SI9300110A - A method of producing herbicidal granular products - Google Patents

Abstract

The invention relates to a manufacturing process granular mixtures containing known per se herbicides, the activator used being solid preparation, which include activator components either impregnated with and / or with carrier material mixed

Description

KEMIRA ΟΥ

Process for making herbicidal granular products

The present invention relates to a process for the manufacture of herbicidal granular products containing carbamoyloxyphenylcarbamates and / or substituted benzofurans, which are known per se as active ingredients, surfactants, suspending agents, inert carriers and optionally other auxiliaries such as stabilizers, antifoams, dyes and preservatives. These substances are insoluble in water and act as a foil and are therefore dispersed as aqueous dilutions to the plant site. This makes the granules dispersible in water to give a homogeneous suspension that will not clog the spray if the product is diluted with water.

Carbamoyloxyphenylcarbamate and benzofuran herbicides are usually formulated as emulsion concentrates in which the active ingredient is dissolved in organic solvents and can be mixed with water to form a water-soluble emulsion. However, these preparations have disadvantages of product toxicity due to organic solvents, flammability of the products and also difficulty in obtaining a stable emulsion of the product which does not crystallize with water. The crystallization is typical in particular of methyl-3-tolylcarbamoyloxyphenylcarbamate.

Formulations of the product in which the active ingredients are not in dissolved form are, as such, advantageous in that they avoid the problems of toxicity, flammability, packaging material and storage, because, especially in the case of foliar-acting herbicides, penetration and translocation capabilities are required to achieve sufficient biological efficiency. Hydrolytic degradation is also often a disadvantage. The active ingredient in molecular form is able to penetrate the wax and top layer in real fluid much more effectively than a solid. For this reason, insoluble particles of the active substance must be crushed as finely as possible and its penetration and translocation capabilities must be improved by oils, organic solvents and surfactants. In particular in the case of carbamoyloxyphenylcarbamates, it is essential to add extremely large amounts of these auxiliaries in order to achieve sufficient bio-efficacy. For crushing, air jet and suspension mills are used to obtain the maximum finely divided active ingredient, preferably in the order of 1 to 5 µm in size, to achieve biological efficiency and the most stable suspension when the granules are dispersed in water.

In solid form, the active ingredient may be present in a water-dilutable preparation, either as a liquid suspension concentrate or as a water-dispersible granular product. Defects in liquid product designs often include storage problems, high viscosity handling problems, and debris left in containers that do not empty completely. The last defect just mentioned is becoming a major environmental problem in the disposal of used containers. These problems are avoided by solid granular dispersible liquids. In addition, the granular product can be packaged in materials such as cardboard that are less burdensome for the environment and therefore easier to dispose of empty packaging.

The basic properties of water-dispersible granules include, in addition to the chemical stability of the ingredients, a good ability to disperse in water, sufficient strength of the granules so that no harmful dust is formed in connection with storage or handling, the granularity of the granules and the ability to remain unaccepted during storage. In order to achieve these properties, the granule may contain, in addition to the water-insoluble carrier, also a dispersant, a suspending agent, a wetting agent, a preservative, an antifoaming agent and an antifoaming agent.

Carbamoyloxyphenylcarbamates, of which methyl-3m-tolylcarbamoyloxyphenylcarbamate, commonly referred to as phenmedipham, and ethyl-3phenylcarbamoyloxyphenylcarbamate, commonly called desmedipham (BP 679,283), are known to be the most known.

where R 1 and R ₂ = CH ₃ or R _t = H and = CH ₂ CH are selective and good in herbicidal properties. These substances may be used separately or as mixtures of each other and / or other suppressants, in particular for weed control in beet crops.

Typically, the active ingredients are formulated as emulsion concentrates. However, since the purpose is to avoid organic solvents, and because phenmedipham tends to crystallize when diluted with these formulations with water, the present purpose is to make water-dispersible granules of these active ingredients. The preparation of water-dispersible granules of herbicides (US 3,920,442) and also of dispersible herbicidal triazine granules containing surfactant which exudes crystallizing properties (US 4,197,112) or granules whose physical properties improve surfactant are known from before funds (EP 201,417). An obstacle to the commercialization of dispersible carbamoyloxyphenylcarbamates has been the difficulty of incorporating sufficient biological efficacy into a product where the ratio of the amount of liquid oil and / or surfactants to the amounts of active ingredients is very large (about 1: 1) and uneconomical for technical use.

It is known that good bio-efficacy can be achieved with water-dispersible granulars made from certain herbicide ingredients. However, carbamoyloxyphenylcarbamates cannot be sufficiently effected by these processes.

It has now been surprisingly observed that with water-dispersible granular products containing carbamoyloxyphenylcarbamate, it is possible not only to achieve the above properties of the granular product, but also to significantly improve them by preparing a granular product or a tablet-shaped product in which impregnated activator into the carrier, which is added uniformly according to its plate, either as a layer to the surface of the granule or tablet or as a core in the granule or tablet. Alternatively, a special granule or tablet can be made from a liquid activator and carrier. Granules mixed with the granular containing the active ingredient may be packed in one container, in one space therein, as a sufficiently uniform granular mixture to form a single product, or may be used as a separate added agent in the mixture in the tank. A separate tablet may be added together with the granular or tablet formulation to form a combination mix for use.

Using the carrier-impregnated activator, the bio-efficacy of solid carbamoyloxyphenylcarbamate even increased compared to the non-impregnated activator. This was observed in both greenhouse and field tests.

As an activator carrier, we can use inorganic substances that adsorb large quantities of oily substances and are of natural origin, such as silica-based materials, alumina-based substances, attapulgite, montmorillonite, mica-based substances, diatomite, bentonite, talc, kaolin, lime , gypsum and water soluble or water insoluble salts.

Alternatively, it can be used as a carrier of porous organic matter of natural origin, such as wood chips or ground corn cones, ground coconut shells or almonds, ground cereal chaff, cellulose, starch and alginates, or porous structures based on natural polymeric starting materials modified sources 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 can be incorporated into the carrier material by coating the impregnated particles with a polymer such as polyvinyl alcohol, or with sugars or sugars based on sugars such as lactose, CMC and sorbitol. In this case, we can also regulate the rate of release of activatoi.

The liquid activator may also be embedded in capsules, which can later be used in the granular product. The procedures for encapsulation are generally known. Coating materials can also affect the strength of the granules and their abrasion resistance. On the other side, they can be used to improve the fluidity of the product.

An activator containing surfactants and / or oil is not important for the granulation itself; its main purpose is to improve the biological function of the product.

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

The activator can be in solid or liquid form (at 20 ° C) and in this case it can be impregnated into the carrier or mixed with the mixture to be granulated. Alternatively, it may also be impregnated into the product or otherwise attached to it after granulation.

The activator may contain anionic, cationic, nonionic and ampholytic surfactants, or these agents together with mineral oil, vegetable oil or animal oil. The proportion of surfactant in the activator may be 2 to 100%, preferably 50 to 100%. The proportion of oil in this respect may be from 0 to 98%, preferably from 0 to 50%.

Anionic surfactants may be alkyl sulfonates, alkylaryl sulfonates, sulfate ethers, fatty alcohol sulfates, sulfocarboxylic acid sulfate esters and their derivatives, alkyl glycerol ether sulfonates, sulfoesters, sulfonamides and phosphorous mono- and diesters, bile acids and their salts.

The cationic surfactants may be alkylamines or alkylarylamines, alkyl or alkylaryl imidazolines, and alkylaminoamides.

Non-ionic surfactants may be fat alcohol alcohol ethoxylates, fatty acid ethoxylates, alkylaryl ethoxylates, alkyl sugar ethoxylates or alkyl sugar alcohol ethoxylates, alkylamine or alkylarylamine polyglycol ethers, amide fatty acid derivatives, diethanolamides, or polydiethanol monodyethanol triglycerides, acetylene diols, and silicon-based surfactants.

Amopholytic surfactants may be alkyl and alkylaryl betaine derivatives, alkyl and alkylaryl (poly) glycine derivatives, alkylamide and alkylaryl amide carboxylates, and alkylamine and alkylarylamine sulfonates. Surfactants containing fluorine may also be used.

The oily substance may be a mineral oil, preferably with low viscosity, so that it can be easily impregnated into the carrier. On the other hand, the oil should not significantly disturb the sown plant. Low-aromatic paraffinic oil, e.g. Neutral solvent 150 by Εχχοη. The oily substance may be vegetable oil or its hydrolysis products, such as soybean oil or a mixture of fatty acids of soybean oil. The oil may also contain phospholipids and sterols.

The oily substance may be of animal origin, in which case it is preferable if the oil contains a large amount of unsaturated fatty acids and their glycerides.

The first condition for the granulation of the active substance or active substance and its carrier containing the activator or for the granulation of the carrier or active ingredient or activator is that the material to be granulated is finely distributed.

The material can be crushed, e.g. when dry, in an air-jet mill or as a suspension in a ball mill. It is essential that the particle size of the solids average about 10 μτη and the particle size of the active substance is preferably in the order of 5 μτη (measured in the Coulter apparatus) to achieve biological efficiency.

Granulating agents may be used to promote granule formation, re-wetting of the granules and rapid decomposition and dispersion of the granules when the solution is ready for use, as well as agents that prevent foaming of the solution for use. Since the active substance may be degraded in the stock solution for use, inorganic or organic pH control agents such as phosphoric acid or its acid salts and citric acid may be used in the mixture so that the pH of the solution for use is below 7, preferably 3.5 to 5 , 5.

In granules in which the active ingredient and the activator are in the same granule or in separate granules with the active ingredient and granules with the activator, auxiliary granulating agents may be used.

Granule-accelerating agents may be polymers such as polyvinyl pyrrolidone and starch and modified forms, or salts such as ammonium sulfate, or organic water-soluble compounds such as urea, or gaseous substances such as carbonates .

As commonly known as granule-enhancing agents, dispersants such as phenyl sulfonates, alkylnaphthalene sulfonates and polymerized naphthalene sulfonates, polyacrylic acids and their salts, polyacrylamides, polyalkoxydamine derivatives, polyethylene oxides, polypropylene oxide, polypropylene oxide, polypropylene oxide, can be used derivatives and mixtures thereof and sulfonated lignin derivatives. The dispersants can be used in an amount of 0.1 to 50%, preferably 5 to 20% of the granular product.

Similar products can also be used as granulation enhancers, such as polyethylene glycol, in which case it is advantageous to add an activator-containing ingredient in the proportion of 1 to 20% of the final active ingredient-containing granule.

Ί

The foaming of the mixture to be sprayed can be controlled with antifoaming agents, as silica-based agents. It is preferable to use such agents in an amount of 0 to 0.5% of the granular product.

For granulation, methods known from the prior art may be used, such as plate granulation, spray drying (e.g. Niro), fluidized bed granulation (e.g. Glatt and Schugi), blending granulation using a vertical mixer (e.g. Fielder) or a paddle mixer ( e.g., Forberg), extruder granulation (e.g., Nice) or compacting granulation (e.g., Bepex machine) or centrifugal granulation (e.g., CF granulator, Freund Industrial Co.), or diffuse layer granulation.

The activator can be compressed into a water dispersible tablet, in which case its size may vary depending on the matrix. Conventional pills include rotary (Mansty) and eccentric pill (Diaf).

It is also possible to use two granules and tablets more than the above procedures in succession. The surface of the granule can be mechanically hardened by rounding the granule, e.g. using a Spheronizer (Nice) preparation, or by coating the granules with materials suitable for this purpose, as mentioned above.

Importantly, the granular product is dried. The product may be dried either in the preparation used for granulation or in a separate preparation intended for drying (eg in a fluid bed dryer). It is advantageous if the moisture content of the granular product is below 5%, preferably below 1%.

The size of the finished product granules may vary, on average, up to 3 mm or significantly more depending on the granulation process, in the case of water-dispersible tablets.

It is self-evident that other suppressants can be mixed together with carbamoyloxyphenylcarbamates (such as phenmedipham and desmedipham) to form a granular product. Suppressants may be herbicides, plant disease control agents and insecticides as well as growth control agents.

It is advantageous to use herbicides, which are used especially in the cultivation of beet, such as etofumesate, metamitron, chlorodazone, lenasyl, pyridate, metolachlorin, trichloroacetic acid, EPTC, cinmerac, cycloate, clopyralid, fluroxypyr, isocarbimide, profam, allo8 flimid, triam cetoxidime, dialate, fluazifop-butyl, trialate, dalapone or propacisafob.

The products of the invention can be used to originate seedlings of a cultivated plant, preferably in several rounds of use during the ripening time. The appropriate amount of the active ingredient per spray is 0.1 to 1 kg per hectare depending on the number of rounds used.

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

EXAMPLE 1

A separate granular phenmedipham product can be prepared from a mixture of raw materials containing:

phenmedipham 80% lignin sulfonates 7.4% phenyl sulfonates 7.0% diatomite 2.0% kaolin 3.6%

The raw materials used for preparation are previously ground for granulation with an air jet mill (Alpine). Granulation can be carried out by extrusion (Nice), in which case a 10% dry water mixture is mixed. The diameter of the openings in the die is 1 mm. Cut the extruded mixture into granules of about 2 mm in length, which can be rounded off in the Spheronizer. The product is dried in a fluid bed dryer. With this process, the resulting product is perfectly dispersed in water.

The suspension can be checked by experimenting in which 1 g of product is added to a 100 ml graduated tube with a tapered end containing 100 ml of distilled water (+25 ° C). When wetting of the granules is observed, turn the tube 30 times 180 °. Sediment formation is observed for 1 min, 5 min and 10 min.

In the case of the granules mentioned above, the amount of sediment that separated 1 min after stirring was 0.05 ml, 5 min after stirring 0.05 ml and 10 min after stirring 0.05 ml.

The average particle size in suspension determined using the Coulter LS apparatus

130, was approximately 2 μτη.

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

EXAMPLE 2

A separate granular phenmedipham product may be prepared from a previously ground raw material mixture containing:

phenmedipham 89% 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 device. Granules are round in shape. Determined by the method described above, the results of the suspension are: 1 min) 0.15 ml; 5 min) 0.9 ml; 10 min) 1.2 ml. The average particle size of the suspension is 3 μτη.

EXAMPLE 3

A separate granular phenmedipham product can be prepared from the syrups mentioned in Example 1 using granulation on a plate and in this case wetting the mixture to be granulated using 10 wt. % water calculated from dry matter. Suspension results are: 1 min) 0.02 ml; 5 min) 0.15 ml; 10 min) 0.25 ml. The average particle size of the suspension is about 3 μτη.

EXAMPLE 4

Separate granules containing the activator can be prepared by making from a pre-ground mixture of carriers with granulation on a plate granules containing:

silicic acid (precipitated, e.g. Zeolthix 265) ammonium sulfate sodium chloride lignin sulfonates phenyl sulfonates

85%

2%

6%

2%%

and impregnating an activator solution (mixture A) containing:

alkyl sorbitol ethoxylate ethoxylate fatty alcohols ethoxylated fatty acid esters ethoxylated fatty acid phosphate esters 5% alkylaryl sulfonic acid alkylamine ethoxylate paraffin oil

42%

21%

8%% 4% 15% in a 1: 1.5 ratio.

Separate activator-containing granules may also be mixed to form a single granule mixture with the active ingredient-containing granule formulations mentioned above, or may be added separately to form a mixture in the tank. The granules are dispersed medium in water.

EXAMPLE 5

A granular product containing phenmedipham and an activator can be prepared from a mixture of raw materials containing:

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 (colored) bentonite ethoxylates of fatty alcohols polyoxyethylene sorbitols paraffin oil alkylamine ethoxylates

37.5% 2.5% 16.0% 33.8% 5.1% 5.1%

The mixture was granulated on a plate on which the mixture was heated to +70 ° C and the resulting granules were cooled back to room temperature. The suspension properties of the product are medium.

EXAMPLE 6

A layered granular product containing phenmedipham and an activator can be prepared from a mixture containing:

phenmedipham 16.0% lignin sulfonates 2.7% phenyl sulfonates 5.3% kaolin 15.5% diatomite 5.0% polyethylene glycol 5.0% mixture B 50.4% (as in Example 5)

Mixture B is applied as a coating using polyethylene glycol on a granule prepared from other raw materials at +70 ° C on a granular plate. The suspension properties of the granular product are medium.

EXAMPLE 7

A granular product containing phenmedipham and an activator can be prepared by extrusion from a mixture of raw materials containing:

phenmedipham 32.0% lignin sulfonates 7.4% phenyl sulfonates 2.0% kaolin 1.1% diatomite 2.0% naphthenesulfonates 2.0% mixture C 50.0%

Mixture C contains:

silicic acid (precipitated) 34.0% phenyl sulfonates 0.8% ammonium sulfate 0.8% sodium chloride 1.6% lignin sulfonates 0.8% naphthenesulfonates 2.0% mixture A 60.0%

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 containing:

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 may be prepared by a plate-based granulation technique of a mixture containing:

phenmedipham etofumesate lignin sulfonates phenyl sulfonates naphthenes sulfonates bentonite urea

32.0% 40.0% 6.0% 5.0% 9.0% 0.2% 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 prepared by granulating on a plate of a mixture containing:

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 fenmedifam and metamitron can be prepared by granulation on a plate of a mixture containing:

phenmedipham metamitron lignin sulfonates phenyl sulfonates diatomite kaolin

16.0% 64.0% 5.9% 5.6% 2.0% 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 fenmedifam and chlorodazone can be prepared by granulating on a plate a mixture containing:

phenmedipham 25.0% chlorodazone 50.0% lignin sulfonates 5.9% phenyl sulfonates 5.6% diatomite 1.1% 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 fenmedifam and chlorodazone can be prepared by granulating on a plate a mixture containing:

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 fenmedipham, desmedipham and chlorodazone can be prepared by granulating on a plate of a mixture containing:

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 fenmedifam and an activator can be prepared by compression using a pressure of 294,2 bar from a mixture containing:

fenmedifam 24.0% lignin sulfonates 5.9% phenyl sulfonates 3.0% naphthenesulfonates 4,5% potassium hydrogen phosphate 6.0% sodium carbonate 5.0% magnesium stearate 1.0% a mixture of C 50,0% kaolin 0.6%

The tablet can be made in a 50 mm diameter mold, in which case g mixtures are used.

The suspension properties of the tablet are medium when visually observing the dispersion of the tablet in a 500 ml decantato containing 300 ml of water.

BIOLOGICAL EXPERIMENTS

The activities of the manufactured preparations were tested against the weeds commonly found in sugar beet cultivation, such as beetroot (Amaranthus retroflexus), common rape (Brassica napus), butterfly (Chenopodium album), and common asterisk (Stellaria media). In the experiments, we used four pots for each weed species for each test sample. The efficacy was evaluated according to typical evaluation principles on a scale from 0 to 10, describing the complete destruction of the plant by

10. We logged an average of four pots.

We determined the susceptibility of sugar beet (Beta vulgaris) to injury on the same scale.

TEST 1

The biological efficacy of a mixture of granular fenmedifam (as in example 1) and granular activator (as in example 4) was compared with a commercially available emulsion concentrate containing fenmedifam (Kemifam). The amounts of the active substance in the test samples were identical, 640 g of active ingredient per hectare. The efficacy was checked 7 days after spraying.

The active ingredient Efficiency product / a simple hat butterfly ordinary sugar hectare rapeseed star beets

Kemifam 41

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 4.0 8.0 8.3 7.7 0.3 + case 4 1,5 kg Example 1 0,8 kg 7.3 8.2 8.7 7.2 1.0

+ case 4 3.0 kg

The result shows that the granular phenmedipham product without activator is not biologically effective. On the other hand, with granular activatoi, the granular phenmedipham product can be activated such that with the same amount of product (3.8 kg versus 4 L), its effect on the husk, the colza and the asterisk is better than the effect of the comparator and the beet damage is very small.

TEST 2

In this experiment, we compared the efficacy of fenmedifam and activator-containing granular products with that of commercially available emulsion concentrate (Kemifam) and commercially available suspension concentrate (Betaflow). The amount of active ingredient per hectare was 640 g / ha in all experiments. We evaluate the performance 14 days after spraying.

Test Product Efficiency

hats ordinary rapeseed ordinary star sugar beets Kemifam 4 4 4 1 Betaflow 4 4 3 1 Example 5 3 3 4 1 Example 6 4 3 3 1

The results indicate that fenmedifam granular formulations have a biological efficacy equal to that of the comparative emulsion and suspension concentrate. The damage to cultivated crops is the same.

Experiment 3

In the experiment, we compared the efficacy of a mixture of granular product (as in example 8) containing phenmedipham (69%) and desmedipham (20%) and an activator-containing granular product (as in example 4) with commercially available emulsifiable concentrate preparations, containing phenmedipham (129 g / l) and desmedipham (34 g / l). The active substance amounts per hectare were 652 g for Betanal Compact and 640 g for Case 8 + Case 4. The efficacy was determined 14 days after spraying.

Test product Efficiency product / hectare hats ordinary rapeseed metlika total sugar beets Betanal Compact 41 5.5 7.2 7.0 19.7 1.0 Example 8 + case 4 0,8 kg 3,8 kg 8.3 5,3 9.0 22,6 1.0

The experiment also shows that the mixture of phenmedipham and desmedipham performs even better than the corresponding emulsion concentrate product used as a comparison. The sugar beet damage was the same with both products.

TEST 4

In the experiment, we compared the efficacy of phenemifam and ethofumesate-containing granules (as in Example 9) and activator-containing granules (as in Example 4) with the efficacy of a commercially available emulsion concentrate product, Betaron containing 80 g / l phenmedipham and ethofumesate 100 g / l. The efficacy was determined 14 days after spraying. The total number of active substances per experiment was 640 g / ha.

Test Product Efficiency

product / hectare hats ordinary rapeseed ordinary star sugar beets Betaron 3.61 5 6 9 1 Example 9b 0.81 kg 4 5 8 1 Example 9b 0.81 kg 8 7 8 1 + case 4 0.67 kg

The experiment shows that granules require a mixture of phenmedipham and ethofumesate also with the addition of an activator, thereby achieving biologically at least the same good result as with the comparator. The injuries caused are the same.

Experiment 5

In the experiment, the efficacy of a granular product containing phenmedipham and metamitron (as in Example 10) was compared with that of a granular activator (as in Example 4) with the performance of a mixture in a tank consisting of the product of the fenmedifam suspension concentrate containing the active ingredient 160 g / l and granular metamitron product (Goltix) at a concentration of 700 g / kg. The quantities of active ingredients per hectare were the same for all test samples. The efficacy was determined 14 days after spraying.

Test Product Efficiency

product / hectare hats ordinary rapeseed ordinary star sugar beets fenmedifam SC Goltix 1.51 1,37 kg 9.5 9.5 10 0 Example 10 1,5 kg 7.0 7.0 9.0 0 Example 10 + case 4 1,5 kg 1.1 kg 7.0 9.0 9.5 0

Metamitron, which works in both soil and foil applications, does not require activatoys in the same way as phenmedipham requires; this is shown by the relatively high efficacy of the granular product 10. However, even with the addition of activatoi, even in this case, a significant improvement in the effect on the common rapeseed is achieved. Overall, using the fenmedifam + metamitron + activatoi granular product, an excellent selective biological effect is achieved without any signs of damage to the beet.

Experiment 6

In the experiment, we compared the efficacy of a granular product containing phenmedipham and chlorodazone, as in Example 11b, in which the concentrations were 20 and 60%, respectively, and that of a product and granular activator, as in Example 4, and a suspension concentrate containing effective phenmedipham and chlorodazone, with concentrations of 100 and 300 g / l, respectively. On the other hand, we investigated the importance of granular activatoi in a triple-mixture granular product containing phenmedipham, desmedipham and chlorodazone. Substances per hectare are the same for all test samples. The efficacy was determined 14 days after spraying.

Test Product Efficiency

product / hectare ordinary star hats ordinary rapeseed sweetheart beets fenmedifam SC Chlorodazone 4.81 6.0 8.0 8.0 0 Example llb 2,4 kg 5.0 4.0 3.0 0 Example llb 2,4 kg 6.0 6.0 7.0 0 + case 4 2.3 kg Example 12 3,2 kg 7.0 6.0 5.0 1.0 Example 12 3,2 kg 9.0 6.0 7.5 1.0 + case 4 2.3 kg

The experiment clearly demonstrates the importance of increasing efficacy also in the blend of foliar-acting fenmedifam and floor-acting chlorodazone. The same applies to the triple mixture containing, in addition to the previous two, foliar-acting desmedipham.

FIELD TRIALS

Field experiment 1

The purpose of the experiment was to compare the biological action of fenmedifam-containing granular products with that of commercially available emulsion and suspension concentrate products.

The experiments were carried out in accordance with the usual fieldwork technique. We performed three rounds of application, all of which were performed following the emergence of sugar beet seedlings. The efficacy was visualized and evaluated in relation to the untreated plant habitat for which the value was 0. A value of 100 describes the ability to completely suppress. The amount of fenmedifam used in each spray cycle was 480 g / ha.

Test product product / ha efficiency% 1 Kemifam (phenmedipham 160 g / l, EC) 3 * 31 75 2 Batanal Plus (phenmedipham 160 g / l, SC) 3 * 31 83 3 Example 1 Example 4 3 * 0.6 kg 3 * 1.15 kg 83 4 Example 1 Example 4 3 * 0.6 kg 3 * 2.3 kg 93 5 Example 1 Example 4, mixture A 3 * 0.6 kg 3 * 1.4 kg 83

6 Example 7 3 * 1.5 kg 55 / Example 7 3 * 1.5 kg 81 Example 4 3 * 1.15 kg

The effectiveness of the granular product containing the active ingredient used in conjunction with the granular activator, the total amount of material used being

1.75 kg / ha is as good as the efficiency of the suspension product used in the amount of 3 1 / ha. If a granular product containing multiple activatoi was used, and in this case the total amount of material used was 2.75 kg / ha, we obtained significantly better efficacy with the granular product than with the suspension product. In the experiment, the granules containing the activator were administered separately due to the techniques of the assay, but it is clear that the granular mixture containing the active ingredient and the activator can be mixed in advance to obtain a single homogeneous mixture which is administered as such.

Together with the granular product containing the active ingredient, it is possible to use the liquid activator in the usual way as a mixture in the tank, as in test case 5. The activator granules of example 4 contain 60% of the mixture A, in which case test samples 4 and 5 are identical. plural quantities of the liquid ingredient. However, it can be surprisingly observed that the solid carrier material of the granular product increases the effect of the activator granules on the active ingredient efficiency by up to 10%. It is also noteworthy that the granular product is more than 10% more effective than the product of commercial suspension concentrate and up to 20% more effective than the product of commercial emulsion concentrate.

Field experiment 2

In the experiment, the biological efficacy of a granular product containing phenmedipham and ethofumesate (Example 9a) and an activator (Example 4) was compared with the commercially available emulsifiable concentrate product (Betaron). The whole test version was as in field experiment 1. The amount of the active substance used was 540 g / ha per spray cycle.

2i

Test product product / ha efficiency% 1 Betaron phenmedipham 80 g / l ethofumesate 100 g / l 3 * 31 95 2 Example 9a Example 4 3 * 0.75 kg 3 * 0.58 kg 91 3 Example 9a Example 4 3 * 0.75 kg 3 * 1.15 kg 93

With an overall amount of 1.33 kg of granular product, we achieved almost the same efficiency as with the 3 1 emulsion concentrate. Handling of the product containing the active substance and the activator did not cause any problems with the spraying.

Field experiment 3

The experiment compared the effectiveness of a conventional spray program used in sugar beet cultivation and a granule-based spray program. In practice, fenmedifam, metamitron or ethofumesate are not generally used alone, but instead use mixtures thereof in a tank in which, depending on the weeds, the mixing conditions may vary.

Kemiron is an emulsion concentrate containing ethofumesate 200 g / liter, and granules ethofumesate (EFU granules) is a water-dispersible granular product containing 65% of the active substance. The amounts of active ingredient per hectare were identical for both test samples.

Normal program:

1st spray: 1.51 Kemifam + 1 kg Goltix + 0.51 Kemirone

2nd spray: 1.5 1 Kemifam + 1 kg Goltix + 1.01 Kemirone

3rd spray: 1.5 1 Kemifam + 0.5 kg Goltix + 1.01 Kemirone

Granule based program:

1st spray: 0.2 kg of case 1 + 1 kg of Goltix + 1.15 kg of EFU granules

2nd spray: 0.2 kg of case 1 + 1 kg of Goltix + 0.3 kg of EFU granules

3. spray: 0.2 kg of case 1 + 0.5 kg of Goltix + 0.3 kg of EFU granules, each containing 1.15 kg of case 4

Effectiveness: Normal 90% granule based program 89%

The results show that the granulam product-based program worked just as well as the program in which phenmedipham and ethofumesate are in liquid form as emulsion-emulsion concentrates.

Claims (13)

PATENT APPLICATIONS A process for improving the efficacy of granular herbicide products or tablet herbicide products such as methyl-3-m-tolyl-carbamoyloxyphenylcarbamate, ethyl-3-phenyl-carbamoyloxyphenylcarbamate, 2-ethoxy-2,3-dihydro-3,3-dimethylbenzofuran -5-yl-methane sulfonate, 5-amino-4-chloro-2-phenylpyridazin-3 (24) -one, and 4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazine -5-one, using self-known activators, characterized in that the activator substances and activator constituents are impregnated into and / or mixed with a solid carrier material which, if appropriate, contains known auxiliaries to give a solid activator preparation, and the resulting solid activator preparation is contacted with the herbicide product either by a) form its layer on the surface of the granule or tablet; or b) embedded as a core into a granule or tablet; or c) to mix solid constituents with each other. A process according to claim 1, characterized in that the carrier is inorganic or organic in structure or gives a mixture of such substances. Method according to claim 2, characterized in that the carrier is of natural origin. A method according to claim 2, characterized in that the carrier is of synthetic origin. Process according to any one of the preceding claims, characterized in that the activator component is made of already known surfactants and / or oils. Process according to claim 5, characterized in that the surfactants are anionic, cationic, amphotemic or non-ionic surfactants or mixtures thereof. Process according to claim 5, characterized in that the oils are mineral oils, vegetable oils, animal oils, their hydrolysis products or mixtures thereof. Process according to claim 5 or 6, characterized in that the proportion of surfactants is about 50 to 100% of the activator component. Process according to claim 5 or 7, characterized in that the oil content is at most about 50% of the activator component. 10. The method of claim 1, wherein the proportion of activator component is about 10 to 70%, preferably 30 to 90%, of the solid activator preparation. A method according to claim 1, characterized in that the auxiliaries are the agents required for dispersing, wetting, granulating, stabilizing, pH-controlling or foaming the activator. A method according to claim 1, characterized in that the herbicidal products and the solid activator preparation are granulated or pelleted together or separately. Process according to claim 1, characterized in that other plant protection agents, preferably chlorodazone and metamitron, are used in the same granule or as a separate granule together with carbamoyloxyphenylcarbamate, preferably phenmedipham, desmedipham and / or ethofumesate.