SOIL AND PLANT CONDITIONER PRODUCTS

SUBJECT OF THE INVENTION

The subject of the present invention is a soil or plant conditioner product encompassing a solid, porous, vehicle comprising natural zeolite-containing tuff and a salt of the phosphonic acid of the Formula (I) or a mixture of several different salts of phosphonic acid.

TECHNICAL BACKGROUND OF THE INVENTION

A new situation has developed in field agriculture due to the fact that some pesticides have been withdrawn/are being withdrawn from commercial sale because of their increased health deteriorating effects. Thus the possibilities of plant protection using pesticides and efficiency thereof have decreased. Therefore a need arises for the development of new plant protection technologies using agrotechnical methods and non-organic chemicals.

In the development of new plant nutrition and protection methods, primarily phosphorous- containing compounds as well as fertilizers and protection products produced by using said compounds can play important role since one of the most important essential nutritional element is phosphorous having both structural and functional importance, starting from energy storage to the formation of genetic material.

In the agriculture, the oxo-acids of phosphorous and salts thereof are used for phosphorous nutrition. Said oxo-acids and their salts are ^' used alone or optional ly combined with phosphorous acid derivatives in the form of free acid, amonium phosphate, diammonium phosphate, potassium phosphate or magnesium phosphate.

In the agriculture, among the oxo-acids of phosphorous, ortophosphoric acid (H ₃ PO ₄ ) and water-soluble salts thereof, potassium dihydrogenphosphate and ammonium dihydrogenphosphate are used most widely. A second large group of the oxo-acids and oxo- anions of phosphorous are comprised of phosphorous acid (HPO3) and phosphites (HPO3 ^2" ). In an aqueous solution, phosphorous acid is a bivalent acid forming phosphites and acidic salts, hydrogenphosphites. In an aqueous environment, phosphorous acid is mostly present in a tautomeric form as phosphonic acid of the Formula (I).

Fertilizers containing phosphate and polyphosphate as active ingredient are widely used for fertilizing plants. However, such fertilizers inhibit the activity of useful symbiontic organisms, such as mycorrhyzae, while enhancing the activity of algae and fungi, including soil-borne plant-pathogenic fungi. A further issue related to phosphate and polyphosphate containing fertilizers resides in that they bind to the cultivated layer of soil and large amounts of phosphorous are moved into still natural water bodies and watercourses by deflation or erosion, thus increasing the rate of eutrophization.

The oxo-acids of phosphorous, e.g. ortophosphoric acid [trihydrogen-(tetraoxophosphate)] and phosphorous acid [trihydrogen-(trioxophosphate)] differ by one oxygen atom only. Such a difference, however, results in significant deviation between the biological effects of phosphorous fertilizers containing phosphorous acid and phosphoric acid. Calcium phosphite has been characterized in the Merck Index as a derivative of phosphorous acid, while said acid has not been used as a nutrient (M. Widholsed. 1 983 , 10 ^th Edition, page 1678). It is contemplated that calcium phosphite might have formed as an impurity during the manufacture of calcium superphosphate [Mclntyre et aLAgron. J. 42., 453-540 ( 1950)] the effect thereof has been observed in maize [Lucas et aLAgron. J., 71 .. 1 063- 1 065 ( 1 979)]. In US Patent No. 4075324, phosphite as a fungicide has been disclosed, which has been marketed later under the trade name Alliete®. US Patent Nos. 6.929.673 and 5.997.910 disclose compositions of phosphonate- and phosphate-containing fertilizers suitable for stimulating plant growth, similarly to the preparations disclosed in International Patent Application WO 00/46469. US Patent Nos. 4.075.324 and 4. 1 19.724 disclose phosphonates. as fungicides and plant nutrients. Dueret ( in US Patent No. 4. 1 39.616) describes the salts and esters of phosphorous acids as fungicides, while Horsiere et.al. (in US Patent Nos. 4.698.334; US 4.806.445; US 5. 169.646) describe alkyl phosphonates as components of fungicidal compositions. In the disclosures phosphonates are usually mentioned as fungicidal compounds having effect on the immune system of the plants. Phosphonates are especially effective against Phycomycetes (Phytophtora, Peronospora).

Phosphates are in the first place plant nutrients but exhibit fungicidal effect as well. In US Patent No. 5.997.910, the effect of different potassium phosphate and potassium phosphonate mixtures have been disclosed, underlining the effect against Ascomyceles which is not characteristic to the use of phosphonates alone. Phosphoric acid and phosphonic acid salts have been disclosed wherein the salt-forming cation is potassium, an alkali earth metal, aluminium or ammonium. Phosphonates are prepared by neutralizing phosphorous acid with a base, for example, by the reaction of phosphorous acid and potassium hydroxide in an aqueous medium. During this reaction, independetly from the molar ratio of potassium hydroxide and phosphorous acid, dipotassium phosphonate, monopotassium phosphonate and unreacted phosphorous acid is formed. When the reaction conditions are set precisely, at pH 6.7-7.3, e.g. in a 42 w/w% potassium phosphonate solution, the ration of mono- and dipotassium phosphonates is 50-50%.

Hungarian Patent Application No. 0800533 describes rhyolite tuff as being optimally a mixture of zeolite and dolomite which is used as a soil improving material in the recultivation of open works in an amount of 24- 100 kg/m ² .

In Croatian Patent Application No. WO 2010/001 184, a zeolite containing fertilizer has been described wherein the zeolite component is pretreated with an acid, thus providing an acidic pH to the zeolite. Acids used for the treatment of the zeolite are hydrochloric acid, boric acid, nitric acid, acetic acid, benzoic acid, sulfonic acid, methanesulfonic acid and mixtures thereof. Subsequently different metal salts are added to the thus pretreated zeolite exhibiting an acidic pH and the thus obtained microelement-cotaining zeolite is used as a component of the preparation according to the invention. The above-mentioned patent application uses such zeolites of natural and artificial origin, which can be used as plant nutrient only after charging with microelements. In Hungarian Patent Application No. 0800095, a zeolite having acidic character pretreated with acetic acid and ethylenglycol, diethylenglycol, ethers thereof or with mixtures of the same as a vehicle of soil disinfectant. Zeolites are widely used in the industry and in pharmaceutical science as adsorbent, filtration aid, ion exchange material, catalyst and as cosmetic and pharmaceutical active ingredient [R. T. Yang: Adsorbents, Fundamentals and Applications, John Wiley&Sons. Inc. (2003); K. Pavelic. Medical News 26 ( 1998) 21 -22].

During the use of the preparations described above as soi l fertilizer, the following issues may emerge:

- in order to achieve sufficient biological activity, the active ingredient should be placed in intimate proximity to the sown seed or seedl ing. In this situation, a problem may arise due to the concentration of the nutrient, which can hinder the seed germination or burn to root system of the seedling.

- Under weather conditions rich in precipitate, the active ingredients can be washed out rapidly and can pollute watercourses. - Under dry weather conditions, during the use of active ingredients having high vapour tension, large losses of the active ingredient may be expected.

- It should be provided that the vehicle and the agricultural chemicals and plant nutrients contained therein could contact the soil particles and the root system of plants at the largest area.

- The wash-out of the nutrient has disadvantageous effect to the association between soil microorganisms and plants. The proliferating microorganisms may become transient concurrents of the culture plant.

During foliage treatment, the following problems should be expected:

- during dry weather conditions, a thick waxy layer is formed on the surface of the foliage, stomata on the surface of the foliage are closed, therefore the agrochemicals delivered to the foliage are not or not satisfactorily enter the leaf cells.

The precipitation may wash off the materials sprayed onto the fol iage and strong ultraviolet radiaton can decompose the active ingredients of agrochemicals containing organic compounds.

In order to overcome the problems mentioned above, our objective was to develop controlled effect soil and plant conditioning preparations, which influence the plant nutrition, plant physiology, resistance of plants against diseases, the inhabiting conditions of agriculturally advantageous microorganisms, soil structure, air and water balance of soil favourably and which provide for plant nutrition with balanced minerals in a scientifically justified and economically viable manner. Furthermore, we aimed at providing a composition which is suitable for enhancement of the efficiency of fungicidal preparations containing elemental sulphur and inorganic copper salts, thereby allowing the decrease of the dosage of such fungicides per hectare.

According to those described above, our objective was to provide agrochemicals useful in agriculture by using functional and structure-forming elements having most advantageous effects on plant development which contain all the minerals which are required by the plants during their ontogeny. SUMMARY OF THE INVENTION

The above-mentioned objective has been solved by a soil and plant conditioning preparation according to the present invention containing a salt of the phosphonic acid

OH

H-P=O

OH

(I) or the mixture of several different phosphonic acid salts in admixture with a solid porous vehicle of natural zeolite-containing volcanic tuff.

DETAILED DESCRIPTION OF THE INVENTION

According to the first aspect of the present invention, there is provided a soil or plant conditioning preparation, which contains a salt of the phosphonic acid of the Formula (I) or a mixture of several different phosphonic acid salts transferred onto the surface of a natural zeolite-containing solid porous vehicle. In the present specification, the expression „phosphonic acid salt" means dibasic and acidic salt of phosphonic acid as well.

According to a further aspect of the present invention, there is provided a method for producing soil of plant conditioning preparation comprising a natural zeolite-containing solid porous vehicle, which comprises transferring a salt of the phosphonic acid of the Formula (I) or several different phosphonic acid salts onto the solid porous surface or preparing thereof on the solid porous surface of natural zeolite-containing volcanic tuff.

According to a preferable embodiment of the present invention, there is provided a plant conditioning product, which comprises a natural zeolite-containing solid vehicle surface- treated with phosphonic acid and/or one or more different phosphonic acid salt.

We have found that in the case when phosphonates are transferred to the surface of a neutral, slightly acidic or slightly alkaline microporous natural zeolite-containing volcanic tuff having liquid absorption capacity of 5 to 40 g liquid/1 00 g substrate, such a substrate surprisingly not only provides for the increase of yield of the crop compared to untreated crops or crops treated according to known treatment methods in agriculture, but due to the biological activity of the product, simultaneously the resistance to diseases is improved significantly.

According to a preferable embodiment of the present invention, the weight ratio of the solid porous vehicle to the salt of phosphonic acid of the Formula (I) is 0. 1 : 1 to 200: 1 , more preferably 0.4: 1 to 1 00: 1 .

The weight ratio of the phosphorous acid to the applied or formed phosphonate salt on the vehicle is between 100: 1 and 1 : 100, more preferably between 10: 1 and 1 : 10.

The product according to the present invention comprising a solid porous natural zeolite- containing vehicle and a salt of the phosphonic acid of the general Formula (I) or mixture of several different phosphonic acid salts can be formulated as a powder, preferably as a sprayable powder, in form of granules, preferably as a soi l fertilizer, in the form of a dispersion, suspension or suspo-emulsion as a fertilizer applicable to foliage, a foliar fertilizer concentrate or as a contact fungicide.

In order to achieve a specific biological aim more efficiently, the preparation can contain further components as well as auxiliary components for formulation.

The preparations according to the present invention can contain natural silicates, diatomaceous earth, milled natural zeolite, volcanic rock or mixtures thereof as solid porous vehicle. Optionally the solid vehicle can be composed of the above-mentioned solid materials and additional porous solids, such as organic polymers, preferably urea- formaldehyde condensate, milled materials of plant origin, such as milled corncub or inorganic materials, such as defatted bone meal, calcined bone meal, carbon powder, natural or synthetic silicates, silica gel, silicon dioxide, calcium silicate, talc, caolin or synthetic zeolite mill or mixtures thereof.

According to a preferable embodiment of the present invention, the solid porous vehicle comprises natural zeolite-containing tuff alone or in admixture of other material, wherein said natural zeolite containing tuff is preferably a zeolite-containing rhyolite tuff of the formula (Me _n [(A10 ₂ ) _x (Si0 ₂ ) _y ]*mH ₂ 0, wherein Me represents Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Zn ²⁺ , Cu ²⁺ , Mn ²⁺ , vagy Fe ²⁺ ion, the ration of silicone and aluminium y to x ranges between 1 : 1 and 10: 1 , m represents the number of crystal water molecules where m ranges between 0 and 20, and said solid porous vehicle can contain optional ly synthetic zeol ites, preferably faujasite, cabasite, gmelinite, zeolite ZSM-35, zeolite P. mordenite or offretite. Formulae of the preferable silicates are summarized in the table below:

The especially preferable porous vehicle contains zeolite-containing rhyolite tuff of the formula Me ⁿ⁺ ) _x/n [(A10 ₂ ) _x (Si0 ₂ ) _y ] *mH ₂ 0, wherein Me represents Na ⁺ . ⁺ , Mg ² \ Ca ²⁺ , Zn ²⁺ , Cu ²⁺ , Mn" ⁺ . or Fe ² ion, the ratio of silicone and aluminium y to x ranges between 1 : 1 to 10: 1 , m represents the number of crystal water molecules, which ranges between 0 and 20.

It is characteristic to natural rocks of volcanic origin, such a zeolite-containing rhyolite tuffs, that the mineral impurities thereof are catalytically indi fferent and due to high silicone content, the H-forms of Bronstedt-acids are highly stable and Lewis acid forms can also be prepared. Structural forms thereof are resistant to acidic solvents up to pH 3-4, which allows the introduction of transitional metal cations by ion exchange. Due to the composition of such materials during the soil weathering, the trace elements to be mobilized from the devitrificated volcanic glass are present along with the ion exchanger mineral zeolite crystals. Such materials under suitable conditions furthermore are capable of reversible storage and slow continous release of active ingredients of agrochemicals towards plants or propagation medium due to their ion exchange property. It is also possible to transfer rapidly utilizing carbon and nitrogen sources onto the surface of vehicles having high adsorption capacity (see further). Product containing such rapidly utilizing carbon and nitrogen sources generally enhance the activity of microorganisms living in the root zone of the plants. Microorganisms similarly to higher plants require the presence of suitable microelements besides carbon and nitrogen as well.

In the preparation according to the present invention, under„phosphonic acid salts" are meant the salts and acidic salts of phosphorous acid with ammonium, metals or organic compounds. Under the expression „metals salts", salts formed with alkali metals, alkali earth metals, aluminium, transitional metals and heavy metals are meant, including the corresponding acidic salts and optionally the complexes of the salts.

Alkali metals are the elements in the first column of the periodic table, while alkali earth metals are elements belonging to the second column of the same. Transitional metals are elements of group d including lantanides and actinides. According to the present invention, heavy metals are those metals which are referred to this group by the state of the art on the basis of density, number, relative atomic weight or toxicity. The group of heavy metals overlap with the group of transitional metals, lantanides and actinides. On the basis of toxicity, mercury, lead, plutonium, cadmium, arsenic and aluminium are referred to as heavy metals. Iron, cobalt, molibdenum, manganese, zinc, vanadium, tungsten and cadmium belong to the group of biologically important heavy metals. Copper tetramine phosphonate is an example of complex metal salts. It is known that some metal ions are amenable to complex formation with compounds having free electron pair, such as ammonia, amines, ether-type compounds such as crown ethers.

The preparation according to the present invention preferably contain phosphonic acid salts as ammonium salts, alkali metal salts, preferably sodium or potassium phosphonate, alkali earth metal phosphonates, preferably calcium phosphonate or magnesium phosphonate. phosphonates of transitional metals, preferably zinc, copper, iron, manganese, molibdenum, nickel or cobalt phosphonate or heavy metal phosphonate, preferably zinc, cadmium or aluminium phosphonate and/or a phosphonate salt formed with organic compounds, preferably with primary, secondary or tertiary amines, more preferably a phosphonate salt formed with monoethanolamine or piperidine or a mixture consisting of several different phosphonate salts.

The selection of the cation component of the phosphonate salt depends on the requirements of the soil or the crop or the cation can be selected according to the use of the plant conditioning preparation. The determination of this belongs to the general knowledge of a person skilled in the art. The spraying of the preparation according to the present invention containing dipotassium phosphonate transferred onto a solid vehcile to winter wheat resulted in significant increase of the yield and microelement enrichment of the produce. In case of sunflower, the preparation containing magnesium phosphonate not only increased the yield significantly but decreased the occurance of stem disease. The zinc phosphonate containing fertilizer according to the present invention resulted in the significant increase of the quality and shelf life of apples.

During our investigations, we have found that the biological efficiency of phosphonates having mixed active ingredient is often enhanced compared to that of the mono-component containing formulation. In the agriculture, potassium phosphonate is a widely applied fungicide salt applied in all kind of cultured plants. Mixtures of ammonium phosphonate and potassium phosphonate or mixture of ammonium phosphonate and sodium phosphonate are used for soil treatment in root vegetables (carrot, celery, parsley etc.) against their pests, principally against nematodes. Copper tetramine phosphonate optionally in combination with potassium phosphonate is used for the treatment in grapes, apricots, cabbage varieties, corn in the ear, onions, potatoes, berries, sugar beets. Zinc tetramine phosphonate optionally supplemented with potassium phosphonate has been used for the treatment of onions, pears, maize, rapes and root vegetables. Corns in the ear, sunflower, grapes, potato, sugar beet, melons, tomatoes have been treated with magnesium phosphonate optional ly supplemented with potassium phosphonate. Calcium phosphonate has been applied to apple, pepper, cabbage varieties and peach optionally supplemented with potassium phosphonate.

The composition according to the present invention can optionally contain further biologically useful ingredients, plant nutrients or hormones, vitamines or plant extract as well as additives controlling the active ingredient release or mixtures thereof.

Plant nutrients include for example rapidly utilized carbon and nitrogen sources, preferably malonic acid, fumaric acid, succinic acid, ascorbic acid, phosphoric acid or salts thereof, for example, ammonium phosphate, ammonium sulfate, ammonium nitrate, potassium phosphate, potassium nitrate, calcium nitrate or mixtures thereof. These materials are suitable for production of preparations containing the reproduction parts of microorganisms. These control the microbial activity of soil, such as nitrogen fixation, cellulose decomposition or phosphorous and potassium exploration. Optionally these may prevent damages caused by pathogens. As a carbon and nitrogen source, commercially available preparations may also be used, such as Amalgerol Premium® mainly consisting of oils of animal and plant origin, extracts of medicinal herbs, essences and minimal amounts of algal extracts as well as Gullemax® (Hechenbichler GmbH, Ausztria) mainly consisting of oils of animal and plant origin, extracts of medicinal herbs, trace elements and essences as well as Radifarm® (Valagro SpA., Olaszorszag) containing complex carbohydrates, saponins, protein, special amino acids, vitamins and chelate complexes of microelements. The preparation according to the present invention may furthermore contain as plant nutrients plant and animal proteins, peptides, for example, myosine, keratine, myoglobin, hemoglobin, glutathion; amino acids, for example glycine, triptophane, methionine, tyrosine, phenylalanine, alanine, serine, proline, valine, leucine or salts thereof, preferably potassium, calcium or magnesium salts or mixtures thereof. Myoglobin and hemoglobin are rich in polar amino acids forming complex with metal ions released from rhyolite tuff, thus protecting said ions from binding in the soil and controls concentration and avaibility for uptake in the soil solution.

The formulation according to the present invention can furthermore contain as plant nutrient nitrogen-containing fertilizers, preferably potassium, calcium, ammonium or sodium nitrate, ammonium sulfate, ammonium chloride, calcium cyanamide, urea, urea-formaldehyde condensate and/or phosphorous-containing fertilizers, preferably ammonium and potassium phosphates, triple superphosphate, urea-phosphate, potassium phosphate, thermophosphate, oxamide, raw phosphate, bone meal; potassium-cotaining fertilizers such as potassium chloride, potassium nitrate, potassium sulfate, potassium phosphate, patent-kali, or mixtures thereof; vitamines, preferably riboflavine, thiamine, nicotinic acid, nicotinamide, panthotenic acid, pyridoxine, ascorbic acid, biotine, tocopherol, vitamine | or 2 menadione or sodium, potassium, calcium, magnesium salts thereof or derivatives of the same; microelements, preferably iron, manganese, copper, zinc, boron, molybdenum, chlorine, nickel, sodium, silicone, aluminium or cobalt-containing salts and preparations used in the agriculture containing the same.

The preparation according to the present invention can optionally contain plant hormones, preferably 2-(indol-3-yl)acetic acid, 2-(naphtalene- l -yl)acetic acid. 4-(indol-3-yl)butyric acid, abscisic acid, gibbereilic acid or ammonium, potassium, calcium or magnesium salts thereof, zeatine or mixtures thereof, plant extract, preferably algae or algal extracts, phytoalexine elicitors such as laminarine or mixtures thereof.

The formulation according to the present invention containts as microelements preferably iron, manganese, copper, zinc, boron, molybdenum, chlorine, nickel, sodium, silicone, aluminium or cobalt. These are preferably included as agriculturally suitable salts or formulation containing such salts.

The preparation according to the present invention can contain furthermore materials used in the agriculture, auxiliary materials, for example, binders, disintegrants, antiadhesion agents. chemical stabilizers, dispersing agents, tensides, a penetration enhancer, a complexing agent, stabilizers, solvents, suspension stabilizers and mixtures thereof.

As binder and disintegrant, for example, Hgnosulfonates, humates, humic acid extracts, starch, cellulose, natural plant extracts and mixtures thereof can be used. For the purposes of antiadhesion and chemical stabilizing agent, preferably sodium sulfate, zinc sulfate, aluminium sulfate, iron sulfate, magnesium hydroxide, sodium metacrylate or mixtures thereof can be used. As a dispersing agent, sodium or ammonium salts of a sulfonated naphtalene (or methylnaphtalene) and formaldehyde condensate, lignosulfonate, polyethoxylated lignosulfonate sodium, calcium or ammonium salts, sodium taurides or sodium or ammonium salts of copolymers based on maleic acid or mixtures thereof can be used. The preferable tenzides used in the formulation according to the present invention are ethoxylated natural or synthetic alcohols, the compounds of the general Formula

or mixtures thereof. Preferable penetration enhancing agents are ammonium sulfate, ammonium phosphate, ammonium trimethylene phosphoric acid, diammonium hydrogenphosphate, ammonium carbonate, ammonium acetate, triammonium phosphate, ammonium hydrogencarbonate, urea, ammonium hydrogensulfate or mixtures thereof. The concentration of binders and disintegrating agents relative to the weight of the formulation is between 0 and 10 w/w%, preferably 1 to 10 w/w%, more preferably 2 to 5 weight%.

As complexing agent, the formulation can contain for example ammonium sulfate, sodium sulfate, trisodium sulfate, nitrilotriacetic acid trisodium salt, ethylenediamine tetraacetic acid salts, citric acid, malic acid, ammonium phosphates, hydroxy-ethanediphosphoric acid salts, nitrilo-tris-methylene-phosphoric acid salts in the concentration relative to the weight of the formulation preferably between 0.5 to 5.0 w/w%, more preferably 0.75 to 4.5 w/w%. The effect of these materials for increasing the efficiency is related to the fact that most of acids having pesticide activity form sodium and magnesium salt with calcium and magnesium ions causing water hardness and the salts thus formed salts have very poor solubility in water. These insoluble pesticide salts are practically unavailable for absorption, thus the precipitated amount decreases the efficiency. The changing calcium and magnesium content of surface and ground water used for spraying solutions can be effectively neutralized by complex forming additives present in the formulation.

The formulation according to the present invention can contain stabilizing agents, preferably natural or ethoxylated vegetable oils, ethoxylated fatty acid esters or mixture preferably in concentration of 1 to 10 w/w%, more preferably 1 -2 w/w% relative to the weight of the formulation.

Suitable solvents for the formulation are water, ethanol, 1 ,2-propylene glycol, mineral and vegetable oils or mixtures thereof, suspension stabi l izers e.g. polyvinyl alcohols, polyethylene glycols, potassium palmitate, ammonium laurate or mixtures thereof can also be present in the concentration of 0 to 60 w/w ^' %, preferably 1 5 to 60 w/w%, the more preferably in 1 0 to 30 w/w%.

Suitable release controlling materials are inorganic or organic acids or salts thereof, preferably sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid or salts thereof or organic acids and salts thereof, such as acetic acid, oxalic acid, fumaric acid, malonic acid, succinic acid, ascorbic acid or salts thereof, the most advantageously phosphoric acid phosphoric acid salts. As salts, ammonium, alkali metal, alkali earth metal, transition metal or heavy metal salts can be used.

We have found surprisingly that the active ingredient release of the formulation according to the present invention can be controlled by the weight ratio of the phosphonic acid used to other acids or salts. If the weight ratio of the phosphorous acid to other acids and salts expressed in equivalents is between 100: 1 and 5 : 1 , preferably between 10: 1 and 5 : 1 , than rapid dissolution is experienced. If the same ratio ranges between 1 :5 and 1 : 100, preferably between 1 :5 and 1 : 10, than slowly dissolving formulations can be obtained, which are suitable for use in loosely structured, sandy soils having low loam and organic colloid content, where concerns are about the rapid washing out of the nutrients. In order to obtain slow effect, it is preferable to use surface-treated zeolite containing riolit tuff as solid porous vehicle.

When the formulation according to the present invention is used as a soil fertilizer, it can contain optionally besides the treated solid porous vehicle, optionally a nitrogen, phosphorous or potassium containing fertilizer component, such as urea, urea-formaldehyde condensate, urea phosphate, potassium phosphate, oxamide, monoammonium phosphate, diammonium phosphate, superphosphate, triple phosphate, gasfaphosphate; as a potassium-containing nutrient, it can contain for example, potassium chloride, potassium nitrate, potassium sulfate, potassium phosphate. When the formulation is used as soil fertilizer, the nitrogen content of the formulation is preferably between 0.01 and 10 w/w%, its phosphorous content expressed as phosphorous pentoxide is between 0.01 and 20 w/w%, its potassium content expressed as potassium oxide is between 0.01 and 10 w/w%. When the formulation is used as foliage fertilizer, the nitrogen content thereof can be preferably between 0.01 and 20.0 w/w%, phosphorous content can be between 0.01 and 20.0 w/w%, potassium content can be between 0.01 and 20.0 w/w%.

In the case when a further fertilizer is admixed to the formulation according to the present invention containing treated porous vehicle, the ratio of the phosphonate-treated porous vehicle and the fertilizer can be chosen preferably between 1 :2 and 1 :20, more preferably between 1 :5 and 1 : 15.

When the formulation according to the present invention is used as a soil fertilizer, it is not necessary to treat the whole of the surface, it is sufficient to deliver the formulation to the root system of the sown seed or transplanted seedling. The particle size of the fertilizer can range between 0.5 and 4.5 mm according to the requirements of mechanized delivery technology.

The homogeneous particle fraction forming the basis of the preparation can be produced alternatively by milling the mined porous vehicle to a suitable particle size or by granulating a powder in known manner. A formulation wherein the vehicle produced according to the present invention is mixed with a fertilizer having identical particle size and bulk density can be used as soil fertilizer.

The preferable particle size of a preparation according to the present invention useful for foliage treatment is 0.5-5 μηι. The formulation for foliage treatment can be prepared in form of sprayable powder, suspension or suspo-emulsion concentrate. In the formulation suitable for foliage treatment, the weight proportion of the biologically active surface treated solid porous vehicle - preferably zeolite containing rhyolite tuff - can range between 10 and 80 w/w%, preferably between 30 and 60 w/w%. The preparations can contain further plant nutrients. As plant nutrients, preferably nitrogen, phosphorous and potassium containing fertilizers can be used, such as urea, urea-formaldehyde condensate, urea phosphate, potassium phosphate, oxamide. The nitrogen content of the formulations according to the present invention is between 0.0 and 20.0 w/w%, the phosphorous content can be between 0.0 and 20.0 w/w%, the potassium content between 0.0 and 20.0 w/w%. Such formulation can contain preferably humic acids or potassium, sodium or magnesium salts thereof or mixtures thereof, amino acids, such as glycine, triptophane, methionine, tyrosine, phenylalanie or potassium, calcium or magnesium salts thereof, plant hormones such as indolylacetic acid, gibberellic acid, abscisic acid or salts thereof, marine algae, algal extracts, phytoalexine elicitors such as laminarine, yeast extracts, plant oils, preferably natural aromatic oils in an amount of 0.001 to 10 w/w%, preferably 0.01 -8 w/w%.

Foliage treatment formulations according to the present invention can furthermore contain components which are enhancing the delivery or biological efficiency of the formulations according to the present invention. Thus the formulations can contain for example solvents, preferably water, ethanol, 1 ,2-propylene glycol, mineral or vegetable oils or mixtures thereof in a proportion of 15 to 60 w/w%, preferably in a proportion of 10 to 30 w/w% relative to the weight of the formulation; suspension stabilizing agents such as polyvinyl alcohols, polyethylene glycols, potassium palmitate, ammonium laruate or mixtures thereof in a proportion of 1 to 5 w/w%. preferably 1 -2 w/w% relative to the weight of the formulation. An especially effective composition can be prepared by using surface active agents containing a quaternary ammonium moiety. Substances of this type are characterized by the general Formula (II)

R ₂

I

/R _r N-(EO) _n (PO) _m -H/ ⁺ X-

I

(ID wherein R _\ , R2, R3 represents an alkyl group having 1 -3 carbon atoms and EO and PO denotes an ethyleneoxy or propyleneoxy group, respectively; the meaning of m and n is the number of alkyloxy groups. Optimally n+m is 20; X is an acyl residue group.

The properties of a foliage treatment formulation can be improved by using chemical antiadherents and chemical stabilizing agents, such as sodium, zinc, aluminium and iron sulfates, magnesium hydroxide, sodium methacrylate, which can be used preferably in a proportion of 0.1 to 5 w/w%, more preferably in 1 -2 w/w% relative to the weight of the formulation. Dispersing agents also improve the applicability of the formulation. Among such agents, preferably the sodium or ammonium salts of sulfonate naphtalene (or methylnaphtalene) and formaldehyde condensates, sodium, calcium or ammonium salts of lignosulfonates, optionally in polyethoxylated form, sodium taurides or sodium or ammonium salts of the copolymers based on maleic anhydride can be used preferably in a proportion of 1 to 10 w/w%, more preferably in a proportion of 2 to 5 w/w%, calculated on the basis of the weight of the formulation.

The foliage treatment formulation according to the present invention can furthermore optionally contain surfactants and adsorption improving agent in a proportion of 0. 1 - 1 5 w/w%, preferably 0. 1 - 1 0 w/w% calculated for the weight of the formulation, which has positive effect on the efficiency of the preparation. Such compounds are the e ^' thoxylated natural and synthetic alcohols. The formulations prepared according to the method of the present invention can optionally contain up to date, environmentally friendly silicone- containing surfactants, which are effective already in low dose. These compounds are stable only in neutral environment, which restricts their application area in relation to significant groups of active ingredients. Preferably, polydimethylsiloxanes modified with polyalkyloxides characterized by the general Formula (III) wherein n can range widely and Z represents hydrogen or methyl . Such si loxane derivative is Silwet® 77.

If required, the formulation according to the present invention can contain ingredientstwhich improve the shower/(rain) proof property of the formulation, such as polyvinylalcohol, polyvinylpyrrolidone, polyvinylacrylate, polyvinylacetate, hydroxyethyk ethoxycarbonyl- ethyl-methylcellulose, dextrin, hydrolysed peptide, heteropolysaccharide in a proportion of 0.1 to 2 w/w%. preferably in 0.1 to 0.5 w/w% relative to the _¾ weight of the formulation.

Penetration enhancing agents can also be used in the formulations according to the present invention in a proportion of 1 .0 to 10 w/w%, preferably 2.0 to 5.0 w/w% relative to the weight of the formulation. Suitable penetration enhancing agents are those which facilitate the absorption of the active ingredients into the transport system of the plant by increasing the rate of cellular activity. Such penetration enhancing agents are ammonium sul fate, ammonium phosphate, ammonium trimethylene phosphoric acid, diammonium hydrogenphosphate, ammonium carbonate, ammonium acetate, triammonium phosphate, ammonium hydrogen carbonate, urea, ammonium hydrogensulfate etc. The formulation according to the present invention can contain vegetable oils, preferably natural aromatic oils in a proportion of 0.001 to 1 0 w/w%, preferably 0.01 -8 w/w% relative to the weight of the formulation.

The formulation according to the present invention can be used as a contact fungicide, wherein the controlling component is a microporous, neutral, slightly acidic or slightly basic substrate having 5 to 40 g/ l OOg substrate liquid absorption capacity containing phosphorous acid and/or phosphonic acid salts as surface pretreating agent. Such formulations can optionally contain amorphous, rombos or monocline elemental sulfur and/or inorganic copper salt, preferably copper oxychloride, copper hydroxide, copper oxide, copper sulfate or mixtures thereof. When the formulation contains additional inorganic fungicides, the surface- treated porous vehicle is preferably rhyol ite tuff and the proportion of the fungicidal active ingredients is 1 : 10 to 10: 1 , preferably 1 :2 to 2.5 : 1 , more preferably 1 :2 to 1 : 10. Sulfur content of the contact fungicidal formulation is preferably 1 0 to 40 w/w%, inorganic copper content is 10 to 40 w/w%.

According to a further aspect of the present invention, there is provided a method for the preparation of the soil or plant conditioning formulation containing solid porous zeolite according to the present invention, which comprises transferring a salt of the phosphonic acid of the Formula (I) or a mixture of several different phosphonic acid salt onto the surface of the porous solid vehicle or preparing thereof on the surface of the solid porous vehicle.

Natural zeolite containing vehicles suitable for use in the formulation according to the invention have been mentioned above. The solid rhyol ite tuff containing natural zeolite can be used mixed with other vehicles as well, e.g. organic polymers, preferably with urea- formaldehyde condensate, plant millings or inorganic materials, such as defatted bone meal, calcined bone meal, carbon powder, natural or synthetic silicates, silica gel, silicone dioxide, calcium silicate, diatomaceous earth, talc, kaoline.

According to an embodiment of the present invention, the solid porous natural zeolite- containing vehicle is mixed with solution, dispersion or suspension of the salt or acidic salt of phosphorous acid formed with ammonium ion, metal ion or with an organic compound and the thus obtained mixture is homogenized and if desired, dried. In the process, as a phosphonate salt, alkali metal salts of phosphorous acid, preferably potassium or sodium phosphonate, an alkali earth metal phosphonate salt, preferably calcium phosphonate or magnesium phosphonate, phosphonate salt of a transitional metal, preferably zinc, copper. iron, manganese, molybdenum, nickel or cobalt phosphonate or a heavy metal phosphonate, preferably zinc, cadmium or aluminium phosphonate and/or a salt of phosphorous acid formed with organic compounds, preferably with primary, secondary, tertiary amines, more preferably with monoethanolamine or piperidine or mixtures thereof.

The phosphonate salts used can be prepared according to a known method from phosphorous acid in a reaction with inorganic bases and salts. According to our investigations, the biological efficiency of the formulation containing mixed phosphonates is often exceeds that of the formulation with monocomponent phosphonate salt. The active ingredients produced according to the state of the art are optionally isolated by distillation, centrifugation or crystallization according to their solubility in the reaction mixture.

In the case when the salt is insoluble, filtration followed by drying and solvent regeneration is necessary. In case of soluble product, it is isolated by evaporation in vacuo. Both method is excessively energy-consuming and during the operations, significant costs of environmental protection arise in relation to ai r pol lution and due to evaporation residues. Therefore this method can be preferably used when the phosphonate salt intended for use is commercially available.

Preparation of phosphonate salts on a porous, natural zeolite-containing solid vehicle according to the present invention is especially advantageous. By this process, the operative steps of the isolation of phosphonate salts, such as the otherwise optionally required distillation, centrifugation, crystallization or vacuum evaporation can be omitted and no environmental burden arises from the recycling or disposal of byproduct solvents.

The environmental burden of the method is significantly lower compared to the earlier methods used for the preparation of phosphonates. The invention is based on the surprising recognition that one of the reactant of the salt-forming reaction is distributed on the vehicle having large surface area and the reaction is carried out in this state with phosphorous acid or in combination with a derivative thereof. During the reaction, the equivalent weight ratio of the acid and the base is most preferably between 4: 1 to 1 : 1 . The most advantageous among the solid vehicles mentioned above are natural diatomaceous earth and natural zeolite millings. The weight ratio of the solid vehicle and the base is 0.75 : 1 to 75 : 1. The solid vehicle can contain other vehicle mentioned above besides natural zeolit-containing tuff.

The role of the vehicle is allowing the reactants to be contacted with each other at a large surface. Such contact at a large area is necessary since when reacting an acidic phosphorous acid compounds with a base directly, the reaction is rapidly completed even in a minute area. Consequently the temperature rises rapidly and the reactant(s) or the product melts. Such melts can be handled poorly during operations. Furthermore, at a higher temperature, undesirable reactions may occur. The temperature of reaction mixtures containing melts can not be satisfactorily controlled due to the usual lack of possibility of stirring and the effect of cooling surfaces can not be utilized.

During our investigations, we experienced that in the case when one of the reactant is distributed on a vehicle having large surface area, the reaction can be controlled in similar manner to the case when it is carried out in liquid phase. The temperature can be adjusted and set to the optimal value by controlling the rate of addition and stirring-homogenization.

The reaction proceeds by the reaction of the absorbed base (or optionally the vapour thereof) with the surface layer of the acid reactant. Since the reaction takes place at a temperature lower than the melting point of the salt product, a crystalline product rather than a melt is formed. This product is necessarily formed in a different crystalline system than the starting material, therefore only a weak physical linkage is present between them, which can be disrupted by stirring. Due to the motion occurring during homogenization continuously renew the surface of the acidic component, the reaction can be led to practically full conversion. The thus obtained surface-treated zeolite-containing rhyolite tuff itself can be used for microelement fertilization as soil and foliage fertilizer. The product can be used furthermore in mixed or co-formulated for with other different fertilizers as soil fertilizer for continuous microelement fertilization of plants.

According to an advantageous embodiment of the present invention, the weight ratio of the natural solid porous zeolite-containing vehicle to the phosphonic acid of the Formula (I) is between 0.1 : 1 to 200: 1 , preferably 0.4: 1 to 1 00: 1 .

As a further surprising effect, we have experienced that during the phosphonate formation, the zeolite behaves as a reactant and in the reaction with phosphorous acid, a mixture of phosphonate salts is formed corresponding to the rich microelement supply of the zeolite and such a mixture of phosphonate salt has exceptionally advantageous effect to the plant development.

By reacting with the zeolite and digesting the zeolite during the reaction with phosphorous acid, cations of the zeolite are partly exchanged to protons while the acid itself is transformed into phosphonate salt or into a mixture of phosphonates and hydrogenphosphonates depending on the cationic composition of the zeolite.

In the case when the phosphonate formation is carried out on the surface of the vehicle, during the surface treatment of natural zeolite-containing solid vehicle or of the mixture of natural and other above-mentioned solid vehicles, a phosphonic acid salt solution having the concentration of 0.01 - 15 w/w% is admixed with the solid vehicle.

Surprisingly we have found that during the treatment of such rocks of volcanic origin, such as zeolite-containig rhyolite tuff with phosphorous acid, the effect of the phosphonate can be experienced. For example, in the case of maize, when a zeolite treated with 2 w/w% phosphorous acid solution was used, emergence and flowering occurs earlier than in case of untreated control. This effect can be interpreted by the partial exchange of the metal ions of the rock of volcanic origin into protons while the phosphorous acid is transformed ito phosphonate or hydrogenphosphonate. Since many microelement important for plants occurs in rocks of volcanic origin, the phosphonates of these are formed. The use of volcanic rocks, especially the use of zeolite-containing rhyolite tuff is especially advantageous due to the fact that either by coating the rock with phosphonates or preparing phosphonates on the porous surface of said rocks can result in ion-exchange processes which result in providing the most important microelements to plants in form of phosphonate salts. During the preparation of the composition according to the present invention, we experienced that the biological effect of the substrate containing phosphorous acid-treated zeolite-containing rhyolite tuff in regard to disease resistance of the plants was similar to those of phosphonate-containing systemic fungicides.

During the preparation of phosphonic acid salts, it is possible to treat the porous solid vehicle simultaneously with phosphorous acid and other acids or salts. In this case, the solid porous vehicle is treated with a mixture of phosphorous acid and an organic acid, for example malonic acid, fumaric acid, succinic acid, ascorbic acid or an inorganic acid, for example phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid or with a mixture thereof in the proportion when the weight ratio of the formed phosphonate salt, the phosphorous acid used for surface treatment to the other acid used relative to equivalents is 100: 1 to 1 : 10, preferably 10: 1 to 5 : 1 , more preferably 4: 1 to 1 : 1. The most advantageously, phosphoric acid or phosphoric acid salts are used. As a salt, ammonium, alkali metal, alkali earth metal, transitional metal or heavy metal salts can be used. For the treatment of the surface of the solid vehicle, 0.01 to 1 5 w/w% phosphonic acid solution is mixed. If further salt or salts are used, such as ammonium phosphate, ammonium sulfate, ammonium chloride, ammonium nitrate, potassium phosphate, potassium nitrate, potassium chloride, calcium nitrate, calcium chloride or mixtures thereof, such salts can be mixed into the phosphorous acid solution and/or solid vehicle in form of a solution having concentration between 0.01 and 50 w/w%. The weight equivalent ratio of the phosphorous acid solution to the active ingredient of the salt solution is preferably between 100: 1 to 1 : 100, preferably 20: 1 to 1 :20. The mixing is preferably carried out when the temperature of the reaction mixture is 20-70°C, more preferably 20-65 °C, the most advantageously between 20 and 40 °C.

In the case when during the digestion of natural zeolite-cotaining solid vehicle is carried out in addition to phosphorous acid in the presence of malonic acid, fumaric acid, succinic acid, ascorbic acid, phosphoric acid and ammonium phosphate, ammonium sulfate, ammonium nitrate, potassium nitrate, potassium phosphate, calcium nitrate or mixtures thereof suitable for the nutrition of microorganisms is used, a formulation suitable for enhancing the activity and increasing the specific amount (relative to soil weight) of microorganisms living in the root zone of the plants can be produced. The reaction is carried out preferably that the weight ratio of the phosphonate salt active ingredients to other acid or salt ingredients is between 100: 1 to 1 : 10, preferably 10: 1 to 5: 1 , more preferably 4: 1 to 1 : 1 . The reaction is advantageously carried out at a temperature between 20 and 70°C, more preferably between 20 ad 65 °C, the most preferably between 20 and 40 °C.

The surprising effect that a mixture of phosphonate salts corresponding the rich microelement supply of the zeolite is formed which has especially good effect to plant development occurs in this case as. well.

According to one very advantageous method according to the present invention, wherein the solid porous vehicle is mixed with ammonium hydroxide or ammonium salts or metal salts, hydroxides or oxides, organic compounds, preferably organic amines or mixtures thereof or solution, suspension or dispersion thereof and subsequently phosphorous acid or an aqueous solution thereof is added to to homogenate. The mixture thus obtained is homogenized and if desired, dried. In this method, as a metal hydroxide, oxide or salt, alkali metal salts, preferably sodium or potassium salts or hydroxides; alkali earth metal salts, preferably calcium or magnesium salts, oxides, hydroxides; salts or oxides or hydroxides of transitional metals, preferably those of zinc, copper, iron, manganese, molybdenum, nickel, cobalt or heavy metal salts, oxides or hydroxides, preferably zinc, cadmium or aluminium salts, oxides or hydroxides or as an organic base, preferably primary, secondary or tertiary amines are used as solid powder, melt, solution, suspension or dispersion. As metal salts, preferably salts of organic acids for example malonic acid, fumaric acid, succinic acid, ascorbic acid or salts of inorganic acids for example phosphoric acid, sulfuric acid, nitric acid, carbonic acid or mixtures thereof can be used. The ratio of the produced phosphonate salt to other acids and/or salts expressed in weight equivalents is preferably between 100: 1 to 1 : 10, more preferably 10: 1 to 5 : 1 , the most preferably 4: 1 to 1 : 1 . In the advantageous embodiment of the method, the weight ratio of the solid vehicle and the base is between 0.75: 1 to 75: 1 .

The reaction can be carried out by keeping the temperature of the reaction mixture preferably between 20 and 70°C, more preferably between 20 and 65 °C, the most preferably between 20 and 40 °C.

According to an especially advantageous embodiment of the present invention, the solid porous vehicle carrying a salt of the phosphonic acid of the Formula (I) or a mixture of several different phosphonic acid salts can be optionally mixed with further biologically useful components, plant nutrients, plant hormones, vitamins, microelements, plant extracts. Such ingredients have been descibed above in detail . The appl icable amount of such compounds depends on the specific application, such as the plant species and the method of application of the formulation. Selection and mixing the selected suitable biologically useful materials into the treated solid porous vehicle belongs to the knowledge of the person skilled in the art. Mixing is carried out according to methods known from the prior art. Choice of applicable apparatus and process design as well as conducting such processes also belongs to the knowledge of the person skilled i the art.

In the formulation of the preparation, further auxiliary materials can be used. Thus, using a method known from the prior art, further auxiliary materials used in agriculture, for example, a binder, a disintegrant, an antiadherent additive, a chemical stabil izer, a dispersing agent, a tenside, a penetration enhancing agent, a complex forming agent, stabilizers, solvents, shower/rain proofing agents, suspension stabilizers or mixtures thereof can be mixed to the preparation according to the present invention. These components and suggested amounts thereof have been previously described in detail.

It is possible to mix the biologically useful auxiliary agent and/or agriculturally used excipients before transferring or forming of phosphonate salts or such components can be added simultaneously. Alternatively, one may proceed by first transferring the phosphonate salts onto the solid vehicle and the auxiliary agents are mixed into thereafter.

One may also optionally proceed by mixing a fraction of the solid porous vehicle pretreated with salts of phosphonic acid of the Formula (I) having particle size of 0.5 to 4.5 mm, preferably 1 .0 to 3.5 mm optionally with a fertilizer in a ratio that the weight ratio of the solid porous vehicle treated with phosphonic acid salt to the fertilizer ranges between 1 :20 to 2:20. Granules thus obtained can be preferably used as soil fertilizer. It is also possible to mix the ingredients in powder form and producing the desired particle size fraction by granulation.

Furthermore, it is still possible that the fraction of the solid porous zeolite-containing vehicle surface-treated with salts of phosphonic acid of the Formula (I) having a particle size between 0.5 and 5 μηι, preferably 1 and 3.5 μιη is mixed with water, ethanol, 1 ,2-propylene glycol, suspension stabilizer, preferably polyvinylalcohol, polyethylene glycol, potassium palmitate or ammonium laruate and optionally with nitrogen, phosphorous and potassium containing fertilizers, binders, plant hormones, vitamins, plant extracts, vegetable oil. According to a preferable method, 10 to 80 w/w%, preferably 30 to 60 w/w% of solid vehicle, 10 to 60 w/w% solvent and 0.1 to 10 w/w% suspension stabilizer is used relative to the weight of the formulation. The fraction having 0.5 to 5 μιτκ preferably 1 to 3.5 μιη particle size can be produced by analogously treating a vehicle having greater particle size with a suitable phosphonate and milling the thus obtained product to the desired particle size.

When a fast-acting preparation is desired, the porous vehicle, preferably rhyol ite tuff is treated with a solution of phosphorous acid and phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, oxalic acid, malonic acid, succinic acid, ascorbic acid or a mixture thereof having an active ingredient concentration between 0.01 to 80 w/w% and optionally with a solution of a phosphonic acid salt and ammonium phosphate, ammonium sulfate, ammonium chloride, ammonium nitrate, potassium phosphate, potassium nitrate, potassium chloride, calcium nitrate or calcium chloride or a mixture thereof having 0.01 to 50 w/w% concentration in an amount of 0. 01 to 20 w/w%. wherein the equivalent weight ratio of the phosphorous acid to other acids and salt is 1 00-5 : 1 . Such formulations are primarily suitable for accelerating the initial development of plant in loamy soils and where the soil organic colloid concentration is high.

In loosely structured sandy soils poor in loam and organic colloids, where the rapid washing out of the nutrients is a concern, a slowly acting surface treated zeolite containing rhyolite tuff can be advantageously used. These can be produced by treating the porous vehicle, preferably rhyolite tuff preferably in a solution of phosphorous acid and phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, oxalic acid, malonic acid, fumaric acid, succinic acid, ascorbic acid or mixtures thereof, wherein the active ingredient concentration of said solution is between 0.01 and 80 w/w% and optinally with a solution of phosphorous acid and ammonium nitrate, ammonium phosphate, ammonium sulfate, ammonium chloride, potassium phosphate, potassium nitrate, potassium chloride, calcium nitrate, calcium chloride or mixtures thereof, wherein the concentration of said solution is between 0.01 to 50 w/w% and the amount of the solution is 0.01 to 20 w/w% in a way that the equivalent weight ratio of the active ingredient of phosphorous acid used for surface treatment to other acids and/or salts ranges between 1 :5 and 1 : 100.

The preparation according to the present invention containing a solid porous vehicle and a salt of phosphonic acid of the Formula (I) or a mixture of several different phosphonic acid salt can be formulated in solid or liquid form according to methods known from the state of the art. Solid formulations for example can be produced as powders or granules and the powder form can be used as soil fertilizer or sprayable powder, granules can be used as soil fertilizer. The formulation can be produced in liquid form as suspension, dispersion or suspo-emulsion, which can be used as soil fertilizer or foliage fertilizer or as concentrate. Concentrates are mixtures which are diluted prior to use. Sprayable powders for example can be regarded as such concentrate.

In the formulation according to the present invention, the weight ratio of the solid porous vehicle and the salts of the phosphonic acid of the Formula (1) is between 0. 1 : 1 to 200: 1 , preferably 0.4- 1 to 100: 1 .

During our experiments, we surprisedly found that when a natural zeolite containing volcanic rock is surface-treated with a solution of phosphorous acid and/or acidic salt of phosphorous acid and optionally milling the thus obtained product in solid form with a zeolite containing volcanic rock having large surface area and rich in chemical trace element, e.g. zeolite containing rhyolite tuff, the product thus obtained contained phosphorous acid salts having biological efficiency significantly exceeding the efficiency of salts produced by the reaction of phosphorous acid and the corresponding cation base.

The differences between the effects of the formulations prepared on different vehicles are demonstrated in the following examples. 1 . Preparation and effect of potassium and dipotassium phosphonate containing mixtures using different zeolite types:

A. ) rhyolite tuff composite

700g zeolite-containing rhyolite tuff is mixed and surface-treated with 183 g of potassium hydroxide solution having 49 % active ingredient content. The surface-treated material thus obtained is charged into a Lodige mixing apparatus and 1 1 7 g of phosphorous acid solution having 75 w/w% active ingredient content are added dropwise.

B. ) Synthetic zeolite composite

The method of paragraph A was followed with the only modification that as a zeolite, Zeofree 484 (Zeofin O.Y. Hamina Finland) synthetic zeolite was used.

C. ) 1 : 1 mixture of treated synthetic and natural zeolites

The potassium and dipotassium phosphonate containing products obtained according to the method of paragraph A and paragraph B were mixed in 1 : 1 weight ratio.

The zeolites produced according to identical method having identical active ingredient content were transformed into formulations of the following composition:

The effect of the thus obtained formulations containing preparations A, B and C, respectively, has been evaluate with regard to product quality and quantity in grape, tomato and sunflower species. Diseases decreasing crop yield are shown in parentheses.

Results are summarized in the following table: Tomato (Alternaria ssp) Grape (Peronospora ssp) Sunflower (Diaporthe ssp)

A B C A B C A B C

Yield 62 44 53 1 1 9 100 1 0 3 41 5 2 350 3 070 kg/hectare 500 500 200 320 400

Vitamin C content Sugar degree Oil yield %

Quality 3 1 .9 1 7.8 22.6 20.9 1 7.2 1 8.6 48.7 46. 1 48. 1

During the evaluation of the experiments described above, we have surprisingly found that the biological effect of suspensions containg natural zeolit-containing rhyolite tuff is significantly better than that of suspensions containing synthetic zeolite. This pointed to surprising synergistic effect in the case when phosphonates and natural zeolite containing rhyolite tuffs are used simultaneously.

In order to j ustify synergy, the fol lowing experiment has been carried out.

The effect of the suspensions was studied using a tap water control in pepper (capsicum annuum). Experiments were carried out in a greenhouse using 4X5 pots in each experiment. Into each pot, 25 seeds were sown and covered by 2 cm soil. Subsequently the pots were irrigated with the solutions or suspensions given in the next table. Each preparation was used in three different doses ( 10, 20 and 40 1/hectare). The emergence rate (in percents) and the percentage of surviving seedlings at 6-8 leaf age not killed by damping off was determined.

The synergy between active ingredients, which means an effect exceeding the additive effect of the individual active ingredients can be calculated by the following formula (D.L. Richter, Pestic. Sci. 1 987. 19. 4. 303-3 1 5):

100

In the above formula, H _A = calculated additive effect, A|,= effect of ingredient A in percents, Bh= effect of ingredient B in percents, C = portion beyond the effect of ingredient A. Formulation Dose Germination Proportion of

[1/hectare] rate, % surviving plants at

6-8 leaf age [%] mea calculat measu calculated sure ed red

d

Tap water control 56 - 43 -

Phosphorous acid solution 10 10 69 56

w/w%

Phosphorous acid solution 10 20 77 63

w/w%

Phosphorous acid solution 10 40 82 70

w/w%

Zeofree 484 containing 10 57 41

suspension 10 w/w%

Zeofree 484 containing 20 53 38

suspension 10 w/w%

Zeofree 484 containing 40 68 49

suspension 10 w/w%

rhyolite tuff zeolite containing 10 64 5 1

suspension 1 0 w/w%

rhyolite tuff zeolite containing 20 77 56

suspension 10 w/w%

rhyolite tuff zeolite containing 40 80 61

suspension 10 w/w%

Phosphorous acid 10 w/w% + 5+5 81 86.7 75 74.1 Zeofree 484 10 w/w%

suspension

Phosphorous acid 10 w/w% + 10+ 10 83 89.2 79 77. 1 Zeofree 484 10 w/w%

suspension

Phosphorous acid 10 w/w% + 20+20 86 92.2 81 84.7 Zeofree 484 10 w/w%

suspension

Phosphorous acid 10 w/w% + 5+5 92 88.8 85 78.1 rhyolite tuff 10 w/w%

suspension 5. Phosphorous acid 10 w/w% + 1 0+ 1 0 97 94.7 91 83.7 rhyolite tuff 10 w/w%

suspension

6. Phosphorous acid 10 w/w% + 20+20 97 96.4 93 88,3 rhyolite tuff 10 w/w%

suspension

The above table demonstrates (see experiments 14 to 16) that by using 10 w/w% phosphorous acid solution + 10 w/w% zeolite containing rhyolite tuff both the germination rate and the surviving seedlings not killed in damping off was greater than the calculated, thus proving that non-expected synergistic effect takes place when using phosphorous acid or phosphonates present in alkal ine medium or on the surface of the zeolite and zeolite- containing volcanic rhyolite tuff simultaneously.

In Example 18, the yield of tomatoes and the changes in microelement composition has been studied using a rhyolite tuff vehicle treated with phosphorous acid, phosphoric acid and with the mixture of phosphorous and phosphoric acids compared to untreated control plantations and plantations treated with Radistart Eco® in known manner. Results show that the amount of the produce is by 65 percent higher than the untreated and by 50% higher than in case of tomato plants treated in known manner.

Winter wheat was treated twice in the vegetative period with the formulation according to the present invention containing dipotassium phosphonate (Example 20). The yield of the crop has significantly increased as compared to untreated control and the control treated with Wuxal Super product known in the state of the art.

Studies were carried out to determine the biological effect of the mixture of the microgranulated starter fertilizer and a microelement fertil izer containing increased amount of magnesium phosphonate under field conditions in sunflower (Example 21 ). It was concluded on the basis of the results that the formulation according to the present invention increased the yield of the crop as well as moderated the proportion of infectious stem diseases originating from the soil.

Application of increased zinc (II) phosphonate containing microelement fertilizer has been studied in apple culture (Example 22). Quality determining parameters have been evaluated before storage-in and after 90 day storage in JONIKA variety. The formulation according to the present invention has been worked into the root zone of plant trees before the starting of vegetation period in 50 kg/hectare dose. Better supply of microelements improved the storage properties of apples.

The advantage of the present invention resides in that plants treated with the formulation develop better than the control and even better than plants treated according to the state of the art and these plants are less susceptible to damages caused by pests.

Controlled release of nutrients hinders the fast release of great amounts of plant nutrients, which may prohibit seed germination or burn the root system of the seedling.

It assures that the vehicle - in the present case, the porous vehicle - and the agricultural and chemical compounds as well as plant nutrients contact soil particles and the root system of the plants at the largest possible area. Phosphonates can be delivered in such a form either as soil or as foliage fertilizer, which provides controlled dissolution of the active ingredient, said active ingredient is not washed out by rain nor contaminates watercourses.

The fact that due to controlled active ingredient release, the soil is not enriched in nutrients, thus microorganisms which may appear as transitional concurrents of the cultured crop can not proliferate.

The present invention allows for providing controlled release formulations having combined effect, wherein, besides the plant protecting and growth enhancing properties of phosphonates, other nutrients, vitamins, hormones useful for the plant can be included.

During the manufacture of the formulation, operating steps can be spared. Furthermore in the case when natural zeolite tuffs are used, due to the ion exchange property of the tuffs, a composition containing phosphonate salts rich in microelements and especially useful for plants can be prepared.

The general plant growth promoting effect of the thus produced formulations resulting from enhanced microelement nutrition manifests itself in the following:

- more intense photosynthesis and accordingly intensified formation of primary assimilates (starch, lignin, cellulose etc.)

- the plants become more tolerant towards high enviromental temperature and negative effects of water shortage. - the plants become more tolerant towards plant diseases, especially to infections caused by fungi and bacteria, thus the amount of delivered pesticides can be reduced.

- The biosynthesis of secondary metabolism products becomes intensified (terpenes, alkaloids, flavonoids, vitamins, triglycerides stb.), thus improving the the efficiency of the plants treated with the formulation according to the present invention from the viewpoint of nutritional physiology.

-due to the treatments, the root system of the plants is greater, thus penetrating into greater layer of the soil, whereby the nutrient and water supply of the plants is improved.

Our invention is demonstrated by the following examples without limiting our claim to said examples.

Example 1

Preparation of the mixture of potassium and dipotassium phosphonate

In a suitable mixing apparatus. 1 83 g of potassium hydroxide solution having 49% active ingredient content are transferred dropwise to the surface of 700 g of rhyolite tuff. The surface-treated powder thus obtained is charged into a Lodige type mixer and 1 1 7 g of phosphorous acid having 75% active ingredient content are added dropwise. The temperature is not allowed to raise above 60°C. At the end of dosage, homogenization is continued for 30 minutes, thus a dry homogeneous powder is obtained having potassium and dipotassium phosphonate content of 25 l g/kg.

Example 2

Preparation of the mixture of potassium phosphate and potassium phosphonate

In a suitable mixing apparatus, 78 g of potassium hydroxide solution having 49% active ingredient content is transferred dropwise to the surface of 583g of Zeofree 484 (Zeofin O.Y., Hamina, Finland, synthetic silicon dioxide derivative). The thus obtained surface-treated powder is charged into a Lodige type mixer and 40.5 g of phosphorous acid solution having 75% active ingredient content and 48.5g of phosphoric acid solution having 75% active ingredient content are added thereto dropwise while the temperature is kept below 60°C. After the end of dosage, homogenization continued for 30 minutes. Thus a dry homogeneous powder is obtained. The product thus produced contains a 1 : 1 mixture of 196 g/kg monopotassium phosphonate and monopotassium phosphate.

Example 3

Preparation of ammonium phosphonate

In a suitable mixer, 47 g of ammonium hydroxide solution having 25% active ingredient content are added with continous stirring to 587g of silica gel. The powder thus obtained is charged into a Lodige type mixer and 37 g of phosphorous acid solution having 75% active ingredient content are added dropwise. The temperature was not al lowed to raise above 40°C. After the end of addition, homogenization is continued for further 30 minutes. The ammonium phosphonate content of the thus obtained dry powder is 106g/kg.

Example 4

Preparation of zinc (II) phosphite

In a suitable stirrer, 50 g of zinc(II) nitrate solution having 30% active ingredient content is added to 840g of calcium silicate with continuous stirring. The powder thus treated is charged into a Lodige type mixer and 1 0 g of phosphorous acid solution having 75% active ingredient content are added dropwise. The temperature is not allowed to raise above 50°C. After the addition, the homogenization is continued for further 30 minutes. Thus a powder having 14g/kg cink(II)-phosphite content is obtained.

Example 5

Preparation of monoethanolamine phosphonate

In a suitable mixer, 5 g of monoethanolamine having 99% active ingredient content is added to 986g of zeolite of natural origin with continous stirring. After homogenization, while stirred, 9 g of phosphorous acid solution having 75% active ingredient content are added dropwise. The temperature is not allowed to raise above 50°C. After the addition, homogenization is continued for further 30 minutes. The monoethanolamine phosphonate content of the thus obtained dry powder is 12g/kg. Example 6

Preparation of copper tetramine phosphonate a. ) Preparation of copper tetramine

An Erlenmeyer flask equipped with magnetic stirrer is charged with 1 5 g (0.8333mol) ion- exchanged water and 6.5g (0.043 l mol) of D-tartaric acid are dissolved therein. Into this solution while stirring and cooling continously, 46.5g of 25% ammonium hydroxide solution are added. Into this solution, 14.9g (0, 1478mol) of copper(II) hydroxide having the purity of 96.72% are weighed gradually. b. ) The solution prepared according to a) is added dropwise to 900g gmelinit [( a2Ca) ₄ Al ₈ Si i60 ₄ 8* ₂₄ H ₂ 0] type synthetic zeolite and after homogenization, 1 7.1 g (0.2008mol) of phoshorous acid powder having an active ingredient content of 96.3% are added. Thus the reaction takes place only partially, the full amount is converted into salt in the spraying tank before delivery. At that time the effective copper tetramine phosphonate content is 3 1 .2g/kg.

Example 7

Preparation of magnesium phosphonate

In a suitable mixer, 64 g of 96% magnesium oxide powder are added to the mixture of 21 0g zeolite having natural origin and 2 lOg of faujarite [(KNai 3Cai2Mg Al ₅ 5Si i ₃ 70 ₃ g ₄ )*23 ₅ H ₂ 0] type synthetic zeolite. After sufficient homogenization, 1 16g of phosphorous acid solution having 75% active ingredient content are added. During mixing, the temperature is kept preferably between 50 and 80 °C. After the end of addition, the homogenization is continued for further 30 minutes. The magnesium phosphonate content of the dry powder thus obtained is 223g/kg.

Example 8

Preparation of aluminium phosphonate a.) preparation of ammonium phosphonate solution

A suitable mixer is charged with 30.84g (0.3mol) of 96.3% phosphorous acid powder. While continuously stirring, 50.46g (2.8mol) ion-exchanged water are added, followed by 1 18.8g (0.3mol) of 25% ammonium hydroxide solution with stirring and cooling. The temperature is not allowed to raise above 40 °C. The ammonium phosphonate content of the solution thus obtained is 148.5g/kg. b.) In a mixer equipped with cooling/heating jacket, 44.84g (0.2mol) of 95% aluminium(III)- nitrate is reacted with 200g of ammonium phosphonate produced according to the method of paragraph a.)- During the reaction, the temperature is kept preferably below 40 °C. The ready solution is added portionwise with continuous stirring to a mixture of 1336.5g of natural zeolite and 148.5g of calcium silicate. After achieving suitable homogeneity, a powder containing 20g/kg of aluminium-phosphonate is obtained.

Example 9

Preparation of the monoethanolamine salt of phosphorous acid

In a suitable mixer 1 03 g of Toxilis 38 A (Rhone-Poulenc, Geronezzo, Italy; synthetic silicate) and 3 g of air-dry alginite are homogenized with 95 g of monoethanolamine. The powder thus obtained is added in small portions into 280 g of phosphorous acid having 95% active ingredient content residing in a V-shaped mixer. During continuous mixing and addition in small portions, the material becomes sl ightly sticky and gets warm. The temperature is not allowed to raise above 50 °C. After the end of the addition, the

homogenization is continued for further 30 minutes, thus a dry homogeneous powder having 745g/kg of phosphorous acid monoethanolamine salt content is obtained.

Example 10

Preparation of piperidinium salt of phosphorous acid

In a V-shaped mixer, 81 g of Vessalon-S (synthetic silicone dioxide derivative, Degussa, Germany) and 8 1 g of ankerite [Ca(MgFeMnZn)*(C0 )2] are mixed with 15g of piperidine. Into this mixture are weighed 50g of nitrilo-tris-methylene-phosphonic acid sodium salt, 50g of urea, 1 7g of Pluronic F 108 (ethylene oxide propylene oxide block polymer, BASF), and 30g of renex 30 (ethoxylated alcohol, ICI). The mixture is homogenized and 379g of 95% phosphorous acid are added in portions. During the addition, the temperature of the system raises to 65-75 °C due to reaction heat. At this temperature, pluronic F 108 melts and binds the salt formed thus forming granules. After the end of addition, mixing is continued for 30 minutes and the system is cooled to room temperature. Thus granules containing 520g/kg of phosphorous acid piperidinium salt are obtained which is milled in a hammer mill unti l the suitable particle size is reached.

Preparation of formulations containing phosphorous acid salts

Example 11

Preparation of potassium phosphonate 24 WP

44 g of Silwet L-77 excipient (ethoxylated dimethyl si loxane derivative, OSi) are added to 356g of material prepared according to Example 1 with continous stirring. After achieving appropriate homogeneity, a further 600 g of the material prepared according to Example 1 are added and mixed until homogeneity. By this method, a preparation having potassium and dipotassium phosphonate content of 240 g/kg with good storage properties is obtained.

Example 12

Preparation of phosphorous acid piperidinium 24.8 WP

In a suitable mixer. 500g (particle size 0.5- 1 mm) of the preparation produced according to Example 1 1 are homogenized with 500g of phosphorous acid piperidinium salt containing product produced according to Example 1 0 which has been previously milled to the same particle size in a hammer mill and subsequently the thus obtained homogenate is mixed with 50g of Silwet L-77 (ethoxylated dimethylsiloxane derivative. Osi). The phosphorous acid piperidinium salt content of the thus obtained powder is 248 g/kg.

Example 13

Preparation of contact fungicid combination using magnesium phosphonate and elemental sulfur

450g of magnesium phosphonate containing product prepared according to Example 7, 450g of elemental sulfur, 50g of Pluronic L44 (ethylene oxide-propylene oxide block polymer), l Og of Silwet 77 (ethoxylated dimethylsiloxane derivative. OSi), l Og of Agrimer 30 (polyvinylpyrrolidone, ISP) are mixed with 30g of water and compressed using a BR-200 basket extruder. After using a QJ-400 marumerizer, granules containing 100 g/kg magnesium- phosphonate and 450g/kg sulfur are obtained.

Example 14

Preparation of copper tetramine 0.85 G

A mixture of 27.4% of product of Example 6/b, 5% of hydroxyethane-diphosphonic acid tetrasodium salt (Nitrokemia Rt), 2.5% of Genopol 0200-T (ethoxylated alcohol, Hoechst) 2.5% of sodium hydrogencarbonate, 2.5% of Arkopon T-Pulver (2-{methyl-[(9Z)-l -oxo-9- octadecen- l -yl]amino-ethanesulfonic acid sodium salt) and 57.5 w/w% of (NP^SC^ are pelletized between rotating cylinders. The product thus obtained is very well soluble in water with effervescence. The sodium tetramine phosphonate content is 8.5 g/kg.

Example 15

Preparation of monoethanolamine phosphonate 67.5 G

A laboratory scale rotating plate granulating apparatus is charged with 91 Og preparation containing phosphorous acid monoethanolamine salt produced according to Example 9. While mixing, 50g of naphtylsulfonic acid ammonium salt, l Og of magnesium oxide and l Og of diisobutyl-sulfosuccinate sodium salt are added. After achieving homogeneity, into the granulating apparatus is sprayed using suitable drop size and rate with the solution of 20g Agrimer ATF (cross-linked polyvinyl-pyrolidone) in ethanol. After drying, granules with minimal flowing powder content are obtained, which is easy to dose by volume and has good storage properties. The phosphorous acid monoethanolamine salt content of the preparation is 675g/kg.

Example 16

Preparation of magnesium phosphonate 19.3G

The mixture of 86.7 parts of the material prepared according to Example 7, 9.0 parts Emcol CC-55 (propoxylated quarternary ammonium-amine salt containing excipient), 2.0 parts of Syaperonic A 7 (ethoxylated alcohol, IC1), 1 .5 parts of Agrimer VA-5 (polyvinyl-acetate- poly-vinyl-pyrrolidon, ISP) and 7.0 parts of water are compressed using an APV-LM 50 type double screw extruder at 70 °C jacket temperature using 1 mm hole size. The extrudate exiting the apparatus is transferred after short cooling and drying into a spheronizer operating at 1500 rpm where it is broken to rods of 1.5-2.5 mm length. During this treatment, the water content of the material decreases to about 0.8%, and finally a preparation having good solubility-disperibility in water and 193 g/kg magnesium phosphonate active ingredient content is obtained.

Example 17

Preparation of magnesium phosphonate 19.3G

The method of Example 16 is followed with the modification that the amount of Emcol CC- 55 is 2.0 parts (instead of 9.0 parts) and instead of 7.0 parts of water, 14 parts of 50% aqueous solution of 2,4,7,9-tetramethyl-6-dodemin-5,8- are used. Thus a formulation having 193 g/kg magnesium phosphonate active ingredient content is obtained.

Example 18

Preparation of rhyolite tuff treated with phosphoric acid and phosphorous acid and testing of its effect in tomatoes

Tests were carried out in a greenhouse using a Mitscherlich type propagating vessel, one plant per vessel. The humus content of the soil H%= 1 . 1 3 ; the pH= 5.2; calcium carbonat CaCO ₃ =0; nitrite + nitrate N: N0 ₃ +N0 ₂ -N= 5.2 ppm; phosphorous as P ₂ 0 ₅ = 55ppm; potassium as K ₂ 0= 79ppm, Ακ=28.

A Lodige type mixer is charged with 90 weight% rhyolite tuff having the particle size of 0.4 to 1 .0 mm, which is sprayed during continous stirring with 10 w/w% weight of solutions having the concentration of 20 w/w %

a) phosphorous acid solution ( 1 .66 w/w% 2O )

b) phosphoric acid solution( l .44 w/w% P ₂ 0 ₅ )

c) 1 : 1 mixture of phosphorous acid and phosphoric acid solutions ( 1 .55 m/m% P2O5) After the liquid is adsorbed, the particles are powdered with talc.

Durig the transplantation of the seedling, 10 g portions of the preparations were delivered to each plant. The yield of produce and the microelement content of the produce were determined. Data are given in relative percent. Standard Standard Rhyolite tuff Rhyolite tuff Rhyolite tuff control I. control II. treated with treated with treated with

(untreated (Radistart phosphorous phosphoric mixture tuff) Eco) acid acid c)

(a) (b)

Yield % 1 00 1 14.0 165. 1 1 30.9 1 54.1

Fe% 100 98.1 91 .8 96. 8 95.6

Mn% 100 101 .5 1 1 8. 1 106.0 1 1 1 .5

Cu% 100 109. 1 133.3 123.5 1 15.9

Zn% 100 1 13.2 1 30.7 122.9 121 .5

Mo% 100 102.9 1 52.7 142. 1 143.2

B% 100 104.7 130.8 129.5 122.7

Radistart Eco® is a fertilizer produced by Plantaco Ltd. having the composition: N=7 w/w%, P ₂ 0 ₅ = 40 w/w%; K ₂ 0=6 w/w%

The yield results showed that the biological effect of rhyolite tuff treated with phosphorous acid was significantly better than that of a phosphorous containing fertilizer having the usual composition (Radistart Eco).

Example 19

Preparation of rhyolite tuff treated with potassium phosphonate and potassium

phosphate and study of the effects thereof in tomato

The experimental setup was identical to that of Example 1 0. a) preparation of an aqueous solution of potassium phosphonate

Phosphorous trichloride was hydro ly-sed (PC1 ₃ + 3 H ₂ 0) = H ₃ PO ₃ +3HCI. Hydrochloric acid was removed from the system with hydrochloric acid, thus a H3PO ₃ solution having 70 w% concentration is obtained. Phosphorous acid is neutralized with potassium hydroxide: H3PO3 + OH -> H2PO3+H2O is formed, which has the composition in the form used in fertilizers:

N=0 : P ₂ 0 ₅ : - 22 w/w% K ₂ O20 w/w% b) Preparation of aqueous solution of potassium phosphate

Monopotassium phosphate (0-5 1 .5-34.0) is treated with potassium hydroxide solution having

45% concentration

KH2PO4 + KOH > K2HPO4+H2O

The composition of the product N=0 : P ₂ 0 ₅ - 18 w/w% K ₂ O=20 w/w%

The aqueous solution of the thus obtained salts was used for the treatment of rhyolite tuff having particle size of 2.5-4.0 mm according to the method of Example 10, wherein the weight proportion of rhyolite tuff was 95 w/w%. the proportion of the solution used was 5 w/w%. The formulation was delivered in a dose of 500 kg/hectare and was worked into the soil to 5-6 cm depth before transplanting the seedlings.

Formulations according to the invention significantly (40- 120%) improved the yield of tomatoes and kept the leaf diseases below the harmful values.

Example 20 Preparation of dipotassium phosphonate containing sprayable powder a) In a suitable mixer, 700g (particle size 40 to 1 00 microns) rhyolite tuff is treated dropwise with 183 g of 49% potassium hydroxide solution. The surface-treated powder thus obtained is charged into a Lodige type mixer and 1 1 7g of phosphorous acid solution having 75 w/w% active ingredient content are added dropwise while the temperature was not allowed to raise above 60 °C. After the end of addition, homogenization was continued for 30 minutes, thus a dry, homogeneous powder having potassium and dipotassium phosphonate content of 250 g/kg.

b) 80 weight% of preparation prepared according to paragraph a) are mixed with 2 weight% of bentonite, 1 weight% of 2-hydroxycellulose, 2 weight% of nonylphenol ethoxylate and 15 weight% of urea-formaldehyde condensate.

The mixture is milled in a peg mill apparatus to the particle size of 5-6 microns and thus a sprayable powder having good floatability with 200 g/kg of potassium and dipotassium phosphonate content and 5.7 weight% nitrogen content.

The sprayable powder thus obtained was used for the treatment of winter wheat twice during the vegetation period. The treatments were carried out at the end of bush formation and at the beginning of flowering with 5.0 kg/hectare and 1 0.0 kg/hectare doses. As a standard control, WUXAL SUPER (Aglukon Spezialdiinger GmBH and Co. K.G. Germany) was used in similar periods of vegetation and in similar dose. The yield of the crop and the microelement content thereof were determined. Results are given as percentages of untreated control.

kg/he Yield Fe Mn Cu Zn Mo B ctare %

Untreated

- 100.0 100.0 100.0 100.0 100.0 100.0 1 00.0 control

WUXAL

5 + 5 103.5 1 00.5 100.4 95.4 99.6 1 1 3.5 100.3 SUPER

WUXAL 10 +

107.9 1 03.2 99.7 1 05.2 103.1 1 22.0 1 03.6 SUPER 1 0

Formulation

according to

the 5 + 5 1 1 1 .3 106..3 108.1 103.4 108.2 1 3 1 .4 109.4 invention

formula b)

Formulation

according to

10 +

the 122.4 109.7 1 13.2 108.9 1 13. 1 163.6 1 15.8

10

invention

formula b) Comparing the biological effect of the formulation according to the present invention and that of the most widely used cereal foliage fertilizer, it can be concluded that the efficacy of the formulation according to the present invention exceeded the biological efficacy of the standard formulation.

Example 21

Preparation and testing of biological efficiency of a microgranulated starting fertilizer and microelement fertilizer mixture having increased magnesium phosphonate content

Magnesium phosphonate is produced by adding 64 g of magnesium hydroxide powder having 96 w% active ingredient content to 41 Og of rhyolite tuff of natural origin (particle size 0.5- 1 mm) in a suitable mixer. After appropriate homogenization, 1 16 g of phosphorous acid solution having 75 weight% active ingredient content are added. During mixing, the temperature is preferably kept between 50 and 80°C. After the end of the addition, homogenization is continued for further 30 minutes and the magnesium phosphonate content of the thus obtained dry powder is 220 g/kg.

The formulation according to the invention has been tested in sunflower under field conditions. The yield of the crop and the proportion of stem diseases was measured. Data are given as percentages of untreated control.

On the basis of the results, it was concluded that the formulation according to the present invention not only increased the yield of the crop but moderated the proportion of stem diseases originating from the soil as well . Example 22

Preparation of microelement fertilizer having increased zinc(II) phosphonate content and application thereof in apple culture

In a suitable mixer, 70 g of zinc(II)nitrate solution having 30 weight% active ingredient content is sprayed onto the surface of 815g of rhyolite tuff (particle size 2.5-4.5 mm). Particles thus treated were charged into a Lodige type mixer and at spraying, 15g of phosphorous acid solution having 75 weight % active ingredient content are added. The temperature is not allowed to raise above 50 °C. At the end of the addition, particles having 20g/kg of zinc(II)phosphonate are obtained.

The biological effect of the preparation according to the present invention was tested in apple. The quality characteristics were evaluated in JONIKA variety before storage-in and 90 days after storage. The formulation according to the present invention was worked into the root zone of the fruit trees in 50 kg/hectare dose before the starting of the vegetation period.

The improved microelement supply of the plant enhanced storage characteristics.

Example 23 Preparation of stabilized plant conditioning suspo-emulsion and effect thereof on potato yield and development of leaf disease

The formulation according to Example 23 was used for the treatment of potato in two occasions from the beginning of flowering. After the drying of the foliage, the yield was measured and the Phytophtora infection was evaluated 27 days after the second treatment.

(Amalgerol Premium Hechenbichler, GmbH. Austria)

The yield of potatoes after treatment with the formulation of Example 23 exceeded the yield obtained after treatment with Almagerol Premium, while the degree of Phytophtora infection was lower in case of the formulation according to Example 23 than that experienced with Amalgerol Preminum.

Example 24 Testing of the rate of effectiveness during the use of rhyolite tuff treated with different phosphorous derivatives

The effect of a single treatment of rhyolite tuff was tested in field conditions for the emergence and initial development of maize delivered at the time of sowing. The test was carried out in sandy soil. Beside the sown seed, 50-50 kg of granules pretreated according to the procedure below and having a particle size of 2 to 4 mm were dispersed.

Formulation 16/a :

- 10 w/w% of phosphorous acid solution having 20w/w% concentration and

- 1 w/w% of phosphoric acid solution having 0.5 w/w% concentration.

Formulation 16/b

- 10 w/w% of potassium phosphonate solution having 20 m/m% concentration and

- 1 w/w% of potassium phosphate solution having 0.5 w/w% concetration.

The emergence rate was determined 5, 7 and 10 day after sowing as well as the date of 50% of tassel flowering and the date of 50% carpel flowering. Results are summarized in the table below.

The emergence and flowering data show that the biological effect of rhyolite tuff treated with phosphorous acid and phosphoric acid develops faster.

Example 25

Testing of yield increasing effect Formulations according to the present invention increase the yield of the plants, whicn nas been tested in cucumber.

In a closed production apparatus (cold greenhouse production) 100- 100 pieces of cucumber seedlings were planted. Among these, 100 pieces were treated with the formulation according to Example 1 1 and the other 100 pieces were left untreated. During the test, treatments were the following.

1 . At the time of planting, irrigation with the preparation of Example 1 1 , 1 ml/plant, formulation of the Example 1 1.

2. At week 2, irrigation with the preparation of Example 1 1 , 1 ml/plant, formulation of Example 1 1

3. At week 4, irrigation with the preparation of Example 1 1 , 1 ml/plant, formulation of Example 1 1

4. At week 6, irrigation with the preparation of Example 1 1 , 1 ml/plant, formulation of Example 1 1

5. At week 8, irrigation with the preparation of Example 1 1 , 1 ml/plant, formulation of Example 1 1

The produce was collected 45 times from the plants. In the case of plants treated with the formulation according to the present invention, the yield of produce was 5.87 kg/plant, in the untreated plants the yield was 3.17 kg/plant.

Example 26

Effect on the quality of product and on Peronospora disease

In Harslevelu grape cultivar the effect of the preparation of Example 1 2 was investigated on sugar and acid degree, the yield and Peronospora infestation. The preparation was sprayed six times during the vegetation period in an amount of 5 kg/hectare. Results are summarized in the table below.

The formulation according to the invention has advantageous effect on sugar degree and yield while at the same time it did not affected acid degree but increased the resistance of the plant against Peronospora infestation.

Example 27 Investigation of nematicid effect in pepper (capsicum anniiuW)

Th success of pepper production is greatly prohibited by the nematodes present in the soil in great number, which may often cause 50-60% decrease in yield. The nematicide effect of the formulation prepared according to Example 15 was compared in pepper (paprika) intended for consumption in closed production apparatus (greenhouse) with the effect of Nemathorin 10 G ((RS)-S-sec-butyl-0-ethyl-2-oxo- l ,3-thiazolidine-3-ylphosphonothioate; Fosthiazate) formulation. The formulations were delivered at the time of planting to the root zone of the plants and the effects were evaluated 42, 63 and 84 days after planting. The doses of the preparations were the following.

On the basis of test results, it can be concluded that due to the fertilizer and nematicid effect of the formulation according to the present invention, the yield per square meter increased significantly while the ratio of plants infested with nematodes decreased.

Example 28

Preparation of stabilized, concentrated sulfur containing suspension

Calcium acetate 3.00

Sodium bentonite clay 2.00

Sodium benzoate 0.05

Xanthan gum 0.20

Ion-exchanged water 41 .67

Example 29

Preparation of granules containing copper having systemic and contact effect and investigation of the biological effect thereof on Phytophtora disease in tomato

The mixture of the preparation produced according to Example 6/b (27.4 w/w%), 5 w/w% hydroxy-ethanediphosphonic acid tetrasodium salt (Nitrokemia Rt.), 2.5 w/w% Genopol® 0 200-T (ethoxylated alcohol, Hoechst) 2.5 w/w% sodium hydrogencarbonate, 2.5 w/w% 2- {methyl-[(9Z)- l -oxo-9-octadecene- l -yl]amino-ethanesulphonic acid sodium salt (Arkopon T- powder), 30 w/w% copper-oxychloride and 30.1 w/w % ammonium sulphate are pelletized. The mixture thus obtained easily dissolves in water with effervescence. The copper-tetramine- phosphonate content is 8.5g/kg. the copper-oxychloride content is 300 g/kg, total elemental copper content 1 71 . 1 g/kg.

Treatments were commenced at the appearance of the furst buds and was carried out six times in 10 to 14 day intervals. The amount of the elemental copper delivered was 9.0- 1 5 kg/hectare in case of copper oxychloride 50WP, while in the case of the formulation according to the present invention, the amount of eiementar copper was 2-4 kg/hectare. Thus the amount of the delivered copper decreased by 75% without the decrease in the biological efficiency of the formulation.