxyphenylcarbamate in the latter product.

The activator may be in a solid or liquid state (at a temperature of 20 ° C), in which case it may be impregnated into a carrier or mixed with a granular mixture. Alternatively, it may also be impregnated in or attached to the product in any other processing method used after granulation.

The activator may comprise anionic, cationic, nonionic or spherical surfactants, or these together with mineral oils, vegetable oils or oils of animal origin. The proportion of surfactants in the activator may range from 2 to 100% by weight, preferably from 50 to 100% by weight. The proportion of oil may be up to 98% by weight, preferably up to 50% by weight.

The anionic surfactants may be alkylsulfonates, alkylarylsulfonates, ether sulfates, fatty alcohol sulfates, sulfocarboxylic acid sulfate esters and derivatives thereof, alkyl glycerol ether sulfonates sulfoesters, sulfonamides and monoesters orthophosphoric acid diesters, bile salts and their salts.

The cationic surfactants may be alkylamines

- or alkylarylamines, alkyl or alkylaryl imidazolines by alkyl-. amino8midy.

The melon surfactants may be fatty alcohol ethoxylates, fatty acid ethoxylates, alkyl aryl ethoxylates, sugar alkyl ethoxylates, or alcohol alkyl sugar ethoxylates, alkyl amine or polyglycol ether alkylarylamines, derivatives of fatty acid amides, diethanolamide or fatty acid diethanolamides, mono-, diethanolamide, mono-, di- and triglycerides, acetylindiols, and silicon-based surfactants.

The amino-surfactants may be alkyl and alkylaryl derivatives of betaine, alkyl and alkylaryl derivatives of (poly) glycine, alkylamide and alkylarylamide carboxylates, and alkylamine and alkylarylamine sulfonates. Fluorine-containing surfactants can also be used.

The oily substance may be an oil, preferably having a low viscosity, so that it may be easily impregnated into the carrier.

On the other hand, oil may not significantly hinder the harvesting of plants. It is most preferred to use a low aromatic paraffin oil such as Neutral Solvent 150, Exxon. The oily substance may be, for example, rasilin oil or its hydrolysis products, such as soybean oil or a mixture of soybean oil fatty acids. Such an oil may also contain phospholipids and sterols.

The oily substances may be of animal origin, in which case it is preferred that such oil contains a plurality of unsaturated fatty acids and their glycerides.

It is believed that for granulating the active ingredient or active ingredient with its carrier containing the activator, or for granulating the carrier or active ingredient or activator, the material to be granulated is finely ground.

The material may be finely divided, for example, by drying in a jet mill or as a suspension in a bead mill. It is essential that the particle size in the solid state will be 10 µm in diameter, so that the active ingredients are preferably 5 µm (measured on a Coulter aperature) to achieve the desired biological effect.

In granulation S8, auxiliary agents that promote granule formation, re-incorporation of granules, rapid disintegration and dispersion of granules at dissolution time for use, as well as solution foaming inhibiting agents, can be used. Kečže aktiv

The 7 component may be subject to disintegration in a basic solution for use, it is possible to use in the mixture inorganic or organic pH control agents such as orthophosphoric acid or its acid salts 8 citric acid so that the pH of the solution is less than 7, preferably 3.5 to 5.5.

Granulating auxiliaries may be used in granules where the active ingredient and the activator are in the same granule, or granules with the active ingredient and granules with the activator are separated.

granular disintegrants may be polymers such as polyvinylpyrrolidone and starch, and modified forms thereof, or salts such as ammonium sulfate, or water-soluble organic compounds, such as urea, or gas release agents such as carbonates.

As is well known, dispersants such as phenylsulfonates, alkylnaphthalenesulfonates and polymerized naphthalenesulfonates, polyacrylic acids and their salts, polyacrylamides, polyalkoxydiamine derivatives, polyethylene oxide, polypropylene oxide, poly (ethylene oxide), poly (ethylene oxide), poly (ethylene oxide), poly (ethylene oxide), poly (ethylene oxide), and mixtures thereof, and further sulfonated lignin derivatives. The dispersants may be used in an amount of from 0.1 to 50% by weight, preferably from 5 to 20% by weight of the granular product.

Similar products such as polyethylene glycol can also be used as granulating agents; in this case, it is preferable to add the activator-containing component in an amount of from 1 to 20% by weight to the completed granules (i.e. to the final granulism) containing the active component.

The foaming of the mixture in the preparation of ηθ spraying can be controlled by antifoams such as silica-based reagents. It is preferred to use such agents in an amount of up to 0.5% by weight of the granular product.

Previously known methods such as disk granulation, spray drying (e.g. Niro), fluid bed granulation (e.g. Glatt and Schugi), mixing granulation using a vertical mixer (e.g. Fielder) or a paddle mixer (e.g. Forberg), granulation with an extruder (e.g. Nica) or compact granulation (e.g. Bepex apparatus) or centrifugal granulation

- 8 (e.g., CF granulator, Freund Industrial Co.) or pellet bed granulation.

The activator may be compressed into water dispersible tablets, in which case their size varies greatly depending on the matrix. Conventionally, tablets are compressed by rotary methods (Mansty) and tabletting by eccentric compression (Diaf).

Two or more of the above-mentioned methods in series can also be used for granulation and tableting. The surface of the granules can be mechanically hardened by rounding the granules, for example using Spheronizer Apparatus (Nica), or materials suitable for the purpose as described above can be applied to the granules.

It is important to dry the granular product. The product can be dried either in the eparatore used for granulation or in a separate apparatus to be dried (e.g. fluidized bed drying). The high moisture content of the granular product is less than 5% by weight, more preferably less than 1% by weight.

The granule size of the final product may vary, depending on the granulation method, to an average size of up to 3 mm or, if desired, higher than that of water-dispersible tablets.

It is understood that other pesticides can also be mixed with carbemoyloxycarbamutes (such as phenmedipham and desmedipham) to form the granular product. These pesticides can be herbicides, agents for control, plant disease control and insecticides, as well as agents affecting plant growth.

It is advantageous to use herbicides, in particular used in sugar beet cultivation, such as etofumezate, meth. tron, chlorodazone, lenazil, pyridate, metolachlorine, trichloroacetic acid, EPTC, qiunmerac, cycloate, chloropyralid, fluorroxipyr, isocarbimide, propham, trifluralin, sodium allox.ydim, ceotxydim, dialute, flunzifopalbutylpentis, or trialobot.

The products according to the invention can be used after the crops harvesting, preferably in several repeated rounds during the growth period of the treated plants. A suitable amount of active ingredient per spray is 0.1 to 1 kg per hectare, depending on the number of rounds of the individual application of the products of the present invention.

The invention will now be described in more detail in the following Examples, which in no way limit the scope or scope of the invention, but merely illustrate it.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

A separate granular phenmedipham product is prepared from a raw material mixture comprising:

phenmedipham ligninsulfonates phenylsulfonates diatomite kaolin 7.4% by weight 7.0% by weight 2.0% by weight 3.6% by weight

The raw materials used for the preparation are milled in an Alpine mill for granulation. Granulation is performed by extrusion (Nica); in this case, water is mixed with the dry mixture in an amount of 10% by weight based on the weight of the mixture. The diameter of the cavities in the matrix is 1 mm. The extruded mixture is cut into granules of 2 mm in length, which are spherically rounded in a Spheronizer Apparetus. The product was further dried in a fluid-bed dryer. The product obtained in this way disperses perfectly in water.

The suspension can be verified by experiment in which the product is dispensed into a 100 ml tapered bottomed tube containing 100 distilled water (+ 25 ° C). After wetting, the granules are observed and the tube is rotated 180 degrees thirty times. Sedimentation is observed at 1 minute, 5 minutes and 10 minutes.

In the case of the above granules, the amount of separated sediment is 0.05 ml after 1 minute, 0.05 ml after mixing, 0.05 ml after 5 minutes and 0.05 ml after stirring.

The average particle size in the suspension, determined using a Coulter LS 130 apparatus, is 2 µm.

For comparison purposes, the suspension properties of the suspension were determined on a commercial product called Goltix. The following values were obtained: 1 min) 0.01 ml; 5 min) 0.1 ml; and 10 min) 0.18 ml.

Example 2

A separate granulated phenmedipham product is prepared from a pre-ground feedstock composition comprising: phenmedipham 89% by weight lignin sulphonate derivatives 7.2% by weight phenyl sulphonates 3.6% by weight

The mixture is granulated by spray drying from a 50% aqueous suspension of said mixture (Niro). The average granule size depends on the size of the apparatus. The granules take shape in rounds. The properties of the suspension are determined as described in Example 1. The following results are obtained: 1 min) 0? 5 ml; 5 min) 0.9 ml; 10 min) 1.2 ml. The average particle size in said suspension is 3 µm.

Example 3

A separate granulated fenrzed ifam product is prepared from the raw materials listed in Example 1 using disk granulation; in this case, the granulation mixture is moistened using water in an amount of 10% by weight, calculated on a dry mass. The following results are obtained for the suspension: 1 min) 0.02 ml; 5 min) 0.15 ml; 10 min) 0.25 ml. The average particle size in said suspension is 3 µm.

Example 4

Separate activator-containing granules are prepared from a pre-ground carrier mixture by disk granulation of granules comprising:

orthosilicic acid (precipitated, e.g. Zeolthix 265) 85 wt. ammonium sulfate 2 wt. sodium chloride 6% wt. lignin sulphonates 2% wt. phenylsulfonates 5 wt.

and by impregnation in an activator solution (mixture A), which contains: alkyl sorbitol ethoxylate 42% wt. fatty alcohol ethoxylate 21% wt. ethoxylated fatty acid esters 8% wt. phosphate esters of ethoxylated fatty acids 5% wt. alkylarylsulfonic acid 5% wt. alkylaminetoxylát 4% wt. paraffin oil 15% wt. 1: 1,5-

Jamostatic granules containing the activator may also be blended to form a simple granule mixture with the above grains. formulations that contain the active ingredients, or each formulation may be dosed separately into a stirred container where they are mixed together. These granules disperse moderately in water.

Example 5

A granular product containing phenmedipham and an activator is prepared from a pre-ground feedstock mixture comprising:

femmedifsm 16.0 % hm. 1igninsulfonate 2.6 % hm. phenylsulphonates 5.5 % hm. urea 7.0 % hm. kaolin 5.5 % hm. diatomite 5.0 % hm. mixture B 50.4 % hm. polyethylene glycol 8.0 % hm. Mixture B contains: Ortho-silicic acid (precipitated) 37.5 % hm. bentonite 2.5 % hm. fatty alcohol ethoxylates 16.0 % hm. polyetylénsorbitol.y 33.8 % hm. paraffin oil 5.1 % hm. alkylaminated ethoxylates 5.1 % hm. This mixture is granulated by disc, in kt orom sa mixture heated to + 70 ° C, and formed granulated product the

recool to ambient temperature. The product has medium suspending properties.

- 12 Example 6

A layered granulated product is prepared

phenmedipham and activator of a mixture containing: fenmedifam 16.0% wt. 1ignínsulfonáty 2.7% wt. phenylsulphonates 5.3% wt. kaolin 15.5% wt. diatomite 5.0% wt. polyethylene glycol 5.0% wt. mixture B 50.4% wt. (as in Ex 5) The mixture is applied as a polyethylene glyco-

1 to granules prepared from other raw materials at a temperature of + 70 ° C in a disc granulator. The product has medium suspending properties.

Example 7

A granular product containing fenraedipham and a activator is prepared using an extrusion process from a raw material mixture comprising:

fenmed ifam 32.0 % hm. lignin 7.4 % hm. phenylsulphonates 2.0 % hm. kaolin 1.1 % hm. diatomite 2.0 % hm. naphthene sulfonates 2.0 % hm. mixture C 50.0 % hm. Mixture C contains: Ortho-silicic acid (precipitated). 34.0 % hm. phenylsulphonates 0.8 %> hm. ammonium sulfate 0.8 % hm. sodium chloride 1.6 % hm. 1ignínsulofnáty 0.8 % hm. naphthene sulfonates 2.0 % hm. mixture A 60.0 % hm. Suspension properties are: 1 min) 0.15 mL; 5 min) 0, »3 ml;

min) 0.4 ml;

13 Example 8

A granular product containing fenmedipham and desmedipham is prepared from a mixture comprising:

fenmedifam desmedifam 60.0% wt. 20.0% wt. lignin 5.9% wt. phenylsulphonates 5.6 wt. kaolin 4.0% wt. diatomite 2.0% wt. Suspension properties The following products are:

min) 0.01 ml; 5 min) 0.02 mL; 10 min) 0.03 mL.

Example 9

A granular product containing phenmedipham and etofumezate is prepared by a disk granulation method from a mixture comprising:

fenmedifam 32.0% wt. ethofumesate 40.0% wt. 1ignínsulfonáty 6.0% wt. phenylsulphonates 5.0% wt. naphthene sulfonates 9.0% wt. bentonite 0.2% wt. urea 7.8% wt. The suspending properties of said granular are: 1 min) 0.01 ml; 5 min) 0.03 mL; 10 min) 0.04 mL. product Example 9b Granules containing phenmedipham are prepared and by disk granulation from a mixture comprising: ethofumesate fenmedifam 35.0% wt. ethofumesate 34.7% wt. lignin 5.9% wt. phenylsulfonate 5.6 wt. diatomite 2.0% wt. kaolin 16.8% wt.

Suspension properties are: 1 min) 0.15 mL; 5 min) 0.5 ml, * 10 min) 0.8 ml.

- 14 Example 10

A granular product containing phenmedipham and metamitron is prepared by disk granulation from a mixture containing

hu je: fenmedifam 16.0 # hm. metamitron 64.0 % wt. 1 1ignínsulfonáty 5.9 % wt. phenylsulphonates 5.6 % wt. diatomite 2.0 % wt. kaolin 6.5 % wt. 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 is prepared by disk granulation from a mixture comprising:

fenmedifam 25.0 % hm chlorodazone 50.0 % hm 1ignínsulfonáty 5.9 'YF / 0 hm phenylsulphonates 5.6 % hm diatomite 1.1 % hm kaolin 12.4 % hm

The suspension capacity of the granules is: 1 min) 0.03 ml; 5 min) 0.10 ml; 10 min) 0.15 ml.

Example 11b

A granular product is prepared containing phenmedipham and chlorodazone using disc granulation from a mixture containing: fenmedifam 20.0 % hm. chlorodazone 60.0 % hm. 1ignínsulfonáty 5.9 %> hm. phenylsulphonates 5.6 it hm. diatomite 1.1 % hm. kaolin 7.4 % hm.

The suspending 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 n-n-imifipam and chlorodazone is prepared by disk gponulation from a mixture comprising:

fenmedifam 12.0 % hm. desmed ifam 3.0 % hm. chlorodazone 45.0 % hm. lignin 5.9 % hm. phenylsulphonates 7.0 % hm. Fluorinated surfactant substances 2.0 % hm. alkylarylbetaín 5.0 % hm. diatomite 1.0 % hm. kaolin 19.1 % hm. Suspension capacity Granules are: 1 min) 0.1 ml; 5 min)

0.35 ml; 10 min) 0.45 ml.

Example 13

A tablet containing fenmedifam with an effector is prepared

about compression using a pressure of 300 kg / cm from a mixture containing: fenmedifam 24.0% wt. 1ignínsulfonáty 5.9% wt. phenylsulphonates 3.0 wt. naphthene sulfonates 4.5 wt. Potassium hydrogen phosphate 6.0% wt. sodium carbonate 5.0% wt. magnesium stearate 1.0% wt. mixture C 50.0% wt. kaolin 0.6 wt. Said teblet is produced using a mold having a through

50 mm, in which case 30 g of the mixture is used.

The suspending properties of this tablet are shown to be moderate when the tablet is dispersed in a 500 ml decanter containing 300 ml of water, with visual observation.

- 16 Biological experiments:

The efficacy of the formulations prepared is tested against the weeds that can be encountered in the cultivation of sugar beet, such as Amaranthus retroflexus, Brassica napus, Chenopodium album, and Stellaria media. ). Four pots for weed species are used in the experiments for the test samples. The efficacy of the formulations tested is determined according to typical evaluation principles on a scale of 0 to 10, with a state corresponding to complete weed destruction assigned to a value of 10. This is given (given that four pots with samples are used for each weed species, average of the four pots.

On the same scale, sensitivity to damage to sugar beet (Beta vulgaris) is determined.

Experiment 1

The biological efficacy of a mixture of granulated phenmedipham (as in Example 1) and a granulated activator (as in Example 4) is compared with the emulsion concentrate formulation containing fenmedifam (Kemifam) available on the market. The amount of the active ingredient ^R is ss TESTOVENT same species, and 640 g of active ingredient per hectare. Efficacy was examined 7 days after spraying.

Active Ingredient Product / Efficacy Hectare Amaranth Rape Carrot Starfish Sugar Beet

Kemifam 4 1 5.7 7.8 9.8 7.0 1.0 Example 1 0.8 kg 0.7 0.0 0.0 3.0 0.0 Example 1 + 0.8 kg + Example 4 1,5 kg 4.0 8.0 8.3 7.7 0.3 Example 1 + 0.8 kg + Example 4 3,0 kg 7.3 θ 2 8.7 7.2 1.0

The results show that the granulated phenmediphara product without activator is not effective. However, by means of a granulated activator, the granulated phenmedifem product can be activated so much that the effect of the same amount of product (3.8 kg compared to 4 L) on the amaranth, rape and starfish is better than the compared and the beet damage is very small.

- 17 Experiment 2

In this experiment, the efficacy of the granular product containing phenmedipham and activator is compared with the emulsion concentrate product (kemifam) available on the market and the suspension concentrate product (Betaflow) available on the market. The amount of active ingredient per hectare was 640 g / ha and the same in all experiments. Evaluation is performed 14 days after spraying.

Test product amaranth

Efficacy of canola star beet

Kemifam 4 Betaflow 4 Example 5 3 Example 6 4

4 1

3 1

4 1

3 1

The results show that granular formulations of fenmedifam have the same biological activity as both concentrates, emulsion and suspension. Also the damage to the harvested crop is the same.

experiment 3

In this experiment, the efficacy of a mixture of a granular product (such as Example 8) containing phenmedipham (69% by weight) and desmedifam (20% by weight) and a granular product (such as Example 4) containing the ectator and a commercially available emulsified concentrated formulation containing phenmedifam (129 / g) / l) and desmedipham (34 g / l). The amount of active ingredient per hectare was 625 g for Betanal Compact and 640 g in Example 8 + Example 4. Efficacy was determined 14 days after spraying.

Teslovaný product/ Ú č i n n o s ť product hekátr amaranth colza mrlík maximum wiring sugar. beet Betanal Compact 4 1 5.5 7.2 7.0 19.7 1.0 Example 8 + Example + 4 0.8 kg 3.8 kg B 3 5.3 9.0 22.6 1.0 experiment shows that mixture fenmedifam and de smed if 8in

it even performs better than the corresponding emulsion concentrate product, which serves as a reference. Sugar beet damage is the same for both products.

Experiment 4

In this experiment, ss compares the efficacy of granules (such as Example 9) containing fenmedifam and etofuire plugs and granules (as in Example 4) containing 8 activator with a commercially available emulsion concentrate product, Betaron, which contains phenmedifam

80 g / l 8 etofumazate 100 g / l. Effectiveness down 14 days after atomization. Overall quantity active of components n and experiment is 640 g / ha. Tested product / Ú č i n n o s ť product hectare amaranth colza starfish sugar beet Betaron 3.6 1 5 6 9 1 Example 9b 0.81 kg 4 5 8 1 Example 9b + 0.81 kg + Example 4 0.67 kg 8 7 8 1 experiment proves to be granulated fenfen-

of phama and etofumezate also requires the addition of an activator, which gives biologically good results compared to the comparator. The damage is identical.

Experiment 5

In this experiment, the efficacy of a granular product containing phenmedipham and metamitron (as in Example 10) and this product and a granular activator (as in Example 4) is compared with the performance of a stock composition consisting of a phenmedipham suspension concentrate product containing the active ingredient 160 g / la granular metamitron product (Goltix) having a concentration of 700 g / kg. The amount of active ingredients per hectare was the same for all species tested. The efficacy is determined 14 days after spraying.

tested product product/ hectare A favor or kindness n n o s ť rapeseed starfish sugar beet fenmedipham SC Goltix 1.5 1 1.37 kg 9.5 9.5 10 0 Example 10 1,5 kg 7.0 7.0 9.0 0 Example 10 + + Example 4  1,5 kg 7.0 9.0 9.5 0

Metemitron, which acts eco for both soil and foliage applications, does not require activators in the same sense as phenmedipham; this is indicated by the relatively high efficiency of the granulated product - 10. In all cases, using a granulated product of the medifam + methammitron + activator ingredients, excellent selective biological effects are achieved without any symptoms of sugar beet damage.

Experiment 6

In this experiment, the efficacy of the granular product containing phenmedifine and chlorodazone as in Example 11b, where the concentrations were 20 or 60% by weight and the composition and the granular activator, as in Example 4, was compared with the suspension concentrate containing the active phenmedifam and chlorodazone. up to 300 g / l. However, the significance of a granular activator in a triple mixture of granular product containing phenmedipham, desmedipham and chlorodazone was also investigated. Mno-

Λ active ingredient species. Efficiency per hectare lays down was the same for all test 14 days after spraying. tested product product/ hectare Ú č starfish i n n o s ť Amaranth rape ceukrová r. fenmedifem 4.8 1 6.0 8.0 8.0 0

SC chlorodazone

Example 11b 2.4 kg 5,0 4,0 3,0 0 Example 11b 2.4 kg 6 0 kg 6.0 7.0 0 + Example 4 2.3 Example 12 3.2 kg 7,0 6.0 5.0 1.0 Example 12 + Example 4 3.2 ^kg 9,0 6.0 7.5 1.0 Experiments clearly show increase efficiency, who

also important in the mixed formulation of leaf-acting fenmedifam and soil-acting chlorodazone. This also applies to the triple mixture which contains the leaf-acting desmedipham in addition to the two previous mixtures.

Field experiments

Field experiment 1

For the purpose of this experiment, the biological activity of granular products containing fenmedipham is compared with the action of emulsion and suspension concentrate products already commercially available.

Experiments are carried out according to conventional field experiment methods. They are carried out in three rounds, all after the emergence of sugar beet seedlings. Efficacy is assessed visually and evaluated in comparison to an untreated plant opinion of 0. The value 100 is attributed to totally regulated capacity (where weeds are not at all). The amount of phenmedipham used in each spray cycle was 480 g / h a.

Tested product

1. Kemifam (fenmedifam 160 g / l)

2. Batanal Plus (fenmedifem 160)

Third

4th

5th

6th

7th

Example

Príkled

Example

Example

Example

Example

Example

Example

Example mixture A

product / ha efficiency% EC) 3x31 75 g / 1, SC) 3x31 83 3 x 0.6 kg 3 x 1.15 kg 83 3 x 0.6 kg 3 x 2.3 kg 93 3 x 0.6 kg 3 x 1.4 kg 83 3 x 1.5 kg 55 3 x 1.5 kg 3 x 1.15 kg 81

The efficiency of the granular product containing the active ingredient used together with the granular activator, the total amount of material used being 1.75 kg / ha, is practically the same as the efficiency of the suspension product when used in an amount of 3 l / h. If a granulated product containing an activator is used (in this case the total amount of material used is 2.75 kg / ha), a significantly better efficiency of the granulated product than the suspension product is obtained. In this experiment, the granules containing the activator are dispersed separately according to the purpose of the tests carried out, but it is clear that the granular mixture containing the active ingredient and the activator can be premixed to form a simple homogeneous mixture which can be dispersed as a single mixture.

A liquid activator used conventionally as a mixture from a container such as test species 5 can be used together with a granulated product containing the active ingredient. The activator granules in Example 4 contain a mixture A of 60% by weight, in this case test species 4 and 5 are included. the same amount of liquid component. However, surprisingly, it has been found that the solid carrier of the granular product increases the action of the activator granules on the efficacy of the active ingredient to 10 > 6. It is also noteworthy that this granular product is more than 10% more effective than a commercial suspension concentrate product and up to 20% more efficient than a commercial emulsion concentrate product.

Field experiment 2

In this experiment, the biological activity of a granulated product containing phenmedipham and etofumezate (Example 9a) and activator (Example 4) is compared with that of an emulsion concentrate product (Betaron) available on the market. The conditions and arrangement of all tests are the same as in the Field Experiment

1. The quantity of active ingredient used shall be 540 g per hectare.

Tested product product / ha efficiency% 1 Betaron 3x31 95 fenmedipham 80 g / l etofumazate 100 g / l 2 Example 9a 3 x 0.75 kg 91 Example 4 3 x 0.58 kg 3 Example 9a 3 x 0.75 kg 93 Example 4 3 x 1.15 kg

With a total amount of 1.33 kg of granulated product, almost the same efficiency as with 3 L of emulsion concentrate is achieved. Handling a product containing the active ingredient and activator does not cause difficulty in spraying.

Field experiment 3

This experiment compares the effectiveness of a conventional sugar oil spraying program and a granule-based spraying program. Usually, sp fenformamide, methamitrone or etofumezate are not used alone, but mixtures from containers are used in which they are mixed in varying proportions, depending on the weed species.

Kemiron is an emulsion concentrate containing 200 g per liter of etofumezate, and granulated etofumezate (B1fU granules) is a water dispersible granular product containing an active ingredient of 65%. The amount of active ingredient per hectare is always the same and this applies to all species tested.

Conventional program:

1. Spraying 1.5 1 Kemifam + 1 kg Goltix + 0.5 1 Kemiron

2. Spray 1.5 1 Kemifam + 1 kg Goltix + 1.0 1 Kemiron

J. Spraying 1.5 L Kemifam + 0.5 kg Goltix + 1.0 L Kemiron

Granule-based program;

1. Spray 0.2 kg Example 1 + 1 kg Goltix + 1.15 kg EFUgranules

2. Spray 0.2 kg Example 1 + 1 kg Goltix + 0.3 kg EFUgranules

3. Spray 0.2 kg Example 1 + 0.5 kg Goltix + 0.3 kg

ERF-granules

1.15 kg is contained in each spray. Example 4

Efficiency: conventional 90% granule-based program 89%

The results show that the granule-based program acts as a program in which fenmedifam and etofumezate are in liquid form as emulsion-emulsion concentrates.

Industrial usability

The process according to the invention makes it possible to prepare granular herbicidal products with very good water dispersibility and good biological activity. The nature of these products allows for very good spraying without clogging the sprayers.

Claims (12)

PATENT CLAIMS A process for preparing a herbicidal composition in granular form, said product comprising methyl 3-m-tolylcarbamoyloxyphenylcarbamate or ethyl 3-phenylcarbamoyloxyphenylcarbamate as a herbicidally active compound and surfactants and / or oils as an activator ingredient, characterized in that: wherein said activator ingredient is combined with a solid carrier material so as to form a solid composition with an ectator, and the composition thus obtained is combined with the herbicidally active compound to form a herbicidal product, said composition and said compound being contained in two separate individual solid phases; is forming (a) formation of grams containing the herbicidally active compound and coating the granules with a layer of a solid activator; or (b) forming granules consisting of a solid activator composition and coating the granules with a solid layer consisting of a herbicidally active compound; or c) forming first granules consisting of the herbicidally active compound and second granules consisting of a solid activator composition and mixing said first and second granules together. Method according to claim 1, characterized in that the activator ingredient is a liquid which is soaked into a solid carrier material. The method of claim 2, wherein the activator ingredient is a solid that is mixed with a solid carrier. Method according to claim 1, characterized in that the carrier material is of natural origin. The method of claim 1, wherein the carrier material is of synthetic origin. - 24 a The method of claim 1, wherein said activator ingredient comprises anionic, cationic, amphoteric or nonionic surfactants or mixtures thereof, 7. The method of claim 1 wherein said activator ingredient comprises a mineral olet I is vegetable oils, animal oils, their hydrolysis products or mixtures thereof. The process according to claim 1, wherein the proportion of surfactants is 50 to 100% by weight of the activator ingredient. The process according to claim 1, wherein the proportion of oil is at most 50% by weight of the activator ingredient. The method of claim 1, wherein the proportion of activator ingredient is 10 to 70% by weight of ⁴ wt. t • The method of claim 1 wherein auxiliary agents for dispersing, wetting, granulating, stabilizing, controlling pH or defoaming of the activator composition are included in the solid activator composition. Process according to claim 1, characterized in that in addition to said herbicidally active compounds, other plant protection agents, such as chlorodezone, metamitron or etofumezate, are also incorporated into the product into the same granules as said herbicidally active compounds or as individual discrete granules. .