DE10143086A1 - Use of calcium formate in plant treatment products - Google Patents

Abstract

The invention relates to the use of calcium formiate as a component of plant treatment agents containing active substances. The invention also relates to corresponding plant treatment agents containing between 0.005 and 99.9 wt. % calcium formiate, in addition to one or more agrochemical active substances and between 0.1 and 99.0 wt. % additives or water.

Description

The present invention relates to the new use of calcium formate as Inert substance and / or calcium fertilizer and / or calcium supplier in formulations of Plant treatment products.

Such use of calcium formate is not yet known become.

The calcium formate is commercially available and avoids problems that occur with the calcium salts commonly used in agrochemical formulations. Calcium formate is e.g. B. not hygroscopic like CaCl ₂ , in which intolerances were observed when sprayed directly onto young plants (commercially available calcium chloride usually contains traces of Ca (OH) ₂ ), and not as water-soluble as CaCO ₃ . The new formulations containing calcium formate are also better rainproof than the commonly used calcium salts (nitrate, carbonate and chloride). According to the invention, the plant treatment compositions containing calcium formate are allowed to act on the plant or its surroundings.

• - zwischen 0,005 und 99,9 Gew.-% an Calciumformiat sowie
• - zusätzlich gegebenenfalls einen oder mehrere agrochemische Wirkstoffe, und zwischen 0,1 und 99,995 Gew.-% an Zusatzstoffen oder Wasser enthalten.

The invention therefore relates to the use of calcium formate as a component of plant treatment agents. The invention also relates to plant treatment agents which

• - Between 0.005 and 99.9% by weight of calcium formate and
• - additionally optionally contain one or more agrochemical active substances, and between 0.1 and 99.995% by weight of additives or water.

• - zwischen 0,01 und 90 Gew.-% an Calciumformiat sowie
• - zusätzlich gegebenenfalls einen oder mehrere agrochemische Wirkstoffe, und zwischen 0,1 und 99,99 Gew.-% an Zusatzstoffen oder Wasser enthalten, sind bevorzugt.

Plant treatment products that

• - Between 0.01 and 90 wt .-% of calcium formate and
• - In addition, optionally one or more agrochemical active substances and containing between 0.1 and 99.99% by weight of additives or water are preferred.

• - zwischen 1 und 30 Gew.-% an Calciumformiat sowie
• - zusätzlich gegebenenfalls einen oder mehrere agrochemische Wirkstoffe, und zwischen 0,1 und 99 Gew.-% an Zusatzstoffen oder Wasser enthalten, sind besonders bevorzugt.

Plant treatment products that

• - Between 1 and 30 wt .-% of calcium formate and
• - In addition, optionally one or more agrochemical active ingredients and containing between 0.1 and 99% by weight of additives or water are particularly preferred.

As additives in the plant treatment products according to the invention can be included, other agrochemical agents come as well Crystallization inhibitors, wetting agents, emulsifiers and also water in question.

As agrochemical active substances come substances with herbicidal, insecticidal, growth-regulating, acaricidal and / or fungicidal properties into consideration.

Active substances from the group of nicotinyls, pyrethroids or ketoenol derivatives are preferred as insecticides or acaricides. May be mentioned as an example
Imidacloprid, thiametoxam
cypermethrin,
deltamethrin,
permethrin,
natural pyrethrum,
fenpropathrin
cyfluthrin,
β-cyfluthrin as well
from the group of the ketoneol derivatives, the 3- (2,4-dichlorophenyl) -4- (1,1-dimethylpropyl-carbonyloxy) -5-spiro-cyclohexyl-3-dihydrofuranon-2 and the 3- (2,4, 6-trimethylphenyl) -4- (2,2-dimethylpropyl-carbonyloxy) -5-spiro-cyclopentyl-3-dihydrofuranone-2.

Active ingredients from the group of azoles, strobilurin derivatives and amino acid derivatives are preferred as fungicides. May be mentioned as an example
tolylfluanid
tebuconazole,
cyproconazole,
triadimenol,
myclobutanil,
trifloxystrobin,
azoxystrobin,
Kresoxim-methyl,
picoxystrobin,
pyraclostrobin,
3- [1- (2- [4- (2-chlorophenoxy) -5-fluoropyrimid-6-yloxy] phenyl) -1- (methoximino) methyl] -5,6-dihydro-1,4,2- dioxazin and
Iprovalicarb.

Examples of herbicides are:
metribuzin,
rimsulfuron,
flufenacet,
sulcotrione,
metosulam,
nicosulfuron,
pyridate,
Terbutylazine,
bentazone,
metamitron,
Dicamba.

Ethephon is an example of a growth regulator.

Crystallization inhibitors which can be present in the plant treatment compositions according to the invention are all substances which can normally be used for such purposes in agrochemical compositions. N-Alkylpyrrolidones, such as N-octylpyrrolidone and N-dodecylpyrrolidone, may also be mentioned, further copolymers of polyvinylpyrrolidone and polyvinyl alcohol, such as, for example, the polyvinylpyrrolidone / polyvinyl alcohol known under the name Luviskol® VA 64 (from BASF). Copolymer, further alkylcarboxylic acid dimethylamides, such as decanoic acid dimethylamide or the C _6-12 alkanecarboxylic acid / dimethylamide mixture known under the name Hallcomid® (Hall Comp.), And also copolymers of ethylenediamine with ethylene oxide and propylene oxide, such as for example the product known under the name Synperonic® T 304 (Uniqema).

All usual for such purposes come in as wetting agents Substances that can be used in plant treatment agents. May be mentioned Alkylphenol ethoxylates, dialkyl sulfosuccinates, such as sodium dioctyl sulfosuccinate, Lauryl ether sulfates and polyoxyethylene sorbitan fatty acid esters.

Suitable emulsifiers are all customary nonionic, anionic, cationic and zwitterionic substances with surface-active properties, which are usually used in agrochemical compositions. These substances include reaction products of fatty acids, fatty acid esters, fatty alcohols, fatty amines, alkylphenols or alkylarylphenols with ethylene oxide, propylene oxide and / or butylene oxide, as well as their sulfuric acid esters, phosphoric acid monoesters and phosphoric acid di-esters, as well as reaction products of ethylene oxide with propylene oxide Alkyl sulfonates, alkyl sulfates, aryl sulfates, tetra-alkyl ammonium halides, trialkylaryl ammonium halides and alkyl amine sulfonates. The emulsifiers can be used individually or in a mixture. Reaction products of castor oil with ethylene oxide in a molar ratio of 1:20 to 1:60, reaction products of C ₆ -C ₂₀ alcohols with ethylene oxide in a molar ratio of 1: 5 to 1:50, reaction products of fatty amines with ethylene oxide in a molar ratio of 1: 2 to 1:20, reaction products of 1 mole of phenol with 2 to 3 moles of styrene and 10 to 50 moles of ethylene oxide, reaction products of C ₈ -C ₁₂ alkylphenols with ethylene oxide in a molar ratio of 1: 5 to 1:30, alkyl glycosides, C ₈ -C ₁₆ -Alkylbenzene sulfonic acid salts, such as. B. calcium, monoethanolammonium, diethanolammonium and triethanolammonium salts.

The agrochemical compositions according to the invention can also contain urea clathrates of liquid surfactants can be added. In particular solid formulations of the Plant treatment agents according to the invention can be those in the solid state Conveniently transferred surfactants are admixed.

Examples of non-ionic emulsifiers are those under the names Pluronic PE® 10 100 (from BASF) and Atlox® 4913 (from Uniqema) are known Called products. Tristyrylphenyl ethoxylates are also suitable. As examples for anionic emulsifiers that are known as Baykanol SL® (= Condensation product of sulfonated ditolyl ether with formaldehyde) in Commercial product from Bayer AG called as well as phosphated or sulfated tristyryl phenol ethoxylates, with Soprophor SLK® and Soprophor® 4D 384 (from Rhodia) may be specifically mentioned.

The plant treatment agents according to the invention are produced in the Way that the components in the desired proportions mixed together.

The temperatures in the preparation of the invention Plant treatment products can be varied within a certain range. You work in generally at temperatures between 10 ° C and 50 ° C, preferably at Room temperature.

The plant treatment agents according to the invention can either as such or after previous dilution with water or other diluents are applied, for example as emulsions, suspensions, solutions or Aerosols. The application takes place according to usual methods, for example by spraying, pouring, spraying, injecting, pickling or painting.

The application rate of the plant treatment agents according to the invention can can be varied within a wide range. It depends on the respective Active substances contained and according to their concentration in the formulations.

For the production of the plant treatment agents according to the invention Usual equipment into consideration for the preparation of agrochemical formulations be used.

The formulations according to the invention can in particular be used as calcium fertilizers. containing formulations of agrochemical active ingredients are used, the due to the combination of active ingredient and fertilizer, a surprising part Have increased effectiveness.

Combinations of agrochemical active ingredients are generally known To formulate fertilizers. To produce these formulations, the presented fertilizer in a mixer without rubbing internals Suitable adhesive added and the surface thus obtained with the active ingredient in micronized form can be coated. This approach has the disadvantage that only low drug concentrations can be achieved. Moreover problems can occur that the water insoluble active ingredient insufficiently dispersed outer layer and the production of a homogeneous Spray liquor from the formulations is insufficient or does not work at all.

It is therefore more advantageous to use the active ingredient and possibly other additives first mix homogeneously into a powdery fertilizer component and then granulate.

According to the invention, it has now surprisingly been found that Calcium formate in a special way for such a preparation of formulations Suitable as a plant treatment agent and the above problems avoids. As a commercially available powder, it can be used easily Active ingredients or active ingredient premixes and other additives such as wetting agents, Mix dispersants and fillers.

The plant treatment agents containing calcium formate are particularly suitable Way to formulate agrochemical active ingredients as water-dispersible Granules (WG formulation).

• - zwischen 1 und 99 Gew.-% an Calciumformiat,
• - zwischen 1 und 70 Gew.-% an einem agrochemischen Wirkstoff, und gegebenenfalls bis zu 98 Gew.-% an Zusatzstoffen.

The WG formulations according to the invention preferably contain

• between 1 and 99% by weight of calcium formate,
• - Between 1 and 70 wt .-% of an agrochemical active ingredient, and optionally up to 98 wt .-% of additives.

• - zwischen 10 und 90 Gew.-% an Calciumformiat,
• - zwischen 1 und 50 Gew.-% an einem agrochemischen Wirkstoff, und zwischen 0,1 und 89 Gew.-% an Zusatzstoffen.

The WG formulations according to the invention particularly preferably contain

• between 10 and 90% by weight of calcium formate,
• - Between 1 and 50 wt .-% of an agrochemical active ingredient, and between 0.1 and 89 wt .-% of additives.

The WG formulations according to the invention most preferably contain between 10 and 30% or 80 and 90% by weight of calcium formate.

The moistening process necessary for the granulation is technically without greater effort possible, d. H. it becomes a homogeneous distribution of the water in achieved the premixes containing the active ingredient based on calcium formate.

A moist premix is used to prepare the WG formulation Components of the agents according to the invention (preferably containing 12 to 25% water) extruded. The feed into the extruder (e.g. radial, hood or basket extruder) is advantageously carried out using a differential dosing scale in continuously and evenly. Usually matrices with a Hole diameters from 0.5 to 2 mm are used. Those emerging from the die Product strands are shortened using a spheronizer and if necessary rounded and then dried with a vortex dryer.

When examining the WG formulations produced in this way, it was found that the good granules according to the invention when stored properly Storage stability and very good application properties, so that no problems with spraying the plant treatment products occur.

The calcium fertilizer-containing plant treatment agents according to the invention can but also as a water-dispersible powder (WP formulation) or in formulate in liquid form. The advantageous properties of Calcium formate especially mentioned: quick and high water solubility, more neutral pH of the solutions.

The plant treatment compositions according to the invention containing calcium formate are also particularly suitable for application to leaves and fruits in numerous horticultural and agricultural crops. A lack of calcium in the supply of fruits and leaves leads to the development of physiological diseases in these cultures and to a reduction in resistance to pathogens. This is described in the literature:
Bangerth, F., Dilley, DR, Dewey, DH (1972), Effect of post harvest calcium treatments on internal reakdown and respiration of apple fruits, J. Amer. Soc. Hort. Sci. 97, 679-682.
Bramlage, WJ, Drake, M. Baker, JH (1974), Relationships of calcium content to respiration and postharvest condition of apples, J. Amer. Soc. Hort. Sci. 99, 376-378.
Bramlage, WJ, Drake, M., Weis, SA (1985), Comparison of calcium chloride, calcium phosphate, and a calcium chelate as foliar sprays for "Mclntosh" apple tress, J. Amer. Soc. Hort. Sci. 110, 786-789.
Conway, WS (1982), Effect of postharvest calcium treatment on decay of Delicious apples, Plant Dis. 66, 402-403.
Hepler, PK, Wayne, RO (1985) Calcium and plant development, Ann. Rev Plant Physiol. 36, 397-439.
Klein, JD, Lurie, S. (1994), Time, temperature and calcium interact in scald reduction and firmness retention in reated apples, HortScience 29, 194-195.
OVR, guide through the fruit year 1996, announcements of the fruit growing trial ring of the old country, 1996.
Scott, KJ, Wills, RBH (1979), Effect of vacuum and pressure infiltration of calcium chloride and storage temperature on the incidence of bitter pit and low temperature breakdown of apples, Austral. J. Agr. Res. 30, 917-928.
Shear, CB (1975), Calcium related disorders of fruits and vegetables, HortScience 10, 361-365.
Sonneveld, C., Mook, E. (1983), Lettuce tipburn as related to the cation contents of different plant parts, Plant and soil 75, 29-40.
Stoll, K. (1997), The Apple, Ingredients, Fruit Structure, Quality Recognition, Enrico Negri Verlag, Zurich.

Through the use of calcium fertilizers and the easy to produce calcium containing formulations according to the invention, the emergence of these Diseases effectively avoided. Known illnesses are, for example, stubbornness of the apple (Malus domestica), the inner fire of lettuce (Lactuca sativa), the Flower rot in tomatoes (Lycopersicon esculentum) and peppers (Capsicum annun), Calcium deficiency in strawberries (Fragaria spec.), Black rot in celery (Apium graveolens), chlorosis of young plants in potatoes (Solanum tuberosum) and Corn (Zea mays) and leaf margin necrosis of the bracts of poinsettia (Euphorbia pulcherrima).

Due to its excellent properties, the invention Plant treatment agents are also particularly good for treating perennial pot cultures, particularly suitable for container plants (such as coffee).

In addition, the calcium formate is well tolerated by plants. In addition, calcium and formic acid are widespread natural products in nature, so that excellent environmental compatibility can be expected.

The invention therefore relates in particular to the use of the invention Plant treatment agent with or without additive / additive as Calcium fertilizer for application to the plant organs. The Treatment advantageously by spraying the invention Links. The spraying usually takes place between flowering until the time of Harvest.

In this case, the spraying takes place directly onto the plant organs, in particular the Leaves or fruits. Are common in apple crops such. B. 5 to 7 injections in one Vegetation period from the time of full bloom to about three weeks before the harvest.

It was also found that the calcium formate in additive (wetting agent, Injection broths containing pentetration conveyor) is capable of damaging the Effectively reduce crops through the additives. So it was found that a concentration of 0.3 g / l calcium formate in the spray mixture is sufficient to Additive-related necrosis increased significantly at additive concentrations of 0.3-1 g / l reduce (the ratio of additive / calcium formate based on 0.3 g / l calcium formate in this case is 1: 1 to 1: 3.3).

The plant treatment agents according to the invention, which as calcium fertilizer on the Plant organs are applied advantageously, but not necessarily made for the application on an aqueous basis. she preferably contain 0.1 to 50 g / l (0.01-5% by weight) of calcium formate, a Calcium content of 0.1-2 wt .-% is preferred. The addition of usual wetting agents or uptake promoters as additives in the formulations according to the invention deserve special mention.

As cultures for the use of the plant treatment compositions according to the invention all usual agricultural and horticultural crops are calcium fertilizers Cultures called, especially pome fruit crops, such as. B. apple crops and all cultures mentioned above, in which calcium deficiency diseases can occur.

All plant treatment agents containing calcium formate fertilizers described above are particularly suitable for certain fields of application, if additional an agrochemical active ingredient, e.g. B. a fungicide, herbicide or insecticide is added.

The fungicide tolylfluanid should be emphasized (but also others in fruit growing typically used fungicides), the herbicide metamitron and the insecticides Imidacloprid or cyfluthrin.

The plant treatment agents according to the invention, in particular those above mentioned plant protection products containing calcium fertilizer for application to leaves and fruits, can be used advantageously in an additional way. Harvested plant organs (e.g. fruits, such as apples) can be subjected to a dip treatment (e.g. by vacuum or pressure infiltration) with the agents according to the invention undergo what their durability (pulp firmness, shelf life) in increased significantly. Even in this case, the means that are little Contain hygroscopic, but readily water-soluble calcium formate, surprisingly well suitable to avoid symptoms of calcium deficiency. The formate component leads in addition to the growth of microorganisms (bacteria and fungi) inhibitory effect (antiseptic effect) because formic acid is a good one Preservative is. Therefore it is also effective against pathogens and thus coherent possible positive influence on rusting. The means of Fruit treatments preferably contain 0.1 to 4% by weight of calcium formate.

The invention is illustrated by the following examples.

Preparation Examples Formulation 1 (active ingredient formulation for a herbicide, WG 10) 1. Preparation of the premix

627 g of the active ingredient metamitron (99%) and 5573 g of calcium formate are mixed in a ploughshare mixer with chopper for 10 minutes. The premix is then micronized in an air jet mill with 5.6 bar injector air and 5.6 bar grinding air. The premix prepared in this way has an average particle size d ₅₀ of approximately 6 μm.

2. Moisten the premix

The above premix is placed in a high-speed mixer. It will 992 g of water are now added continuously with mixing over 2 minutes.

3. Extrusion and drying

The moistened premix is slowly and controlled in a laboratory Hood extruder (Fuji-Paudal DG-L1) filled and with low power consumption extruded through a sieve with 0.8 mm holes. The granules are then transferred to a fluid bed dryer and up to a maximum exhaust air temperature dried from 55 ° C to a final moisture of <2%. After cooling, it will Bottled product.

4. Properties of the formulation

The granules produced have a uniform size. They are dust free abrasion-resistant and have good storage stability. Dissolve in water after stirring briefly. The resulting spray liquor is clear and results no precipitation even after long standing.

Formulation 2 (active ingredient formulation for a fungicide, WG 50)

130 g of tolylfluanid are mixed with 10 g of highly disperse silica, 25 g of dispersant, 12.5 g of glue, 35.5 g of calcium formate and 34.9 g of fine quartz powder on the usual Mixed way and crushed by gas jet grinding.

The mixture is mixed with 30 g of water and applied to the with a laboratory extruder converted into granules in the usual way.

Formulation 3 (active ingredient formulation for an insecticide, WG 50) 1. Preparation of the premix

20.4 g imidachloprid active ingredient (98%), 20 g Stepsperse DF-300 and 359.6 g calcium formate are mixed in a high-speed mixer for 5 minutes. The premix is then micronized in an air jet mill with 5.6 bar injector air and 5.6 bar grinding air. The premix produced in this way has an average particle size d ₅₀ of approximately 5 μm.

2. Moisten the premix

The above premix is placed in a high-speed mixer. It will 72 g of water are now added continuously with mixing over 2 minutes.

3. Extrusion and drying

The moistened premix is slowly and controlled in a laboratory Hood extruder (Fuji-Paudal DG-L1) filled and with low power consumption extruded through a sieve with 0.8 mm holes. The granules are then transferred to a fluid bed dryer and up to a maximum exhaust air temperature dried from 40 ° C to a final moisture of <2%. After cooling, it will Bottled product.

4. Features of the Confidor WG 50

The granules produced have a uniform size. They are dust free abrasion-resistant and have good storage stability. They loosen when put in water after stirring briefly. The slightly cloudy spray mixture also gives way long standing no precipitation.

compatibility tests

A 10 µl drop of a solution of 5 g calcium formate / l was placed on a sheet of Test plants applied and later with an aerosol sprayer Calcium formate solution (20 g / l or 2% by weight) completely wetted.

No symptoms of damage were found in the following plants according to the optical rating:
Apricot, fig, apple (Golden Delicious), hornbeam, laurel and mate tea.

Claims (11)

1. Use of calcium formate as a component of Plant treatment products. 2. Process for the treatment of plants, characterized in that one Calcium formate-containing agent on the plants or their environment can act. 3. Plant treatment agent containing between 0.005 and 99.9% by weight Calcium formate as well as optionally one or more agrochemical active ingredients, and between 0.1 and 99.995% by weight Additives or water. 4. Plant treatment composition according to claim 3, containing between 0.01 and 90% by weight of calcium formate and, if appropriate, additionally one or several agrochemical active ingredients, and between 0.1 and 99.99% by weight Additives or water. 5. Water-dispersible granules containing between 1 and 99% by weight Calcium formate, between 1 and 50% by weight of an agrochemical Active ingredient, and optionally up to 98 wt .-% of additives. 6. Water-dispersible granules according to claim 4, containing between 10 and 70% by weight of calcium formate, between 1 and 50% by weight of one agrochemical active ingredient, and between 0.1 and 89% by weight Additives. 7. Process for treating plants by applying the agents according to Claim 3 to the plant organs. 8. Plant treatment agent according to claim 3, characterized in that they contain 0.01-5% by weight of calcium formate. 9. Plant treatment composition according to one of claims 3 to 8 containing an agrochemical active ingredient, characterized in that this Active ingredient is tolylfluanid, metamitron or imidacloprid. 10. Process for the treatment of harvested plant organs, thereby characterized in that an agent according to claim 3 is applied to the fruit. 11. Use of an agent according to claim 3 for the treatment of harvested Plant organs.