FI93416C - Process for the preparation of a herbicide product in granular or tablet form - Google Patents

Description

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The present invention relates to a process for preparing a herbicidal product in the form of a granule or a tablet, which contains methyl 3-tolyl-carbamoyloxyphenylcarbamate or ethyl-3-phenylcarbamoyloxyphenylcarbamate as a herbicidal active ingredient and and / or oils. These active ingredients are insoluble in water and mainly foliar and are therefore sprayed as aqueous dilutions on the crop. For this reason, the granules are prepared to be dispersible in water so as to obtain a uniform and non-syringe-like slurry when the product is diluted in water.

Carbamoyloxyphenylcarbamate and benzofuran herbicides have traditionally been formulated as emulsion concentrates in which the active ingredient is dissolved in organic solvents and which are mixed with water to emulsion by means of solution emulsifiers. However, the disadvantages of these formulations are the toxicity and flammability of the product caused by organic solvents and the difficulty of causing the product to form a permanent non-crystalline emulsion with water. Crystallization is specific to methyl 3-tolylcarbamoyloxyphenylcarbamate.

Formulations in which the active ingredients are not dissolved are in themselves advantageous, since toxicity, flammability, packaging material and storage problems are generally avoided, since permeability and transportability are required to achieve sufficient biological efficacy, especially in foliar weed killers. Hydrolytic decomposition is also often a disadvantage.

. *: The active substance as a molecule is able to penetrate through the wax and cuticle layer in a real liquid much more efficiently than a solid particle. For this reason, the insoluble active ingredient particles must be finely ground as much as possible and their penetration and translocation capacity must be improved with oils, organic solvent additions and surfactants. In particular, it is necessary to add exceptionally large amounts of these excipients to carbamoyloxyphenylcarbamates in order to achieve sufficient biological efficacy. Air jet and suspension mills are used in grinding to provide the finest possible active ingredient, preferably of the order of 1 to 5 microns, to provide biological performance and as stable a slurry as possible when the granule is dispersed in water.

In solid form, the active ingredient may be present in a water-dilutable formulation, either as a liquid suspension concentrate or as a water-soluble granule. Disadvantages of the liquid formulation are often storage difficulties, handling problems due to high viscosity, and the waste remains in incompletely emptied containers. The latter disadvantage is becoming a major environmental problem in the disposal of used containers. Solid breastfeeding granules avoid these difficulties. In addition, the granular product can be packed in materials that are less harmful to the environment, such as cardboard, which makes it easier to dispose of empty packages.

In addition to the chemical stability of the active ingredients, the basic properties of the slurry include good slurry in water, sufficient grain strength so that no harmful dust is released during storage or handling, the free flowability of the granules and the ability not to clump during storage. In order to achieve these properties, the granule may contain, in addition to a water-insoluble carrier, a dispersing, suspending, wetting, preserving, antifoaming and anti-caking agent.

It is known that carbamoyloxyphenylcarbamates, the most important of which are methyl 3-m-tolylcarbamoyloxyphenylcarbamate, commonly known as phenmedicam, and ethyl-3-phenylcarbamoyloxyphenylcarbamate, generally known as desmedipharine.23).

3 r ~ \ 93416 V y— nhcoor2 ^ ^ - NHCOO / \ r *

Where R1 and R2 = CH3 or R1 = H and R2 = CH2CH are selective and good in herbicidal properties. These active ingredients can be used alone or in mixtures with each other and / or with other pesticides, in particular for controlling sugar beet weeds.

Traditionally, the above-mentioned active ingredients have been formulated as emulsion concentrates. But because of the tendency to avoid organic solvents and because phenmedipham readily crystallizes when these formulations are diluted in water, the goal has now been to prepare slurry granules from these active ingredients. It is previously known to prepare water-suspended granules (US 3,920,442) from pesticides as well as a dispersible triazine herbicide containing a surfactant to improve crystallization properties (US 4,197,112) or granules whose physical properties are improved by surfactants. EP 201.417). As a barrier to the commercialization of breastfeeding carbamoyloxyphenyl carbamate granules, it has been difficult to incorporate sufficient biological potency into the product due to the proportion of liquid oil and / or surfactants in the ratio: very high (about 1: 1) and economically difficult to technically implement.

It is known that water-slurry granules made from certain pesticide active ingredients provide good biological efficacy. However, with carbamoyloxyphenyl carbamates, sufficient efficacy cannot be obtained by these methods.

It has now surprisingly been found that water-suspended granular products containing carbamoyloxyphenylcarbamate, in addition to achieving the above granular product properties, can also be significantly improved by preparing a granular or tablet product by combining the enhancer component with a solid carrier. solid enhancer composition and that the resulting composition is combined with said herbicidal ingredient into a herbicidal product in which the enhancer composition and the herbicidal ingredient belong to two separate solid phases by a) forming granules or tablets containing with a solid layer containing the herbicidal ingredient, or (c) by forming granules containing the herbicidal ingredient and granules of the composition and mixing these granules with each other.

By using an enhancer absorbed on the carrier, the biological potency enhancing effect of the solid carbamoyloxyphenyl carbamate preparation has even been increased compared to its non-absorbed, which has been found in both greenhouse and field experiments.

Inorganic substances of natural origin, such as silicic acid-based substances, alumina-based substances, attapulgite, montmorillonite, mica-based substances (Mica), diatomaceous earth, kaleite, benignite, naturally occurring inorganic substances, such as silicic acid-based substances, and water-insoluble or water-soluble salts.

On the other hand, porous organic substances of natural origin, such as wood or corn cob flour, coconut, almond, olive or cereal peel flour, cellulose, starch and alginates, or porous structures based on naturally occurring polymeric starting materials, can be used. e.g. lignin derivatives, cellulose derivatives, starch derivatives and cyclodextrins, or synthetic polymers such as polyacrylates, polyacrylamides, polyvinyl derivatives, maleic acid polymers, polyurethanes, polylactides and glycols.

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The enhancer can be encapsulated in the carrier material by coating the absorbed particles with a polymer such as polyvinyl alcohol, or with sugar or sugar alcohol-based substances such as lactose, CMC and sorbitol. In this case, the release rate of the booster is also adjustable.

The liquid enhancer can also be enclosed in capsules that can still be used in the granule formulation. Encapsulation methods are well known. Peeling agents can also affect the strength and abrasion resistance of the granules. On the other hand, they can be used to improve the flowability of the product.

An enhancer containing surfactants and / or oil is not important for the actual granulation, but its main purpose is to enhance the biological activity of the product.

The proportion of enhancer may generally be 1 to 80% by weight of the granular product, preferably 0.5 to 5 times the amount of carbamoyloxyphenyl carbamate in the preparation.

The enhancer may be in solid or liquid form (at 20 ° C) so that it can be absorbed into the carrier or mixed with the granulation mass. Alternatively, it can also be; absorbed or otherwise attached to the product after granulation.

The enhancer may contain anionic, cationic, nonionic or ampholytic surfactants or in combination with a mineral or vegetable or animal oil. The proportion of surfactants in the enhancer may be 2 to 100%, preferably 50 to 100%. The proportion of oil may accordingly be 0 to 98%, preferably 0 to 50 *.

Anionic surfactants may include alkyl sulfonates, alkyl aryl sulfonates, sulfate ethers, fatty alcohol sulfates, sulfate ester sulfocarboxylic acids and derivatives thereof, alkyl glycerol ether sulfonates, sulfoesters, sulfoamides, and di-phosphoric acid derivatives.

Cationic surfactants can be alkyl or alkylarylamines, alkyl or alkylarylimidazolines, and alkylaminoamides.

Nonionic surfactants may include fatty alcohol ethoxylates, fatty acid ethoxylates, alkylaryl ethoxylates, alkyl sugar or alkyl sugar alcohol ethoxylates, diethylamide amides of alkyl or alkylarylamine polyglycol ethers, fatty acid amides, fatty acid amides, fatty acid amides and derivatives of tri-glycerides, acetylene diols, silicone-based surfactants.

Ampholytic surfactants may include alkyl and alkylaryl betaine derivatives, alkyl and alkylaryl (poly) glycine derivatives, alkyl and alkylarylamine dicarboxylates, and alkyl and alkylarylamine sulfonates. Fluorine-containing surfactants can also be used.

The oily substance may be a mineral oil, preferably having a low viscosity, so that it can be readily absorbed by the carrier. On the other hand, the oil must not significantly impair the useful. It is most preferred to use a paraffin oil with a low degree of aromaticity, e.g. Neutral solvent 150, Exxon, the oily substance may be a vegetable oil or a hydrolysis product thereof such as soybean oil and a fatty acid mixture of soybean oil. The oil may also contain phospholipids and sterols.

• The oily substance may be of animal origin, in which case the oil is preferably rich in unsaturated fatty acids and their glycerides.

Granulation of the active ingredient or its and the carrier containing the enhancer, or granulation of the carrier or the active ingredient and the carrier, is conditional on the material to be granulated being finely divided.

The material can be ground, for example, dry with an air jet mill or as a slurry with a bead mill. It is essential that the solid have an average particle size of about. 10 yum and the active ingredient is preferably of the order of 5 yum (measured with a Coulter device) in order to achieve biological efficacy.

The granulation can be carried out with auxiliaries which promote the formation of the granule, the rewetting of the granule, the rapid disintegration and slurry of the granule during the preparation of the working solution, and substances which prevent the foamability of the working solution. Since the active ingredient can be decomposed in a basic working solution, inorganic and organic pH-adjusting substances such as phosphoric acid or its acid salts and citric acid can be used in the mixture so that the pH in the working solution is less than 7, preferably 3.5 to 5.5.

Granulation aids can be used in granules where the active ingredient and the enhancer are in the same granule or in separate active ingredient and enhancer granules.

Granular disintegrants, which may be polymers such as polyvinylpyrrolidone and starch. and its modified forms, or salts, such as, for example, ammonium sulfate, or organic water-soluble compounds, such as, for example, urea or gas-releasing substances, such as, for example, carbonates.

Dispersants such as, for example, phenylsulfonates, alkylnaphthalenesulfonates and polymerized naphthalenesulfonates, polyacrylic acids and their salts, polyacrylamide oxyethylene oxides, polyacrylamides, polyalkoxydiamine derivatives, polyethylene, can be used as granule slurries. Dispersants 93416 8 can be used in 0.1 to 50%, preferably 5 to 20% of the granular product.

Similar substances can also be used as granulation aids, such as, for example, polyethylene glycol, in which the incorporation of an enhancer-containing part into the finished active ingredient-containing granule is preferred at a concentration of 1-20%.

The foamability of the spray mixture to be prepared for spraying can be limited by antifoaming agents, such as silicone-based agents. The substances are preferably used in an amount of 0 to 0.5% of the amount of granular product.

Known methods can be used for granulation, such as plate granulation, spray drying (such as Niro), Lei fluid bed granulation (such as Glatt and Schugi), mixing granulation with a vertical mixer (such as Fielder) or a blade mixer (such as Forberg), extruder ( such as Nica) or compaction granulation (such as Bepex equipment) or centrifugal granulation (such as CF granulator, Freund Industrial Co.) or spray bed granulation.

The enhancer can be compressed into a water-dispersible tablet, whereby its size may vary due to the matrix. Conventional tableting devices are, for example, rotary (Mans-ty) or eccentric tableting devices (Diaf).

Two or more of the above methods in series can also be used for granulation and tableting. The surface of the granule can be mechanically hardened by rounding the granule, e.g. with a Spheronizer (Nica), or by coating the granules with suitable substances as mentioned above.

It is important that the granular product is dried. The product can be dried either in a device used for granulation or in a separate device for drying (such as a fluid bed dryer). The moisture content of the granular product should preferably be less than 5%, preferably less than 1%.

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Due to the granulation method, the grain size of the final product can vary on average up to 3 mm or considerably larger in the case of water-dispersible tablets.

It goes without saying that other pesticides can also be mixed together with carbamoyloxyphenyl carbamates (such as phenmedipham and desmedipham) to form a granular product. Pesticides can be herbicides, pesticides for plants and insects, and growth regulators.

It is preferred to use herbicides especially used in sugar beet cultivation, such as ethofumesate, metamitron, chloridazon, lenasilium, pyridate, meto-chloro, trichloroacetic acid, EPTC, quinmerac, cycloate, clopyralid, triocarbide, isocarbipid, isofuripyr, isofuripyr, diime, dihalate, fluazifop-butyl, triallate, dalapone or propaqizaphobia.

The preparations according to the invention can be used after the seedling of the useful plant, preferably several times during the growing season. A suitable amount of active ingredient per application is 0.1 to 1 kg per hectare, depending on the number of applications.

The invention is described in more detail below by means of examples.

Example 1

A separate phenmedipham granule product can be prepared from a raw material mixture containing: phenmedipham 80%; ·, lignin sulfonates 7.4% phenyl sulfonates 7.0% diatomaceous earth 2.0% kaolin 3.6%

The raw materials used in 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 as 93416 10 in 10% by weight. The diameter of the openings in the matrix is 1 mm. The extruded mass is cut into granules of about 2 mm in length, which can be further rounded in a Spheronizer. The product is dried in a fluid bed dryer. The product obtained by the method is highly soluble in water.

Slurrying can be detected by an experiment in which 1 g of product is dispensed into a 100 ml narrow-ended graduated test tube containing 100 ml of distilled water (+ 25 ° C). When wetting of the granule is observed, the tube is turned 30 times 180 degrees. Sediment formation is monitored for 1 min, 5 min, 10 min.

With the above-mentioned granule, the sediment layer separates after mixing after 1 min of 0.05 ml, after 5 min from 0.05 ml and after 10 min from 0.05 ml.

The average particle size of the slurry, determined with a Coulter LS 130, was about 2.

For comparison, a precipitation property assay was performed on a commercial product called Goltix. The values were 1 min) 0.01 ml, 5 min) 0.1 ml and 10 min) 0.18 ml.

Example 2

A separate granular phenmedipham product can be prepared from a pre-ground raw material mixture containing: phenmedipham 89% lignin sulfonate derivatives 7.2% phenyl sulfonates 3.6%

The mixture can be granulated by spray-drying a 50% aqueous suspension of the mixture (Miro). The average size of the granules depends on the size of the equipment. The granules are round in shape. The precipitation results are determined according to the method described above (1 min) 0.15 ml, 5 min) 0.9 ml, 10 min) 1.2 ml. The average particle size of the slurry is 3 μm.

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Example 3

A separate granular phenmedipham product can be prepared from the raw materials mentioned in Example 1 using plate granulation, whereby the granulation mass is moistened with 10% by weight of water based on the amount of dry matter. The precipitation results are 1 min) 0.02 ml, 5 min) 0.15 ml, 10 min) 0.25 ml. The average particle size of the slurry is about 3.

Example 4

A separate enhancer-containing granule can be prepared by making a pre-milled carrier mixture by plate granulation granule containing: silicic acid (precipitated, e.g., Zeolthix 265) 85% ammonium sulfate 2% table salt 6% lignin sulfonates 2% alkyl sulfonates % fatty alcohol ethoxylate 21% ethoxylated fatty acid esters 8% ethoxylated phosphate esters of fatty acids 5% alkylarylsulfonic acid 5% alkylamine ethoxylate 4% paraffin oil 15% in a ratio of 1: 1.5

The separate enhancer-containing granule can be mixed into a single granule mixture with the above-mentioned granule formulations containing active ingredients or dispensed separately into a tank mixture with these. The grain settles moderately in the water.

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Example 5

The granular product containing phenmediphar and enhancer can be prepared from a raw material mixture containing: phenmedipharn 16.0% lignin sulfonates 2.6% phenylsulfonates 5.5% urea 7.0% kaolin 5.5% diatomaceous earth 5.0% mixture B 50.4% polyethylene glycol 8.0%

Mixture B contains: silicic acid (doped) 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 plate where the mass is heated to +70 ° C and the formed granular product is cooled back to room temperature. The slurry properties of the product are moderate.

: Example 6

The layered granular product containing phenmedipham and enhancer can be prepared from a mixture containing: phenmedipham 16.0% lignin sulfonates 2.7% phenylsulfonates 5.3%. kaolin 15.5% diatomaceous earth 5.0%. polyethylene glycol 5.0%

Mixture B 50.4% (as in Example 5)

Mixture B is coated with polyethylene glycol on a granule made from other raw materials at + 70 ° C in a plate granulator. The sedimentation properties of the granule are moderate.

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Example 7

The granular product containing phenmedipham and enhancer can be prepared by extrusion from a raw material mixture containing: phenmedipham 32.0% lignin sulfonates 7.4% phenyl sulfonates 2.0% kaolin 1.1% diatomaceous earth 2.0% naphthenene sulfonates 2.0%

Mixture C 50.0%

Mixture C contains: silicic acid (precipitated) 34.0% phenyl sulphonates 0.8% ammonium sulphate 0.8% table salt 1.6% lignin sulphonates 0.8% naphthenisulphonates 2.0%

Mixture A: 60.0%

The slurry 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 desmedipharn can be prepared from a mixture containing: phenmedipham 60.0% desmedipharn 20.0% lignin sulfonates 5.9% phenylsulfonates 5.6% kaolin 4.0% * <diatomaceous earth 2.0%

The slurry properties of the granule are 1 min) 0.01 ml, 5 min) 0.02 ml, 10 min) 0.03 ml.

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Example 9

The granular product containing phenmediphar and ethofumesate can be prepared by a plate granulation technique from a mixture containing: phenmedipharn 32.0% ethofumesate 40.0% lignin sulfonates 6.0% phenylsulfonates 5.0% naphthenene sulfonates 9.0% bentonite 0.2% urea 7.8%

The slurry properties of the granule 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 prepared by plate granulation from a mixture containing: phenmedipham 35.0% ethofumesate 34.7% lignin sulfonates 5.9% phenylsulfonates 5.6% diatomaceous earth 2.0% kaolin 16.8%

The slurry properties were 1 min) 0.15 ml, 5 min) 0.5 ml, 10 min) 0.8 ml.

Example 10

The granular product containing phenmedipham and metamitron can be prepared by plate granulation from a mixture containing: phenmedipham 16.0% metamitron 64.0% lignin sulfonates 5.9% phenylsulfonates 5.6% diatomaceous earth 2.0%. j .: kaolin 6.5% 93416 15

The slurry properties of the granule are 1 min) 0.01 ml, 5 min) 0.02 ml, 10 min) 0.03 ml.

Example 11

The granular product containing phenmedipharine and chloridazon can be prepared by plate granulation from a mixture containing: phenmedipharn 25.0% chloridiazone 50.0% lignin sulfonates 5.9% phenylsulfonates 5.6% diatomaceous earth l.1% kaolin 12.4%

The slurry capacity of the granule is 1 min) 0.03 ml, 5 min) 0.10 ml, 10 min) 0.15 ml.

Example 11 b

The granular product containing phenmedipharine and chloridazon can be prepared by disc granulation from a mixture containing: phenmedipharn 20.0% chloridiazone 60.0% lignin sulfonates 5.9% phenylsulfonates 5.6% diatomaceous earth 1.1% kaolin 7.4%

The slurry properties of the product are 1 min) 0.03 ml, 5 min) 0.10 ml, 10 min) 0.15 ml.

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Example 12

The granular product containing phenmediphar, desmediphar and chloridiazone can be prepared by disc granulation from a mixture containing: phenmediphar 12.0% desmedipharn 3.0% chloridazone 45.0% lignin sulfonates 5.9% phenylsulfonates 10.0% kaolinyl

The slurry capacity of the granule is 1 min) 0.1 ml, 5 min) 0.35 ml, 10 min) 0.45.

Example 13

A tablet containing phenmedipham and an enhancer can be prepared by compression at a pressure of 300 kg) cm2 of a mixture containing: phenmedipham 24.0% lignin sulfonates 5.9% phenylsulfonates 3.0% naphthenesulfonates 4.5% potassium dihydrogen phosphate 6.0% sodium carbonate 1.0%% stearate 5.0% magnesium stearate • j The tablet can be made into a 50 mm diameter mold using 30 g of the mixture.

The tablet slurry properties are moderate when visually dispersing the tablet in a 500 ml beaker with 300 ml of water.

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Biological tests:

The activities of the prepared formulations were tested against common weeds in sugar beet cultivation, such as Amaranthus retroflexus, oilseed rape (Brassica napus), clay (Chenopodium album) and water grass (Stellaria media). Four pots / rich species / experimental member were used in the experiment. Effects were evaluated according to typical evaluation criteria on a scale of 0-10, giving 10 images of complete plant destruction. The average of the four pots was reported.

On the same scale, the susceptibility of sugar beet (Beta vulgaris) to trout damage was determined.

Test 1

The biological activity of the mixture of phenmedipham granule (such as 1) and enhancer granule (such as 4) was compared with a commercial emulsion concentrate preparation containing phenmedipham (Kemifam). The amounts of active ingredient in the test members were the same 640 g of active ingredient per hectare. Efficacy was checked 7 days after injection.

Active ingredient Power product / ha revonh. rapeseed clay water. sj. Kemifam 4 1 5.7 7.8 9.8 7.0 1.0 eg 1. 0.8 kg 0.7 0.0 0.0 3.0 0.0 · eg 1. 0.8 kg 4.0 8.0 8.3 7.7 0.3 + eg 4. 1.5 kg eg 1. 0.8 kg 7.3 8.2 8.7 7.2 1.0 + eg 4. 3.0 kg

The result shows that phenmedipham granule without enhancer is not biologically effective. On the other hand, phenmedipham granule can be activated with a booster granule so that with the same amount of product (3.8 kg compared to 4 l) the potency is better than the reference for northern tail, oilseed rape and water grass and the damage to sugar beet is very small.

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Test 2

The experiment compared the efficacy of granules containing phenmedipham and enhancer with a commercial emulsion concentrate product (Kemifam) and a commercial suspension concentrate product (Betaflow). The amount of active substance used per hectare was 640 g / ha in all of them. Evaluation was performed 14 days after injection.

Test substance Power revonh. rapeseed water. S.J.

Kemifam 4,441

Betaflow 4 431 eg 5. 3 341 eg 6. 4 331

The results show that the granulate formulations of phenmedipharine are biologically equivalent to both emulsion and suspension concentrate references. The damage to useful plants is also the same.

Test 3

The experiment compared the efficacy of a mixture of phenmedipharn (69%) and desmedipharn (20%) -containing granule (such as 8.) and enhancer-containing granule (such as esm 4.) with phenmedipharine (129 g / l) and desmedipharn (34 g / l) on the market. ) emulsion concentrate. The amounts of active ingredient per hectare were 652 g for Betanal Compact and 640 g for Example 8 + Example 4. Effects were determined 14 days after injection.

Test substance Power product / ha revonh. rapeseed clay tot. S.J. Betanal / 4 1 5.5 7.2 7.0 19.7 1.0

Compact

Eg 8 0.8 kg 8.3 5.3 9.0 22.6 1.0

Eg 4 3.8 kg 19 9341 6

The experiment also shows that the mixture of phenmedipham and desmedipham performs even better than the corresponding corresponding emulsion concentrate preparation. The damage to sugar beet is the same for both products.

Test 4

The experiment compared the efficacy of a granule containing phenmedipham and ethofumesate (such as Example 9) and a granule containing an enhancer (such as Example 4) to a commercial emulsion concentrate preparation, Betaron, containing 80 g / l of phenmedipham and 100 g / l of ethofumesate. Effects were determined 14 days after injection. The total amount of active substances per experiment was 640 g / ha.

Test substance Power product / ha revonh. rapeseed water. S.J.

Betaron 3.61 5 6 9 1

First 9b 0.81 kg 4 5 8 1

Eg 9 b + 0.81 kg 8 7 8 1

Example 4 0.67 kg

The experiment shows that the mixture of phenmedipham and ethofumesate also requires the addition of an enhancer in granular form, which results in at least the same biological result as the reference. The damage is identical.

Test 5

The experiment compared the efficacy of a granule containing phenmedipham and metamitron (such as Example 10) and a booster granule (such as Example 4) of a tank mixture consisting of a suspension concentrate of phenmedipham containing 160 g / l of active ingredient and a preparation of metamitron (Goltix) containing 700 g / kg. The amounts of active ingredient per hectare are the same for the test members. Effects were determined 14 days after injection.

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Test substance Power product / ha revonh. rapeseed water. S.J. fenmedif. 1.5 1 9.5 9.5 10 0 SC Goltix 1.37 kg

Eg 10 1.5 kg 7.0 7.0 9.0 0

Eg 10+ 1.5 kg 7.0 9.0 9.5 0

Eg 4 1.1 kg

Metamitron, which acts as both a soil and a foliar, does not require enhancers in the same way as phenmedipham, as demonstrated by the relatively good potency of e.g. 10-granule. However, even in this case, with the addition of an enhancer, a significant improvement in efficacy is obtained in oilseed rape; overall, the phenmedipham + metamitron + enhancer granule achieves an excellent selective biological effect without any symptoms of damage to sugar beet.

Test 6

The experiment compared a granule containing phenmedipham and chloridiazone, such as 11b at 20 and 60%, respectively, with a suspension concentrate containing phenmedipham and chloridazon containing 100 and 300 g / l, respectively. , to power. On the other hand, the role of the enhancer granule in the triple mixture granule containing phenmedipham, desmedipharn and chloridazon was investigated. The amounts of active ingredient per hectare are the same for the test members. Efficacy was determined 14 days after injection.

Test substance Effect of product / ha of water. revonh. rapeseed s.j.

fenmedif. 4.81 6.0 8.0 8.0 0 SC chloride.

Example 11 b 2.4 kg 5.0 4.0 3.0 0

Eg 11 b + 2.4 kg 6.0 6.0 7.0 0

Example 4 2.3

Example 12 3.2 kg 7.0 6.0 5.0 1.0

Eg 12+ 3.2 kg 9.0 6.0 7.5 1.0

First 4 2.3 kg «•« 93416 21

The experiment clearly shows the importance of increasing potency in the mixture formulation of leaf-acting phenmediphar and ground-acting chloridiazone. The same is true for the ternary mixture, which, in addition to the above, contains leaf-acting desmedipham.

field tests

Field test 1

The aim of the experiment was to compare the biological efficacy of granular phenmedipham-containing products with already commercially available emulsion and suspension concentrate products.

The tests have been performed in accordance with standard field test practice. There were three treatments, all done after the sugar beet seedlings. Efficacy was checked visually and evaluated for an untreated ratio of o. A rating of 100 describes complete control. The application rate of fenmedifar was 480 g / ha in each application.

Test substance product / ha power% 1 Kemifam 3 * 31 75 (phenmedipham 160 g / l, EC) 2 Batanal Plus 3 * 31 83

(phenmedipham 160 g / l, SC

3 First 1 3 * 0.6 kg 83

Example 4 3 * 1.15 kg 4 Example 1 3 * 0.6 kg 93

Example 4 3 * 2.3 kg 5 Example 1 3 * 0.6 kg 83

Example 4 relationship A 3 * 1.4 kg 6 Example 7 3 * 1.5 kg 55 7 Example 7 3 * 1.5 kg 81

Example 4 3 * 1.15 kg

The potency of the granular active ingredient-containing preparation when used in combination with the granular enhancer, with a total amount of 93416 22 material applied of 1.75 kg / ha, is as good as that of the suspension preparation when applied at 3 l / ha. When a granule containing more enhancer is used, in which case the total amount of the applied substance is 2.75 kg / ha, the granular preparation gives a significantly better efficiency than the suspension product. In the experiment, the enhancer-containing granule was dosed separately for technical reasons, but it is clear that the active ingredient-containing and enhancer-containing granules can be premixed into one homogeneous uniformly dispensable mass.

With the pesticide-containing granule, a liquid enhancer can be used in a conventional manner as a tank mix, as in Test Member 5. The enhancer granule of Example 4 contains 60% of mixture A, with the liquid portion being equal in Test Members 4 and 5. However, it can surprisingly be found that the solid base of the granule increases the effect of the enhancer granule on the potency of the active substance by more than 10%. It is also noteworthy that this granule preparation is more than 10% more effective than a commercial suspension concentrate preparation and even more than 20% more effective than a commercial emulsion concentrate preparation.

Field test 2

The experiment compared the biological efficacy of a granular product containing phenmediphar and ethofumesate (Example 9a) and an enhancer (Example 4) with a commercially available emulsion concentrate preparation (Betaron) containing the same active ingredients. General experimental arrangements were made as in field experiment 1. The application rate of the active ingredients was 540 g / ha / application.

Test substances product / ha power% 1 Betaron 3 * 31 95 • phenmedipharn 80 g / l ethofumesate 100 g / l 2 Eg 9a 3 * 0.75 kg 91

First 4 3 * 0.58 kg 3 Eg 9a 3 * 0.75 kg 93

Eg 4 3 * 1.15 kg 93416 23

With a total amount of 1.33 kg of granular product, almost the same potency was obtained as with 3 l of emulsion concentrate. The handling of the product containing the active ingredient and the enhancer during spraying has not caused any difficulties.

Field test 3

The experiment compared the efficiencies of a standard spraying program used in sugar beet cultivation and a granular-based spraying program. In practice, phenmedipharine, metamitron or ethofumesate are generally not used alone, but tank mixtures of these, where the mixing ratios may vary depending on the offenses.

Kemiron is an emulsion concentrate containing 200 g ethofumesate per liter and an ethofumesate granule (EFU granule) containing 65% of the active substance in a water-tolerable granule. The amounts of active ingredient per hectare were the same for the experimental members.

Standard schedule: 1st injection 1.5 1 Kemifam + 1 kg Goltix + 0.5 1 Kemiron 2nd injection 1.5 1 Kemifam + 1 kg Goltix + 1.0 1 Kemiron 3rd injection 1.5 1 Kemifam + 0.5 kg Goltix +1.0 1 Kemiron

Granule-based program: 1st spray 0.2 kg Eg l + 1 kg Goltix + 0.15 kg EFU grain ... 2nd spray 0.2 kg Eg 1 + 1 kg Goltix + 0.3 kg EFU grain 3rd spray 0.2 kg Eg 1 + 0.5 kg Goltix + 0.3 kg EFU granule in each included 1.15 kg Ex 4.

Power: standard program 90% granule-based program 89%

From the results, it can be seen that the program based on granular preparations has worked as well as the program in which phenmedipham and ethofumesate are in liquid form as emulsion-emulsion concentrates.

Claims (12)

A process for the preparation of a granular or tablet herbicide product which contains as herbicidally active component methyl 3-tolylcarbamoyloxyphenylcarbamate or ethyl 3-phenylcarbamoyloxyphenylcarbamate, and as a reinforcing component, a surfactant and / or oleaginate, by combining the reinforcing component with a solid support into a solid reinforcing composition and combining the obtained composition with said herbicide component into a herbicide product in which the reinforcing composition and herbicide component belong to two separate phases, granules or tablets containing the herbicide component and coating them with a layer of the reinforcing composition, or b) forming granules or tablets of the reinforcing composition and coating them with a solid layer containing the herbicide component, or c) forming granules containing the herbicide component zeros of the reinforcing composition and mixing these granules with each other. Process according to Claim 1, characterized in that the reinforcing component is a liquid, water-solid carrier. . impregnated. Process according to claim 1, characterized in that the reinforcing component is a solid which is mixed with the solid support. Method according to claim 1, characterized in that the carrier is of natural origin. 5. A method according to claim 1, characterized in that the carrier is a synthetic agent. Method according to claim 1, characterized in that the reinforcing component contains an anionic, cationic, amphoteric or nonionic surfactant or a mixture thereof. 7. A process according to claim 1, characterized in that the reinforcing component contains mineral oil, vegetable oil, animal oil, hydrolysis products thereof or a mixture thereof. Method according to claim 1, characterized in that the surfactant forms 50 - 100% of the reinforcing component. Method according to claim 1, characterized in that the oil forms a maximum of 50% of the reinforcing component. Process according to claim 1, characterized in that the reinforcing component forms 10 - 70% of the solid reinforcing composition. 11. A method according to claim 1, characterized in that aids for dispersing, wetting, granulating, stabilizing, acidifying the reinforcing composition or preventing foaming thereof are included in the solid reinforcing composition. A method according to claim 1, characterized in that in addition to the herbicide component, other herbicides such as chloridazone, metamitron or etofumesate are included in the product, either in the same granules as the herbicide component or as separate granules. . ·