AU2014351863B2 - Fluidized bed granulation with aqueous solutions of prohexadione-calcium and inorganic sulfate - Google Patents

Abstract

The present invention provides a process for producing a granular material comprising prohexadione-calcium and an inorganic sulfate, comprising the fluidized bed granulation of an aqueous dispersion comprising prohexadione-calcium and an aqueous solution comprising at least one inorganic sulfate. The invention further relates to a homogeneous granular material comprising an inorganic sulfate and prohexadione-calcium, wherein the inorganic sulfate and the prohexadione-calcium are distributed homogeneously in the granular material and the granular material has a porous matrix structure. The present invention further relates to the use of the homogeneous granular material for regulating the growth of plants, especially in the form of a spray liquor.

Description

Fluidized bed granulation with aqueous solutions of prohexadione-calcium and inorganic sulfate TECHNICAL FIELD OF THE INVENTION

The present invention provides a process for producing a granular material comprising prohexadione-calcium and an inorganic sulfate, comprising the fluidized bed granulation of an aqueous dispersion comprising prohexadione-calcium and an aqueous solution comprising at least one inorganic sulfate. The invention further relates to a homogeneous granular material comprising an inorganic sulfate and prohexadione-calcium, wherein the inorganic sulfate and the prohexadione-calcium are distributed homogeneously in the granular material. The present invention further relates to the use of the homogeneous granular material for regulation of the growth of plants, especially in the form of a spray liquor.

BACKGROUND

Prohexadione-calcium (calcium 3-oxido-5-oxo-4-propionylcyclohexanecarboxylate) is a cyclohexane derivative which acts as a plant growth regulator. Prohexadione-calcium inhibits particular steps in gibberellin biosynthesis, as a result of which the content of growth-active gibberellins is reduced, which leads to reduced shoot length growth in the plants treated. In addition, there is a positive effect on particular secondary metabolic processes of the plant. The use of prohexadione-calcium has especially been described for control of fireblight, or reduction of proneness to secondary fireblight of the blossom, for control of bacterial leaf spot pathogens, and for loosening of the grapestalk structure in grapevines. Additionally known from the literature are formulations of prohexadione-calcium and production processes therefor.

For instance, EP 0 598 404 discloses a composition comprising a plant growth regulator from the group of cyclohexane derivatives and a nitrogen-containing water-soluble inorganic compound or urea. The nitrogen-containing compound may, for example, be ammonium sulfate. The composition described was characterized here as a granular wettable powder.

In addition, WO 2007/042404 discloses a fungicidal and bioregulatory mixture comprising epoxiconazole and prohexadione-calcium in a synergistically effective amount. Suitable formulations mentioned here include granules, and one solid carrier material used is ammonium sulfate.

Prohexadione-calcium formulations are typically sprayed by the user, an applicable solution or suspension being produced by significant dilution with water (e.g. tap water or spring water). The absorption of prohexadione-calcium can be improved here by adding ammonium sulfate in the case of hard water. For instance, the addition of 1 to 2 kg of ammonium sulfate per 1000 L of water has been found to be useful in the case of a very high lime content in the water. In addition, suspension concentrates of prohexadione-calcium are also commercially available (for example Medax Top® with Turbo from BASF SE), which already comprise the suspension concentrate and, separately therefrom, ammonium sulfate in a combined package.

However, this way of proceeding is restricted by the fact that sulfates in conjunction with calcium salts (as from prohexadione-calcium) can form calcium sulfate hydrate precipitates (i.e. gypsum) in an aqueous medium (see also figs. 3 to 5). This makes spray application of the prohexadione-calcium formulations very difficult or impossible. A solution to this problem has already been described in the prior art in WO 2011/012495, in which a process for producing prohexadione-calcium-containing formulations which comprise large amounts of sulfates and, even in the case of dilution with hard water, are said to give a suspension having high biological efficacy is presented. This process envisages a fluidized bed granulation of an aqueous prohexadione-calcium dispersion and an inorganic sulfate not in liquid form which is to be introduced separately (typically a sulfate powder). The granular material produced has a particle form with an inorganic sulfate core and a prohexadionecalcium outer layer. However, the particles produced in this production process do not exhibit completely homogeneous distribution of prohexadione-calcium and sulfate, and the granular material produced has suboptimal solubility in aqueous suspensions, especially at low temperatures.

There is a need to provide an improved process for producing a granular material consisting of prohexadione-calcium and an inorganic sulfate, wherein the particles produced by this process have homogeneous distribution of prohexadione-calcium and sulfate, and should exhibit quicker solubility, especially at low temperatures.

SUBJECT MATTER AND SUMMARY OF THE INVENTION

The present invention solves this technical problem by a process for producing a granular material comprising prohexadione-calcium and an inorganic sulfate, wherein the process comprises the fluidized bed granulation of an aqueous dispersion comprising prohexadionecalcium and an aqueous solution comprising at least one inorganic sulfate. This process makes it possible to dispense with the use of non-liquid sulfate, i.e. especially pulverulent sulfate, during the fluidized bed granulation. The typically expected formation of insoluble precipitates (gypsum) as a result of the use of aqueous calcium and sulfate solutions surprisingly does not occur in the process of the invention. This could be attributable to the very rapid vaporization of the dispersion water during the introduction of the aqueous dispersion or sulfate solution. The process of the invention allows attainment of a homogeneous granular material with homogeneous distribution of prohexadione-calcium and sulfates. The granules produced therefore do not have the structure, known from the prior art, of a sulfate core with a prohexadione-calcium envelope, but instead have a porous matrix structure having no sulfate core. In addition, it is possible to conduct the production process continuously, which constitutes a considerable simplification of the process and generally greater throughputs compared to the conventional batchwise process. The matrix structure of the granular material and the pores present in this structure make it possible to distinctly increase the solubility of the granular material in water, especially in relatively hard water and particularly in water with a low temperature, for example below 10°C, especially at about 5°C, for production of a spray suspension, since the water can easily and quickly wet the granular material via the pore structure.

In a preferred embodiment of the process of the invention, the prohexadione-calcium dispersion and the solution of the inorganic sulfate are introduced separately into a fluidized bed chamber.

In a further preferred embodiment of the process of the invention, the prohexadione-calcium dispersion and the solution of the inorganic sulfate are introduced simultaneously into a fluidized bed chamber.

It is further preferable that the prohexadione-calcium dispersion comprises not more than 5% by weight of inorganic sulfate.

In a particularly preferred embodiment of the process of the invention, the inorganic sulfate is an ammonium sulfate or a hydrogensulfate, for example sodium hydrogensulfate or potassium hydrogensulfate.

The invention relates, in a further aspect, to a homogeneous granular material comprising inorganic sulfate and prohexadione-calcium, wherein the inorganic sulfate and the prohexadione-calcium are distributed homogeneously in the granular material and the granular material preferably has a porous matrix structure.

In a preferred embodiment of the homogeneous granular material, the inorganic sulfate is an ammonium sulfate or a hydrogensulfate, for example sodium hydrogensulfate or potassium hydrogensulfate.

In a further preferred embodiment, the homogeneous granular material of the invention comprises a further pesticide.

In a further preferred embodiment, the pesticide is a growth regulator.

The present invention further encompasses homogeneous granular materials as described above, additionally comprising an acidifier.

In a particularly preferred embodiment, the granular material of the invention comprises 1% to 30% by weight of prohexadione-calcium, 10% to 60% by weight of ammonium sulfate, optionally 1% to 50% by weight of further pesticide, and ad 100% by weight formulation auxiliaries, and optionally an acidifier.

In an additional embodiment, the invention relates to a granular material obtainable by a process as described above.

The invention relates, in a further aspect, to the use of the homogeneous granular material as described above or produced by one of the processes described above for production of a spray liquor.

In addition, the invention relates to the use of the homogeneous granular material as described above or produced by one of the processes described above for regulation of the growth of plants, and optionally additionally for increasing plant health or the control of bacterial or fungal infections of plants.

FIGURES

Fig. 1 shows particles having a sulfate core and prohexadione-calcium envelope which have been produced by the process from the prior art (WO 2011/012495). The upper image shows the particles in a size scale of 2 mm, the one below that in a size scale of 1 mm and in the lower image in a size scale of 100 pm.

Fig. 2 shows a homogeneous sulfate/prohexadione-calcium granular material having a porous matrix structure, which has been produced by the process of the invention. The upper image shows the particles in a size scale of 2 mm, the one below that in a size scale of 1 mm and in the lower image in a size scale of 100 pm.

Fig. 3 shows results of studies of particle formation with aqueous 5% prohexadione-calcium/sulfate mixtures immediately after the mixing of the constituents. It is found that particle formation sets in immediately.

Fig. 4 shows results of studies of particle formation with aqueous 5% prohexadione-calcium/sulfate mixtures 5 minutes after the mixing of the constituents. It is found that particle formation has advanced. In addition, the average particle size has risen.

Fig. 5 shows results of studies of particle formation with aqueous 5% prohexadione-calcium/sulfate mixtures 30 minutes after the mixing of the constituents. It is found that particle formation has advanced. In addition, the average particle size has risen significantly.

Fig. 6 shows a comparison of the particle structure which arises from the conventional production process in the prior art (A) and the process of the invention (B). In fig. 6A, the core/shell structure of the conventional granular material is apparent; in other words, ingredients have been coated here onto an ammonium sulfate core. The rate-determining step for the dissolution of the particle in water is the compact ammonium sulfate core (the dissolution may be delayed under unfavorable conditions (for example cold water, low stirring agitation)). Fig. 6B shows a schematic of the matrix structure with pores in the case of homogeneous distribution of the ingredients. The water here, as a result of the porous structure, is able to more quickly wet all areas, which significantly increases dispersibility, especially at low temperatures.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a process for producing a granular material comprising prohexadione-calcium and an inorganic sulfate, wherein the process comprises the fluidized bed granulation of an aqueous dispersion comprising prohexadione-calcium and an aqueous solution comprising at least one inorganic sulfate.

The invention is described hereinafter with reference to specific embodiments, but is not restricted to these embodiments.

There follows an elucidation of some of the terms that are important to the understanding of the invention.

The word “a” used in the singular in the context of the embodiments which follow and the claims likewise encompasses plural forms, unless a specific definition departs from this. In addition, the term “roughly” or “about” refers to intervals of accuracy which will be understood by the person skilled in the art to the effect that the technical effect of the invention is still achieved within these intervals. Typically, these terms refer to a deviation from the given value by ± 20%, preferably by ± 15%, further preferably by ± 10%, most preferably by ± 5%. In addition, the terms “comprising” and “containing” should not be understood in a limiting manner. The expression “consisting of should be understood as a preferred embodiment of the term “comprising” or “containing”. Should a group comprising a certain number of embodiments be defined hereinafter, this likewise means that this group likewise preferably consists of these embodiments.

The terms “firstly” or “first”, “secondly” or “second”, “thirdly” or “third”, “(a)”, “(b)”, “(c)”, “(d)” etc. in the description and the claims are used in order to distinguish between similar elements, but should not necessarily be interpreted as a restriction or sequence in time. The corresponding elements may thus be exchangeable under certain conditions. The embodiments containing these elements may thus likewise be executed in a sequence which does not correspond to the sequence of elements mentioned, unless specific definitions stipulate anything different.

Should the terms “firstly” or “first”, “secondly” or “second”, “thirdly” or “third”, “(a)”, “(b)”, “(c)”, “(d)” etc. relate to process steps or use steps, etc., there is no prescribed relationship in time between these steps. In other words, the steps may be executed simultaneously, or there may be time intervals of seconds, minutes, hours, days, weeks or years between the steps, unless a definition in the description prescribes specific intervals.

Furthermore, the invention is not limited to specific batches, protocols, reagents etc. as described hereinafter, since these can possibly change. Moreover, the terminology used hereinafter shall apply only to the description of the embodiments, but not limit the scope of protection of the invention, since the latter is defined solely by the appended claims. Unless defined otherwise, all technical and scientific terms which are used in this description have the meaning which is usually attributed to them by the person of average skill in the art.

As laid out above, the present invention relates, in one aspect, to a process for producing a granular material comprising prohexadione-calcium and an inorganic sulfate, wherein the process comprises the fluidized bed granulation of an aqueous dispersion comprising prohexadione-calcium and an aqueous solution comprising at least one inorganic sulfate.

Fluidized bed granulation is a well-studied method of producing granular materials. Suitable systems and modes of operation have been described, for example, by Rosch and Probst, Verfahrenstechnik 1975 (9), 59-64 or in EP 0 799 569. A preferred system is sold by DMA Prozesstechnologie in the form of the WFP-Koni multifunctional system (http://www.dmr-prozess.com/). A fluidized bed granulator typically comprises a fluidizing chamber having a sieve tray made from a perforated metal sheet. Heatable fluidizing gas having a particular inlet temperature and flow rate flows through the sieve tray into the fluidizing chamber. By means of a nozzle, liquids or dispersions can be sprayed into the fluidizing chamber.

In the process of the invention comprising the fluidized bed granulation of an aqueous dispersion comprising prohexadione-calcium and an aqueous solution comprising at least one inorganic sulfate, the dispersion and the solution are typically introduced into a fluidized bed chamber. The introduction is usually effected by spraying the dispersion and the solution into a fluidized bed.

The dispersion and the solution are usually sprayed via two or more nozzles, for example two-or three-phase nozzles. Preferably, the dispersion is dried by means of two-phase nozzles with an inert gas, such as pressurized air or nitrogen, at a pressure of 1.2 to 5.0 bar and a bed temperature of 15 to 100°C.

Typically, the nozzle is mounted at a distance from the sieve tray corresponding to 1.5 to 10 times, especially 2 to 8 times, the bed height of the fluidized bed charge at rest. If the nozzle is too close above the fluidized bed or the nozzle dips into the fluidized bed, significant lump formation occurs and the fluidized bed collapses. If the distance of the nozzle from the fluidized bed is too great, the finely atomized particles have time to partly dry, such that a powder and not a granular material, but at least a product having a high dust content, is generally obtained.

The process of the invention can be implemented continuously or batchwise. The advantages of the process are especially that continuous implementation is possible by comparison with alternative processes. This continuous implementation is preferable.

Preferably, the aqueous dispersion comprising prohexadione-calcium and the aqueous solution comprising at least one inorganic sulfate are introduced separately into a fluidized bed chamber. The aqueous dispersion comprising prohexadione-calcium and the aqueous solution comprising at least one inorganic sulfate may be introduced into the fluidized bed chamber simultaneously or successively, or in an alternating sequence. It is preferable that the aqueous dispersion comprising prohexadione-calcium and the aqueous solution comprising at least one inorganic sulfate are sprayed simultaneously into the fluidized bed chambers.

Typically, heatable fluidizing gas, such as air, flows through the sieve tray into the fluidized bed chamber. The inlet temperature of the fluidizing gas is usually from 50 to 220°C, preferably from 70 to 150°C and especially from 90 to 120°C. In a further embodiment, the inlet temperature is below 130°C, preferably below 120°C, especially below 115°C.

The fluidizing gas rate per square meter of inflow area of the fluidized bed may be from 3000 to 20 000 m3/h, preferably from 6000 to 18 000 m3/h and especially 9000 to 14 000 m3/h. It is possible to work with a fluidized bed charge of 50 to 2000 kg/m2 of area of the inflow plate, preferably 100 to 1000 kg/m2. Fluidized bed charge means the “holdup” in the case of a continuous process regime, and the batch size, i.e. the fill volume at the end of granulation, in the case of a batchwise process.

The fines fractions escaping from the fluidized bed together with the offgas are separated out in a customary manner. They can be recycled into the fluidized bed as nuclei for granule formation. In this case, both internal and external recycling of fines is possible. For the separation of the fines fractions and recycling thereof, it is possible to use any apparatuses customarily used for such purposes. The finished granular material can be discharged by means of one or more suitable devices. Useful devices for this purpose include all customary devices, for example countercurrent gravitational sifters, zigzag sifters, or discharge via a flap.

The aqueous dispersion comprising prohexadione-calcium usually comprises 0.5% to 55% by weight, preferably 2% to 45% by weight, 3% to 40% by weight, 5% to 40% by weight and especially 10% to 35% by weight of prohexadione-calcium (CAS no. 127277-53-6). The invention likewise envisages, in alternative embodiments, the use of an aqueous dispersion comprising prohexadione-calcium with 5% to 15% by weight of prohexadione-calcium (CAS no. 127277-53-6). Particular preference is given to the use of an aqueous dispersion comprising prohexadione-calcium having about 35% by weight of prohexadione-calcium (CAS no. 127277-53-6).

As well as prohexadione-calcium (CAS no. 127277-53-6), the aqueous dispersion comprising prohexadione-calcium may comprise further substances. For example, the dispersion may comprise inorganic sulfate. Preferably, the aqueous dispersion comprising prohexadione-calcium comprises not more than 5% by weight, preferably not more than 0.5% by weight and especially not more than 0.05% by weight of inorganic sulfate.

The prohexadione-calcium dispersion may be in the form of an emulsion or suspension. Preference is given to the dispersion of a suspension, for example a suspension of prohexadione-calcium.

The prohexadione-calcium dispersion may, in particular embodiments, as well as prohexadione-calcium, comprise further, such as one or two or more, pesticides. Owing to different physicochemical properties of pesticides or pesticide classes, it may be necessary to produce prohexadione-calcium dispersions with pesticides in a different manner, matched, for example, to the pesticides or pesticide classes or the physicochemical properties thereof. These processes may take account, for example, of a liquid, oily or resinous character of the pesticides. The adaptation of the process may comprise, for example, the introduction of further process steps, for instance an emulsification step or the like. In the case of biological fungal control agents or plant fortifiers or heat-sensitive pesticides, the temperatures of the fluidized bed granulation may, for example, be adjusted, i.e. lowered to a value harmless to the organisms or substances. Alternatively, heat-absorbing components can be added, in order to prevent damage to the organisms. In addition, the biological or heat-sensitive pesticides can be added or blended subsequently. Details of such processes and the application thereof to the pesticides or pesticide classes described herein are known to those skilled in the art and can be found from standard publications in this sector.

The term “pesticide” refers to at least one active ingredient selected from the group of the fungicides, insecticides, nematicides, herbicides, safeners and/or growth regulators. Preferred pesticides are fungicides, insecticides, herbicides and growth regulators. Particularly preferred pesticides are growth regulators. It is also possible to use mixtures of pesticides from two or more of the aforementioned classes. The person skilled in the art is familiar with such pesticides, which can be found, for example, in Pesticide Manual, 15th Ed. (2009), The British Crop Protection Council, London.

The following list of pesticides is intended to illustrate but not limit the possible combinations: A) Strobilurins: azoxystrobin, dimoxystrobin, coumoxystrobin, coumethoxystrobin, enestroburin, fluoxastrobin, kresoxim methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, trifloxystrobin, methyl 2-[2-(2,5-dimethylphenyloxymethyl)phenyl]-3-methoxyacrylate, 2-(2-(3-(2,6-dichlorophenyl)-1-methylallylideneaminooxymethylphenyl)-2-methoxyimino-N-methylacetamide; B) Carboxamides: - carboxanilides: benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, flutolanil, fluxapyroxad, furametpyr, isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4-methyl-thiazole-5-carboxanilide, N-(4'-trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-(2-(1,3,3-trimethylbutyl)phenyl)-1,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide; - carboxylic morpholides: dimethomorph, flumorph, pyrimorph; - benzoamides: flumetover, fluopicolide, fluopyram, zoxamide; - other carboxamides: carpropamid, diclocymet, mandipropamid, oxytetracyclin, silthiofam, N-(6-methoxypyridin-3-yl)cyclopropanecarboxamide; C) Azoles: - triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole; - imidazoles: cyazofamid, imazalil, imazalil sulfate, pefurazoate, prochloraz, triflumizole; - benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole; - others: ethaboxam, etridiazole, hymexazole, 2-(4-chlorophenyl)-N-[4-(3,4-dimethoxy-phenyl)isoxazol-5-yl]-2-prop-2-ynyloxyacetamide; D) Nitrogen-containing heterocyclyl compounds: - pyridines: fluazinam, pyrifenox, 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]-pyridine, 3-[5-(4-methylphenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine; - pyrimidines: bupirimat, cyprodinil, diflumetorim, fenarimol, ferimzone, mepanipyrim, nitrapyrin, nuarimol, pyrimethanil; - piperazines: triforine; - pyrroles: fludioxonil, fenpiclonil; - morpholines: aldimorph, dodemorph, dodemorphacetat, fenpropimorph, tridemorph; - piperidines: fenpropidin; - dicarboximides: fluorimid, iprodione, procymidone, vinclozolin; - nonaromatic 5-membered heterocyclic rings: famoxadone, fenamidone, flutianil, octhilinone, probenazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydropyrazol-1-thiocarboxylic acid S-allyl ester; - others: acibenzolar-S-methyl, amisulbrom, anilazin, blasticidin-S, captafol, captan, chinomethionat, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat methylsulfate, fenoxanil, folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quinoxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo-3-propylchromen-4-one, 5-chloro-1-(4,6-dimethoxypyrimidin-2-yl)-2-methyl-1 H-benzimidazole, 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine, 5-ethyl-6-octyl[1 ,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; E) Carbamates and dithiocarbamates: thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasulfocarb, metiram, propineb, thiram, zineb, ziram; carbamates: diethofencarb, benthiavalicarb, iprovalicarb, propamocarb, propamocarb hydrochloride, valiphenal, 4-fluorophenyl N-(1-(1-(4-cyanophenyl)ethanesulfonyl)-but-2-yl)-carbamate; R Other fungicides: guanidines: dodine, dodine free base, guazatin, guazatine acetate, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate); antibiotics: kasugamycin, kasugamycin hydrochloride hydrate, polyoxine, streptomycin, validamycin A; nitrophenyl derivatives: binapacryl, dicloran, dinobuton, dinocap, nitrothal-isopropyl, tecnazene; organometallic compounds: fentin salts, for example fentin acetate, fentin chloride, fentin hydroxide; sulfur-containing heterocyclyl compounds: dithianone, isoprothiolane; organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, iprobenfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl; organochlorine compounds: chlorthalonil, dichlofluanid, dichlorphen, flusulfamide, hexachlorobenzene, pencycuron, pentachlorphenol and its salts, phthalide, quintozene, thiophanate-methyl, tolylfluanide, N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfon-amide; inorganic active ingredients: phosphorous acid and its salts, Bordeaux mixture, copper salts, for example copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; biological fungal control agents, plant fortifiers: Ampelomyces quisqualis (for example the AQ 1 O® product from Intrachem Bio GmbH & Co. KG, Germany), Aspergillus flavus (for example the AFLAGUARD® product from Syngenta, Switzerland), Aureobasidium pullulans (for example the BOTECTOR® product from bio-ferm GmbH, Germany), Bacillus pumilus (e.g. strain NRRL no. B-30087 in SONATA® and BALLAD® Plus from AgraQuest Inc., USA),

Bacillus subtilis (e.g. strain NRRL-Nr. B-21661 in RHAPSODY®, SERENADE® MAX and SERENADE® ASO from AgraQuest Inc., USA), Bacillus subtilis var. amyloliquefaciens FZB24 (for example the TAEGRO® product from Novozyme Biologicals, Inc., USA), Candida oleophila 1-82 (for example the ASPIRE® product from Ecogen Inc., USA), Candida saitoana (for example the BIOCURE® (mixed with lysozyme) and BIOCOAT® products from MicroFlo Company, USA (BASF SE) and Arysta), chitosan (e.g. ARMOUR-ZEN from BotriZen Ud., New Zealand), Clonostachys rosea f. catenulata, also called Gliocladium catenulatum (e.g. strain J1446: PRESTOp® from Verdera, Finland), Coniothyrium minitans (for example the CONTANS® product from Prophyta, Germany), Cryphonectria parasitica (for example the Endothia parasitica product from CNICM, France), Cryptococcus albidus (for example the YIELD PLUS® product from Anchor Bio-Technologies, South Africa), Fusarium oxysporum (for example the BIOFOX® products from S.I.A.P.A., Italy, and FUSACLEAN® from Natural Plant Protection, France), Metschnikowia fructicola (for example the SHEMER® product from Agrogreen, Israel), Microdochium dimerum (for example the ANTI BOT® product from Agrauxine, France), Phlebiopsis gigantea (for example the ROTSOp® product from Verdera, Finland), Pseudozyma flocculosa (for example the SPORODEX® product from Plant Products Co. Ud., Canada), Pythium oligandrum DV74 (for example the POLYVERSUM® product from Remeslo SSRO, Biopreparaty, Czech Republic), Reynoutria sachlinensis (for example the REGALIA® product from Marrone Bioinnovations, USA), Talaromyces flavus V117b (for example the PROTUS® product from Prophyta, Germany), Trichoderma asperellum SKT-1 (for example the ECO-HOPE® product from Kumiai Chemical Industry Co., Ud., Japan), T. atroviride LC52 (for example the SENTINEL® product from Agrimm Technologies Ud, New Zealand), T. harzianum T-22 (for example the PLANTSHIELD® product from BioWorks Inc., USA), T. harzianum TH 35 (for example the ROOT PRO® product from Mycontrol Ud., Israel), T. harzianum T-39 (for example the TRICHODEX® and TRICHODERMA 2000® products from Mycontrol Ud., Israel and Makhteshim Ud., Israel), T. harzianum and T. viride (for example the product TRICHOPEL from Agrimm Technologies Ud, New Zealand), T. harzianum ICC012 and T. viride ICC080 (for example the REMEDIER® WP product from Isagro Ricerca, Italy), T. polysporum and T. harzianum (for example the BINAB® product from BINAB Bio-Innovation AB, Sweden), T. stromaticum (for example the TRICOVAB® product from C.E.P.L.A.C., Brazil), T. virens GL-21 (for example the SOILGARD® product from Certis LLC, USA), T. viride (for example the TRIECO® products from Ecosense Labs. (India) Pvt. Ud., India and BIO-CURE® F from T. Stanes & Co. Ud., India), T. viride TV1 (for example the T. viride TV1 product from Agribiotec srl, Italy), Ulocladium oudemansii HRU3 (for example the BOTRY-ZEN® product from Botry-Zen Ud, New Zealand); others: biphenyl, bronopol, cyflufenamide, cymoxanil, diphenylamine, metrafenone, pyriofenone, mildiomycin, oxine-copper, spiroxamine, tolylfluanide, N-(cyclopropylmethoxy-imino(6-difluoromethoxy-2,3-difluorophenyl)methyl)-2-phenylacetamide, N'-(4-(4-chloro-3-trifluoromethylphenoxy)-2,5-dimethylphenyl)-N-ethyl-N-methylformamidine, N'-(4-(4-fluoro-3-trifluoromethylphenoxy)-2,5-dimethylphenyl)-N-ethyl-N-methylformamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanylpropoxy)phenyl)-N-ethyl-N-methylformamidine, N'-(5- difluoromethyl-2-methyl-4-(3-trimethylsilanylpropoxy)phenyl)-N-ethyl-N-methylformamidine, 2-N-methyl-N-(1,2,3,4-tetrahydronaphthalen-1-yl)-{1-[2-(5-methyl-3-trifluoromethylpyrazol-1-yl)-acetyl]piperidin-4-yl}thiazole-4-carboxamide, N-methyl-N-(R)-1,2,3,4-tetrahydronaphthalen-1-yl-2-{1-[2-(5-methyl-3-trifluoromethylpyrazol-1-yl)acetyl]piperidin-4-yl}thiazole-4-carboxamide, 6-tert-butyl-8-fluoro-2,3-dimethylquinolin-4-yl acetate, 6-tert-butyl-8-fluoro-2,3-dimethylquinolin-4-yl methoxyacetate, N-methyl-2-{1-[2-(5-methyl-3-trifluoromethyl-1 H-pyrazol-1-yl)acetyl]-piperidin-4-yl}-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamide; G) Growth regulators: abscisic acid, amidochlor, ancymidol, 6-benzylaminopurin, brassinolid, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfid, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), metconazole, naphthaleneacetic acid, N-6-benzyladenine, paclobutrazole, prohydrojasmone, thidiazurone, triapenthenol, tributyl phosphorotrithioate, 2,3,5-triiodobenzoic acid, trinexapac-ethyl and uniconazole; H) Herbicides: - acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor; - amino acid analogs: bilanafos, glyphosate, glufosinate, sulfosate; - aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl; - bipyridyls: diquat, paraquat; - carbamates and thiocarbamates: asulam, butylate, carbetamide, desmedipham, dimepiperat, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate; - cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim; - dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin; - diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen; - hydroxybenzonitriles: bromoxynil, dichlobenil, ioxynil; - imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr; - phenoxyacetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, mecoprop; - pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate; - pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr; - sulfonylureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, lodosulfuron, mesosulfuron, metsulfuron methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1-((2-chlor-6-propylimidazo[1,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea; - triazines: ametryn, atrazin, cyanazin, dimethametryn, ethiozin, hexazinon, metamitron, metribuzin, prometryn, simazin, terbuthylazin, terbutryn, triaziflam; - ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, methabenzthiazuron, tebuthiuron; - other inhibitors of acetolactate synthase: bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, orthosulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfon, pyroxsulam; - others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarbazone, benfluresat, benzofenap, bentazone, benzobicyclon, bromacil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon ethlyl, chlorthai, cinmethylin, clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, fluorochloridone, flurtamon, indanofan, isoxaben, isoxaflutol, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methylarsonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefon, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotol, pyrazoxyfen, pyrazolynat, quinoclamine, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, 4-hydroxy-3-[2-(2-methoxy-ethoxymethyl)-6-trifluoromethylpyridin-3-carbonyl]bicyclo[3.2.1 ]oct-3-en-2-one, ethyl (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)phenoxy]-pyridin-2-yloxy)-acetate, methyl 6-amino-5-chloro-2-cyclopropylpyrimidin-4-carboxylate, 6-chlor-3-(2-cyclopropyl-6-methylphenoxy)pyridazin-4-ol, 4-amino-3-chloro-6-(4-chlor-phenyl)-5-fluoropyridine-2-carboxylic acid, methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)pyridine-2-carboxylate and methyl 4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluorophenyl)pyridine-2-carboxylate; I) Insecticides: - organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methylparathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon; - carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate; - pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerat, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin, - inhibitors of insect growth: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentezine; b) ecdyson antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat; - nicotine receptor agonists/antagonists: clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1-(2-chlorothiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-[1,3,5]-triazinane; - GABA antagonists: endosulfan, ethiprol, fipronil, vaniliprol, pyrafluprol, pyriprol, 5-amino-1-(2 ,6-dichloro-4-methylphenyl)-4-sulfinamoyl-1H-pyrazol-3-thiocarboxamide; - macrocyclic lactones: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram; - mitochondrial electron transport chain inhibitor (METI) I; - acaricides: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim; - METI II and III substances: acequinocyl, fluacyprim, hydramethylnon; - decouplers: chlorfenapyr; - inhibitors of oxidative phosphorylation: cyhexatin, diafenthiuron, fenbutatin oxide, propargite; - inhibitors of insect ecdysis: cyromazine; - inhibitors of "mixed function oxidases": piperonyl butoxide; - sodium channel blockers: indoxacarb, metaflumizone; others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozin, sulfur, thiocyclam, flubendiamide, chlorantraniliprol, cyazypyr (HGW86); cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron and pyrifluquinazon.

Preferably, the prohexadione-calcium dispersion comprises a further growth regulator. Preferred growth regulators are abscisic acid, ancymidol, aviglycine, 6-benzylaminopurine, brassinolide, chlormequat chloride, choline chloride, cyclanilide, diflufenzopyr, dikegulac, ethephon, flurprimidol, forchlorfenuron, gibberellins Ai, A3, A4, A7, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat chloride, metconazole, 1-methylcyclopropene, naphthalene-acetic acid, paclobutrazole, prohydrojasmone, tebuconazole, thidiazuron, triapenthenol, 2,3,5-triiodobenzoic acid, trinexapac-ethyl and uniconazole. More preferably, the growth regulators are mepiquat chloride, chlormequat chloride or ethephon. In a particularly preferred embodiment, the prohexadione-calcium dispersion comprises mepiquat chloride.

In a specific embodiment, the prohexadione-calcium dispersion is free of pesticides that are not growth regulators. Preferably, the prohexadione-calcium dispersion comprises 1% to 70% by weight, preferably 15% to 60% by weight and especially 25% to 40% by weight of a further growth regulator. A particularly preferred example of a further growth regulator is mepiquat chloride.

The prohexadione-calcium dispersion may comprise further formulation auxiliaries, the choice of auxiliaries typically being directed by the specific form of application. Examples of suitable formulation auxiliaries are solvents, solid carriers, surface-active substances (such as surfactants, protective colloids, dispersants, wetters and stickers), organic and inorganic thickeners, bactericides, antifreezes, defoamers, optionally dyes and adhesives (for example for seed treatment).

Useful surface-active substances include, for example as a surfactant, dispersant or wetting agent, the alkali metal, alkaline earth metal or ammonium salts of aromatic sulfonic acids, for example of lignosulfonic acids (Borresperse® products, Borregaard, Norway), of phenol- and naphthalenesulfonic acids (Morwet® products, Akzo Nobel, USA) and of dibutylnaphthalenesulfonic acid (Nekal® products, BASF, Germany), and also of fatty acids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and derivatives thereof with formaldehyde, condensation products of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl and tri butyl phenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors, lignosulfonates, proteins, denatured proteins, polysaccharides (e.g. methyl cellulose), hydrophobically modified starches, polyvinyl alcohol (Mowiol® products, Clariant, Switzerland), polycarboxylates (Sokalan® products, BASF, Germany), polyalkoxylates, polyvinylamine (Lupamin® products, BASF, Germany), polyethyleneimine (Lupasol® products, BASF, Germany), polyvinylpyrrolidone and copolymers thereof. Preference is given to lignosulfonates.

Useful surfactants include particularly anionic, cationic, nonionic and amphoteric surfactants, block polymers and polyelectrolytes. Suitable anionic surfactants are alkali metal, alkaline earth metal or ammonium salts of sulfonates, sulfates, phosphates or carboxylates. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefinsulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of condensed naphthalenes, sulfonates of decyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.

Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates and carboxylated alcohol or alkylphenol ethoxylates. Preferred surfactants are anionic surfactants, more preferably alkali metal, alkaline earth metal or ammonium salts of sulfonates, especially alkali metal salts of sulfonates of naphthalenes and alkylnaphthalenes.

Suitable nonionic surfactants are alkoxylates, N-alkylated fatty acid amides, amine oxides, esters or sugar-based surfactants. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated. Alkoxylation can be accomplished using ethylene oxide and/or propylene oxide, preferably ethylene oxide. Examples of N-alkylated fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol monoesters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose esters and glucose esters, or alkyl polyglycosides. Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds having one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are block polymers of the A-B or AB-A type comprising blocks of polyethylene oxide and polypropylene oxide or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali metal salts of polyacrylic acid. Examples of polybases are polyvinylamines or polyethyleneamines.

Suitable dispersants may be selected from the abovementioned surface-active substances. Preferred dispersants are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example of ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, condensation products of sulfonated naphthalene and derivatives thereof with formaldehyde, condensation products of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, lignosulfite waste liquors, and lignosulfonates.

The prohexadione-calcium dispersion may, in specific embodiments, comprise high amounts of surface-active substances and surfactant. It may comprise a total amount of 0.1% to 40% by weight, preferably 1% to 30% by weight and especially 2% to 20% by weight of surface-active substances and surfactants, based on the total amount of the composition.

Examples of adjuvants are organically modified polysiloxanes such as BreakThru S 10 240®; alcohol alkoxylates such as Atplus®245, Atplus®MBA 1303, Plurafac®LF and Lutensol® ON; EO-PO block polymers, for example Pluronic® RPE 2035 and Genapol® B; alcohol ethoxylates, for example Lutensol® XP 80; and sodium dioctylsulfosuccinate, e.g. Leophen® RA.

Examples of thickeners (i.e. compounds which impart modified flow characteristics to the composition, i.e. high viscosity at rest and low viscosity in the mobile state) are polysaccharides and organic and inorganic laminar minerals such as xanthan gum (Kelzan®, CP Kelco), Rhodopol® 23 (Rhodia) or Veegum® (R.T. Vanderbilt) or Attaclay® (Engelhard Corp.).

Solid carrier materials may, for example, be: a) inorganic compounds: mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, attapulgite, montmorillonite, mica, vermiculite, synthetic silicas, amorphous silicas and synthetic calcium silicates or mixtures thereof; b) organic compounds: ground polymers, fertilizers such as ammonium phosphate, ammonium nitrate, thiourea and urea, vegetable products such as cereal meals, tree bark, wood and nutshell meal, cellulose powder.

The solid carriers can also be used as aggregate formers, such as silicas. Therefore, aggregate formers in the context of the present invention are solid carriers. A preferred solid carrier is an inorganic compound, particular preference being given to silica, especially precipitated silica.

The median particle size of the silica d50 (determined via laser diffraction, for example with Malvern Mastersizer) may be in the range from 0.1 to 100 pm, preferably from 0.5 to 20 pm and especially 1 to 10 pm. The specific surface area may be in the range from 1 to 500 m2/g, preferably 10 to 100 m2/g (determined by means of an areameter analogously to ISO 5794-1, Annex D).

The aqueous solution comprising at least one inorganic sulfate comprises an inorganic sulfate in a concentration just below the saturation point of the sulfate. The inorganic sulfate is preferably soluble in water at 20°C to an extent of at least 1 g/L, preferably to an extent of at least 100 g/L, further preferably to an extent of at least 400 g/L.

Suitable inorganic sulfates are sulfates of metal ions or of quaternary nitrogen compounds (such as ammonium). Preferred inorganic sulfates are ammonium sulfate, and also hydrogensulfates. Suitable hydrogensulfates are salts comprising the anion HSOt, for example alkali metal or ammonium salts. Preferred hydrogen sulfates are sodium hydrogensulfate, ammonium hydrogensulfate, and potassium hydrogensulfate.

The saturation point of the inorganic sulfates differs from molecule to molecule and the concentration of the sulfate can or has to be adjusted appropriately. Examples of saturation points of preferred inorganic sulfates in water at 20°C are 754 g/L for ammonium sulfate, 490 g/L for potassium hydrogensulfate and 1080 g/L in the case of sodium hydrogensulfate.

The concentration to be chosen for ammonium sulfate in the aqueous solution at a temperature of 20°C is 150 g/L to 750 g/L, preferably 400 g/L to 750 g/L, further preferably 600 g/L to 750 g/L. Most preferred is a small range just below the solubility limit of about 680 g/L to 750 g/L or 680 g/L to 740 g/L, or 680 g/L to 730 g/L, or 680 g/L to 720 g/L, or 680 g/L to 710 g/L, or 680 g/L to 700 g/L.

The concentration to be chosen for potassium hydrogensulfate in the aqueous solution at a temperature of 20°C is 50 g/L to 485 g/L, preferably 100 g/L to 485 g/L, further preferably 300 g/L to 485 g/L. Most preferred is a small range just below the solubility limit of about 400 g/L to 485 g/L or 400 g/L to 475 g/L, or 400 g/L to 465 g/L, or 400 g/L to 455 g/L, or 400 g/L to 445 g/L, or 400 g/L to 435 g/L.

The concentration to be chosen for sodium hydrogensulfate in the aqueous solution at a temperature of 20°C is 450 g/L to 1075 g/L, preferably 650 g/L to 1075 g/L, further preferably 850 g/L to 1075 g/L. Most preferred is a small range just below the solubility limit of about 1000 g/L to 1075 g/L or 1000 g/L to 1065 g/L, or 1000 g/L to 1055 g/L, or 1000 g/L to 1045 g/L, or 1000 g/L to 1035 g/L, or 1000 g/L to 1025 g/L.

For other inorganic sulfates which can likewise be used, it is easily possible to determine or infer from the literature the saturation point in water at 20°C. For these too, the abovementioned ranges from 5 up to 600 g/L below the saturation point are applicable, and preferably from about 5 to 75 g/L below the saturation point.

In further embodiments of the invention, the aqueous solution comprising at least one inorganic sulfate may comprise additional constituents or auxiliaries. For example, a pesticide as defined above may be present in the sulfate solution. Preferably, water-soluble pesticides may be present in the sulfate solution. Such water-soluble pesticides may, for example, be of the salt type. By virtue of the addition of salt-type pesticides or other additives to aqueous solutions comprising an inorganic sulfate, the fluidized bed granulation process of the invention can advantageously avoid problems which can arise in the conventional prior art processes as a result of an excessively high salt content in the prohexadione-calcium dispersions (for example disrupted dispersion as a result of an excessively high salt burden) or which make it impossible to use or combine particular additions of pesticides or other substances in the conventional prior art processes. The inventive addition of salt-type pesticides or other additives to aqueous solutions comprising an inorganic sulfate thus enables processing of combinations of substances that have been incompatible to date, especially incompatible combinations of pesticides, to give a homogeneous granular material by the fluidized bed granulation process described herein. Examples of such incompatible substances are chemically incompatible substances and/or physically incompatible substances which typically react unintentionally with one another in a common, for example liquid, or dynamic environment. This can lead, for instance, to unwanted formation of cocrystals or to conglutination of the substances or trigger other adverse effects. By means of the process of the invention as described above, it is possible to avoid such effects.

The present invention relates, in a further aspect, to a homogeneous granular material comprising an inorganic sulfate and prohexadione-calcium. The inorganic sulfate and the prohexadione-calcium are distributed homogeneously in the granular material. The inorganic sulfate may be a sulfate of metal ions or of quaternary nitrogen compounds (such as ammonium). Preferred inorganic sulfates in the granular material are ammonium sulfate, and also hydrogensulfates, especially the preferred sodium hydrogensulfate, ammonium hydrogensulfate, and potassium hydrogensulfate.

The homogeneous granular material may comprise one or more particles. The particles comprise inorganic sulfate and the prohexadione-calcium, distributed homogeneously in the particles. Typically, the term “granular material” relates to an individual particle comprising inorganic sulfate and the prohexadione-calcium in uniform or homogeneous distribution.

The term “homogeneity”, as used in connection with the granular material or particles, refers to a homogeneous, decentralized distribution of the inorganic sulfate and prohexadione-calcium components in the granular material or particles. This means that, in every spatial sector of the granular material/particle, the same or approximately the same ratio of inorganic sulfate and prohexadione-calcium may be discovered. An “approximately equal ratio” is understood to mean a ratio in any spatial sector 1 which differs by not more than 15%, 12%, 10%, preferably not more than 8%, 6%, 5%, 4%, 3%, 2% or more preferably not more than 1% or less than 1% of the mixing ratio of the components of the granular material in any other selected spatial sector 2.

This ratio corresponds in principle to the mixing ratio used for the production of the granular material. In specific embodiments, the ratio in any spatial sectors of the granular material may differ by not more than 15%, 12%, 10%, preferably not more than 8%, 6%, 5%, 4%, 3%, 2% or more preferably not more than 1% or less than 1% from the mixing ratio used for the production of the granular material.

In this way, the granular material of the invention differs from the granular material as described in WO 2011/012495, since the structure therein is a core-shell structure, meaning that the same or approximately the same ratio of inorganic sulfate and prohexadione-calcium is not present in all spatial sectors. Instead, exclusively sulfate is present in the core, while exclusively prohexadione-calcium is present in the shell.

Homogeneity in the granules/particles as described above, in specific embodiments, likewise exists in the case of more complex mixtures or the presence of additional components. These additional components are thus likewise present in uniform or virtually uniform distribution together with inorganic sulfate and prohexadione-calcium in the entirety of the granules/particles.

The particles may have a spheroidal, rounded or bulb-like shape. Usually, the particles have bulges, rounded elements and large cavities or depressions. On the surface there are typically structure reliefs in platelet form in an irregular arrangement. Figure 2 shows these forms in various magnifications. However, the particles in the individual case may differ in shape from the shapes shown and described, for example as a result of the presence of further or different components, the use of different inorganic sulfates, differences in the production process, etc.

The particle size or grain size of the granular material may be from 10 to 10 000 pm, preferably from 50 to 5000 pm, and more preferably from 200 to 2500 pm.

The grain size can be determined by sieving (for example in accordance with DIN 66165). Typically at least 70% by weight, preferably at least 90% by weight, of the particles of granular material have this particle size. The particle size of the granular material can be determined by modern laser diffraction methods (such as Malvern), or preferably with the aid of conventional fractionating methods, such as a sieving tower.

The granular material of the invention preferably has a porous matrix structure. Typically, all the particles of the granular material have a porous matrix structure. The term "porous matrix" refers to a three-dimensional structure having pores or orifices. The pores or orifices may take the form of a meshwork or network in the entirety of the particles or in portions of the particles. The pores may have different sizes. For instance, pores may have a diameter of 2%, 3%, 5%, 10%, 15%, 20%, 30%, 40%, or 50%, 100%, 200%, 400%, or more than 1000% of the diameter of other pores. The pore diameter may, for example, be 0.5 pm to 100 pm, for instance 1 pm, 2pm, 5 pm, 8 pm, 10 pm, 12 pm, 15 pm, 18 pm, 20 pm, 22 pm, 25 pm, 30 pm, 35 pm, 40 pm, 45 pm, 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 85 pm, 90 pm, 95 pm, or 100 pm. The pore diameter is preferably between 10 and 30 pm.

The porous character of the granules or particles may be apparent at the surface or within the entirety or essentially the entirety of the particles. In specific embodiments, the granular material has a porous matrix in one, more than one or all regions of the surface, but is nonporous or only partly porous in the core region. The partial porosity may also occur in other regions of the particles. In other embodiments, the porous matrix structure exists in the entirety or essentially the entirety of the particles.

The pores may have different forms. They may be irregular, round, curved, alveolar, flat, approximately trigonal, approximately tetragonal, approximately hexagonal, etc. Typically, the pores do not have a homogeneous form, but exhibit a mixture of various types of form. Purely geometric forms are barely present, if at all. The pores may have orifices in one direction, for example in the direction of an x, y or z axis, or in two or more directions.

The pores are typically distributed irregularly in the granules or particles, meaning that regions having many pores may alternate with regions having few pores, if any.

The homogeneous granular material may, in particular embodiments, comprise a further pesticide. Likewise envisaged is the presence of more than one further pesticide, for example two, three or more pesticides. The pesticides may be selected from the list of pesticides given above. It is preferable that the pesticide is a further growth regulator. Preferred growth regulators are abscisic acid, ancymidol, aviglycine, 6-benzylaminopurine, brassinolide, chlormequat chloride, choline chloride, cyclanilide, diflufenzopyr, dikegulac, ethephon, flurprimidol, forchlorfenuron, gibberellins Ai, A3, A4, A7, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat chloride, metconazole, 1-methylcyclopropen, naphthaleneacetic acid, paclobutrazole, prohydrojasmone, tebuconazole, thidiazuron, triapenthenol, 2,3,5-triiodobenzoic acid, trinexapac-ethyl and uniconazole. Particular preference is given to the growth regulator mepiquat chloride, chlormequat chloride or ethephon. In a particularly preferred embodiment, the granular material comprises mepiquat chloride.

Preferably, the granular material comprises 1% to 70% by weight, preferably 15% to 60% by weight and especially 25% to 40% by weight of a further growth regulator, such as mepiquat chloride.

The granular material may further comprise one or more of the abovementioned formulation auxiliaries: A preferred solid carrier is an inorganic compound, more preferably silica, especially precipitated silica. The granular material may comprise 0.5% to 50% by weight, preferably 1% to 30 and especially 5% to 15% by weight of solid carrier.

Preferred surface-active substances are alkali metal, alkaline earth metal or ammonium salts of sulfonates, such as lignosulfonates, and sulfonates of naphthalenes and alkylnaphthalenes.

The granular material preferably comprises a mixture of at least two different surface-active substances. Preferably, the granular material comprises at least two different sulfonates. The granular material may comprise 0.5% to 40% by weight, preferably 2% to 25% and especially 5% to 20% by weight of surface-active substances. Preferably, the granular material comprises 0.5% to 40% by weight, preferably 2% to 25% and especially 5% to 20% by weight of lignosulfonate.

Preferred defoamers are silicone-based defoamers. The granular material may comprise 0.1% to 5% by weight of defoamer.

The granular material may optionally further comprise an acidifier. The acidifier is a usually solid chemical. The melting point is usually at least 50°C, preferably at least 100°C and especially at least 150°C.

In a further preferred embodiment, the acidifier is soluble at 20°C in water to an extent of at least 50 g/L, more preferably to an extent of at least 150 g/L and especially to an extent of at least 300 g/L. The granular material may comprise up to 35% by weight, preferably up to 25% by weight and especially up to 15% by weight of acidifier. A preferred solid acidifier is a carboxylic acid having two to 20 carbon atoms, a hydrogensulfate or a hydrogenphosphate. Mixtures of the aforementioned acidifiers are likewise possible. In a further preferred embodiment, the acidifier is a carboxylic acid having two to six carbon atoms (especially oxalic acid), a hydrogensulfate or a hydrogenphosphate. In a further preferred embodiment, the acidifier is a hydrogensulfate or a hydrogenphosphate.

The carboxylic acid may be a linear, branched or cyclic carboxylic acid having two to 20 carbon atoms. The carboxylic acid usually comprises at least one carboxylic acid group (-COOH), for example one, two or three. The carboxylic acid comprises two to 20 carbon atoms, preferably two to 12 and especially two to 8 carbon atoms. It may, as well as carboxylic acid groups, have further functional groups such as alcohol groups. Usually, the carboxylic acid has at least one carboxylic acid group having a pKa at 20°C in the range from 0.5 to 6.0, preferably from 1.0 to 3.5. Examples of carboxylic acids having two to 20 carbon atoms are saturated and unsaturated C8-20 fatty acids, alkanedicarboxylic acids (such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid), hydroxy-functionalized carboxylic acid (such as citric acid, tartaric acid, malic acid), amino-functionalized carboxylic acid (such as glutamic acid, aspartic acid), keto-functionalized carboxylic acid (such as ketoglutaric acid, oxaloacetic acid), aromatic carboxylic acids (such as phthalic acid, isophthalic acid, terephthalic acid, benzoic acid, salicylic acid), unsaturated dicarboxylic acids (such as fumaric acid, maleic acid).

Preferred carboxylic acids having two to 20 carbon atoms are C8-20 fatty acids, alkanedicarboxylic acids and hydroxy-functionalized carboxylic acids, especially alkanedicarboxylic acids and hydroxy-functionalized carboxylic acids. Especially preferred carboxylic acids are citric acid and oxalic acid.

The carboxylic acid is especially oxalic acid (melting point > 157°C, water solubility 1000 g/L). In a further embodiment, the carboxylic acid is especially citric acid (melting point 153°C).

Hydrates of citric acid are also known, such as the monohydrate, which is likewise comprehended here as part of the term “citric acid”.

In a preferred embodiment, the homogeneous granular material comprises 1% to 30% by weight of prohexadione-calcium, 10% to 60% by weight of inorganic sulfate, optionally 1 % to 50% by weight of further pesticide, and ad 100% by weight of formulation auxiliaries, and optionally an acidifier.

In a particularly preferred embodiment, the granular material comprises 1% to 30% by weight of prohexadione-calcium, 10% to 60% by weight of ammonium sulfate, 1 % to 50% by weight of further growth regulator, and ad 100% by weight of formulation auxiliaries and optionally an acidifier.

In an additional embodiment, the invention relates to a granular material obtainable by a process for producing a granular material comprising prohexadione-calcium and an inorganic sulfate, wherein the process comprises the fluidized bed granulation of an aqueous dispersion comprising prohexadione-calcium and an aqueous solution comprising at least one inorganic sulfate.

In a further embodiment, the invention relates to a granular material obtainable by a process for producing a granular material comprising prohexadione-calcium and an inorganic sulfate, wherein the process comprises the fluidized bed granulation of an aqueous dispersion comprising prohexadione-calcium and an aqueous solution comprising at least one inorganic sulfate and wherein the solution of the inorganic sulfate is introduced separately into the fluidized bed chamber.

In a further embodiment, the invention relates to a granular material obtainable by a process for producing a granular material comprising prohexadione-calcium and an inorganic sulfate, wherein the process comprises the fluidized bed granulation of an aqueous dispersion comprising prohexadione-calcium and an aqueous solution comprising at least one inorganic sulfate, wherein the solution of the inorganic sulfate is introduced separately into the fluidized bed chamber and wherein the prohexadione-calcium dispersion and the solution of the inorganic sulfate are introduced simultaneously into the fluidized bed chamber. In a further embodiment, the prohexadione-calcium dispersion may comprise not more than 5% by weight of inorganic sulfate.

In a preferred embodiment, the inorganic sulfate mentioned in the abovementioned processes is ammonium sulfate ora hydrogensulfate, preferably sodium hydrogensulfate or potassium hydrogensulfate.

In further, specific embodiments, the invention relates to a granular material obtainable by any other process described above for production of a granular material comprising prohexadione-calcium and an inorganic sulfate.

The present invention further relates to the use of the granular material of the invention for production of a spray liquor. The spray liquor may be an aqueous solution or an aqueous suspension, according to the solubility and concentration of the individual constituents of the granular material. The spray liquor is typically the ready-to-use composition which can be deployed with prior art application equipment. For production of the spray liquor, the granular material is typically mixed with an excess of water. In this operation, the granular material is advantageously dispersed or dissolved rapidly and completely in water. In a particular embodiment, the present invention likewise relates to the use of the granular material of the invention for accelerated production of a spray liquor at low temperatures, for example in the region below 10°C, preferably at about 5°C. The term "accelerated" as used above implies that the production of the spray liquor via the dissolution of the granular material in water at low temperatures below 10°C, especially 5°C, because of an up to 15% enhancement of solubility of the granular material, can be conducted within a time span of 1 minute to 5 minutes, preferably below 5 minutes, further preferably below 3 minutes, most preferably below 2 minutes, for example below 1.5 minutes. The aqueous spray suspension may comprise up to 5.0 kg, preferably 0.25 to 2.5 kg, of granular material in 100 to 4000 L of water.

The granular material is usually diluted prior to application in order to produce a solution or suspension applicable by spraying (called a spray liquor). Useful diluents include mineral oil fractions of moderate to high boiling point, such as kerosene or diesel oil, and also coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, e.g. dimethyl sulfoxide, N-methylpyrrolidone or water.

Preference is given to using water, so as to form an aqueous solution or suspension. Especially in the case of use of very hard and/or alkaline water, it may be advantageous to add further amounts of inorganic sulfates (e.g. ammonium sulfate) and/or acidifier to the solution or suspension made up for spraying, in order to achieve a pH of 3.5 to 6.5, preferably of 4.0 to 5.5.

Thus, in specific embodiments of the invention, the addition of 0.01% to 2% by weight, preferably 0.1% to 0.5% by weight, of inorganic sulfate may be helpful.

The spray liquor is typically employed by spraying or nebulization. In the form of a tankmix, it is possible to add various types of oil, wetting agents, adjuvants, herbicides, bactericides, fungicides or insecticides immediately prior to application. These agents may be added to the granular materials of the invention in a weight ratio of granular material:tankmix of 1:100 to 100:1, preferably 1:10 to 10:1. The pesticide concentration in the tankmix may be varied within relatively wide ranges. In general, it is between 0.0001% and 10%, preferably between 0.01% and 1%.

The application rates in the case of application in crop protection, according to the type of effect desired, are between 0.001 and 2.0 kg of active ingredient per ha.

The present invention relates, in a further aspect, to the use of the granular material of the invention for regulation of the growth of plants. It is possible to affect virtually all development stages of a plant.

Preferred plants are fruit trees (especially apple, pear and sweet cherry), gramineae (especially wheat, triticale, barley, oats and rye, but also corn, rice, sugarcane and turfgrasses).

Further suitable plants are cotton, soybeans, millet/sorghum, sunflowers, oilseed rape, peanuts, coffee, rice, ornamentals, turfgrasses (such as Kentucky bluegrass, annual and perennial ryegrass, tall fescue, red fescue, creeping bentgrass, annual bluegrass, zoysia, bermuda, centipede, St. Augustine). Plants used may be those which are tolerant by virtue of breeding, including genetic engineering methods, to attack by insects, viruses, bacteria or fungi or to herbicide applications.

The following examples a) to g) elucidate various uses in accordance with the invention: a) For example, it is possible to greatly inhibit the vegetative growth of plants, which is especially manifested in a reduction in the linear growth. The treated plants accordingly have compound growth; in addition, a darker leaf color is observed. It has been found to be advantageous in practice that there is reduced intensity of the growth of grasses at roadsides, hedges, canal banks and in lawn areas such as parks, sports grounds and fruit plantations, ornamental lawns and airfields, such that it is possible to reduce labor-intensive and costly grasscutting. b) Also of economic interest is the increase in the stability of crops that are prone to lodging, such as cereals, corn and sunflowers. This causes stem shortening and stem strengthening, which reduces or eliminates the risk of plants “lodging” (falling over) under unfavorable weather conditions prior to harvest. Also important is the employment of growth regulators for inhibition of linear growth and for alteration of the course of maturation in the case of cotton. This enables more efficient mechanical harvesting of this crop plant. In the case of fruit trees and other trees, it is possible with the growth regulators to save on cutting costs. Moreover, the biennial bearing of fruit trees can be broken by growth regulators. By use of growth regulators, it is also possible to increase the lateral branching of the plants. There is an interest in this when, for example, intensified tillering is desirable in cereal plants. c) Growth regulators, for example in the case of winter barley and winter oilseed rape, can also considerably increase winter hardiness. In this case, firstly the linear growth and the development of unduly vigorous (and hence particularly frost-prone) leaf and plant biomass is inhibited. Secondly, the young plants, after sowing and prior to the onset of winter frosts, are kept in vegetative development in spite of favorable growth conditions. This also eliminates the risk of frost damage to those plants which have a tendency to premature breakdown of floral inhibition and to changeover to the generative phase. In the case of winter barley, it is advantageous when the crops are well into the tillering phase as a result of treatment with growth regulators in the autumn but do not enter the winter with unduly vigorous growth. This can prevent increased frost sensitivity and - because of the relatively low leaf or plant biomass - attack by various diseases (for example fungal disease). In the case of many crop plants, the inhibition of vegetative growth also enables denser planting of the soil, such that an increased yield can be achieved in relation to the soil area. d) With the aid of growth regulators, it is possible to achieve the increased yields both in plant parts and in plant constituents. For example, it is also possible to induce the growth of greater amounts of buds, flowers, leaves, fruit, seeds, roots and tubers, to increase the sugar content in sugarbeet, sugarcane and citrus fruits, to increase the protein content in cereal or soya, or to stimulate rubber trees to increased latex flow. At the same time, the active ingredients can cause increases in yield by interventions into the plant metabolism or by promotion or inhibition of vegetative and/or generative growth. Wth plant growth regulators, it is finally possible to achieve shortening or prolonging of the development stages, and also acceleration or retardation of the maturity of the harvested plant parts before or after harvesting. e) It is of economic interest, for example, to facilitate harvesting, which is enabled by the concentration in time of the falling or reduction in the hold strength on the tree in the case of citrus fruits, olives, or in other species and varieties of pome fruit, stone fruit and shelled fruit. The same mechanism, i.e. the promotion of the formation of separating tissue between the fruit part and the leaf and shoot part of the plant, is also essential for well-controlled defoliation of crop plants, for example cotton. f) With growth regulators, it is additionally possible to reduce the water consumption of plants. This is particularly important for agricultural areas which have to be artificially irrigated at high cost, for example in arid or semiarid regions. Through the use of growth regulators, it is possible to reduce the intensity of irrigation and hence implement less expensive cultivation. Under the influence of growth regulators, there is better exploitation of the water present because, among other reasons, the opening width of the stomata is reduced, a thicker epidermis and cuticle are formed, root penetration of the soil is improved, the transpiring leaf surface area is reduced, or the microclimate in the crop plant stock is favorably affected by more compact growth. g) Wth growth regulators, it is also possible to achieve, through changes in metabolic processes and/or through changes in the cytological structure, physiological resistance to pathogens and harmful insects.

It is an advantage of the present invention that the process can be conducted on the industrial scale with standard apparatus. It allows the combination of prohexadione-calcium with sulfates in a single formulation. The injection both of the component comprising prohexadione-calcium and of the inorganic sulfate component allows the fluidized bed granulation to be conducted continuously, and there is no need to operate it in batchwise mode, as in the conventional approach.

Furthermore, nontoxic starting materials are used. The granular materials produced by the process of the invention are very storage-stable and may comprise high amounts of sulfates. On dilution with water, spray suspensions are rapidly formed, even in the case of dilution with hard water and especially in the case of dilution operations at low temperatures, for example in the range below 10°C, for example at 5°C. There is no need for prior homogenization of the granular material before the dilution step. It is also possible to use modern induction hoppers without prior “slurrying” of the granular material.

In the case of partial removals from the commercial package, the granular material can be metered in a simple manner, since it is a dry flowable. The granules have high bioregulatory efficacy.

The present formulations additionally offer the following advantages: - In general, no addition of adjuvants (e.g. ammonium sulfate or acidifiers) is required, which means less work, an improvement in safety for the user, and less potential sources of error in the production of the spray liquor. - In the presence of an acidifier (slightly acidic pH of the suspension), prohexadione is in undissociated (apolar) form and can thus be absorbed in an accelerated manner by plant cells. This results, especially under unfavorable application conditions (for example rapid drying of the spray coating under warm and dry weather conditions), in elevated active ingredient efficiency. In addition, rain resistance is achieved considerably more quickly. - The porous matrix structure of the granular material enables a significant increase in the dispersibility of the granular material after stirring in cold water for 1 to 5 minutes (see also example 3, bottom). In other words, the solubility of prohexadione-calcium is improved, especially at low (water) temperatures below 10°C, especially at temperatures of 5°C. The enhanced solubility in cold water enables a distinct improvement or simplification in practical use in the early months of the year (at low temperatures in the range below 10°C, for example 5°C).

The examples and figures which follow are intended to illustrate the invention. They do not serve to limit the invention. The person skilled in the art will be able to configure and implement further modifications of the principle of the invention as described herein.

EXAMPLES

Example 1

Process for fluidized bed granulation according to the prior art (Batch 400126) A) Production of a prohexadione-Ca spray suspension:

Each process step was conducted with suitable cooling in order to ensure that the temperature of the spray suspension does not exceed 30°C.

For production of the spray suspension (solids content 35%), the following components were introduced into a stirred tank: - water dispersion agents, wetting agents, carriers, defoamers - prohexadione-Ca techn. (about 94.5%)1) 1) The amount of prohexadione-calcium techn. to be used depends on the actual active ingredient content. Any fluctuations in the active ingredient content were compensated for via the addition of ammonium sulfate.

The suspension was stirred for 30 minutes, and then ground by a return method with a rotor/stator mill (PUC or Siefer). After the preliminary grinding operation had ended, the suspension was transferred into the next vessel. A ball milling process (ball size 0.8-1.2 mm) was conducted therein, in order to obtain the final particle size (d50 < 2 pm, d90 < 10 pm). B) Fluidized bed granulation:

The granulation was conducted in a batchwise process. The amount of ammonium sulfate required was introduced as starting material into the fluidized bed granulator, i.e. initially charged as the fluidized bed.

Subsequently, the prohexadione-calcium spray suspension (solids content 35%) was sprayed into the fluidized bed from two nozzles above and dried with hot air. The spray suspension was stirred uniformly in order to assure homogeneity.

The spraying rate and the position of the nozzles can be varied in order to prevent coarse agglomeration and the formation of formation of lumps.

The granulation was conducted under the following conditions:

Air inflow temperature: 100-130°C

Product temperature: 60-80°C

The air inflow temperature must not exceed 150°C, in order not to damage the active ingredient. C) Sieving of the end product:

After the fluidized bed granulation had ended, the particles from the fluidized bed were cooled and sieved to a size of 2.0 mm-0.3 mm, in order to obtain the end product.

Example 2

Process for fluidized bed granulation according to the present invention (Batch 400131) A) Production of a prohexadione-Ca spray suspension:

Each process step was conducted with suitable cooling in order to ensure that the temperature of the spray suspension does not exceed 30°C.

For production of the spray suspension (solids content 35%), the following components were introduced into a stirred tank: - water - dispersion agents, wetting agents, carriers, defoamers - prohexadione-Ca techn. (about 94.5%)1) 1) The amount of prohexadione-calcium techn. to be used depends on the actual active ingredient content. Any fluctuations in the active ingredient content were compensated for via the addition of ammonium sulfate.

The suspension was stirred for 30 minutes, and then ground by a return method with a rotor/stator mill (PUC or Siefer). After the preliminary grinding operation had ended, the suspension was transferred into the next vessel. A ball milling process (ball size 0.8-1.2 mm) was conducted therein, in order to obtain the final particle size (d50 < 2 pm, d90 <10 pm). B) Production of an ammonium sulfate spray solution:

The amount of ammonium sulfate required was dissolved in water. The concentration of the spray solution is close to saturation point of the solution for ammonium sulfate (i.e. ammonium sulfate in water). C) Fluidized bed granulation:

The granulation was conducted continuously (but can optionally also be conducted in a batchwise process).

The prohexadione-calcium spray suspension (solids content 35%) was sprayed into the fluidized bed from one or two nozzles and the ammonium sulfate spray solution from one or two nozzles, and dried with hot air.

The spray suspension was stirred homogeneously, in order to assure homogeneity.

The spraying rate and the position and number of the nozzles can be varied in order to prevent coarse agglomeration and the formation of formation of lumps.

The granulation was conducted under the following conditions:

Air inflow temperature: 100-130°C

Product temperature: 60-80°C

The air inflow temperature must not exceed 150°C, in order not to damage the active ingredient. D) Sieving of the end product:

After the fluidized bed granulation had ended, the particles from the fluidized bed were cooled and sieved to a size of 2.0 mm-0.3 mm, in order to obtain the end product.

Example 3

Characterization and comparison of the water-dispersible granules obtained in examples 1 and 2

The study results listed in table 3 from comparative analyses of the granular materials from the prior art (Batch 400126) and according to the present invention (Batch 400131) show that the two granular materials obtained from the different production processes have comparable dispersion properties to a broad extent.

In contrast to the granular material produced by the existing process, the granular material produced by the process of the invention, however, exhibits a significant increase in dispersibility at low temperatures of about +5°C. Here, the granular material produced by the process of the invention, by virtue of its specific matrix structure, is already dispersed to an extent of more than 80% after 1 min, whereas the granular material produced by the existing process (core/shell structure) is dispersed only to an extent of 67%.

This offers the advantage that the granular material under conditions in the early months of the year (with cold water and outside temperatures in the region of about 5°C) can be dispersed very much more quickly than the granular material produced in a conventional manner. This simplifies application by virtue of a significantly shortened preparation time in practical application. “Comprises/comprising” when used in this specification is taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

Claims (14)

1. CLAIMS:

   1. A process for producing a granular material comprising prohexadione-calcium and an inorganic sulfate, comprising the fluidized bed granulation of an aqueous dispersion comprising prohexadione-calcium and an aqueous solution comprising at least one inorganic sulfate.
2. 2. The process according to claim 1, wherein the prohexadione-calcium dispersion and the solution of the inorganic sulfate are introduced separately into a fluidized bed chamber.
3. 3. The process according to claim 1 or 2, wherein the prohexadione-calcium dispersion and the solution of the inorganic sulfate are introduced simultaneously into a fluidized bed chamber.
4. 4. The process according to any one of claims 1 to 3, wherein the prohexadione-calcium dispersion comprises not more than 5% by weight of inorganic sulfate.
5. 5. The process according to any one of claims 1 to 4, wherein the inorganic sulfate is ammonium sulfate or a hydrogensulfate, preferably sodium hydrogensulfate or potassium hydrogensulfate.
6. 6. A homogeneous granular material comprising inorganic sulfate and prohexadione-calcium, wherein the inorganic sulfate and the prohexadione-calcium are distributed homogeneously in the granular material and the granular material has a porous matrix structure.
7. 7. The homogeneous granular material according to claim 6, wherein the inorganic sulfate is ammonium sulfate or a hydrogensulfate, preferably sodium hydrogensulfate or potassium hydrogensulfate.
8. 8. The homogeneous granular material according to claim 6 or 7, comprising a further pesticide.
9. 9. The homogeneous granular material according to claim 8, wherein the further pesticide is a growth regulator.
10. 10. The homogeneous granular material according to any one of claims 6 to 9, comprising an acidifier.
11. 11. The homogeneous granular material according to any one of claims 6 to 10 comprising: 1% to 30% by weight of prohexadione-calcium; 10% to 60% by weight of ammonium sulfate; optionally 1% to 50% by weight of further pesticide, ad 100% by weight formulation auxiliaries; and optionally an acidifier.
12. 12. A homogeneous granular material obtained by the process according to any one of claims 1 to 5.
13. 13. The use of the homogeneous granular material according to any one of claims 6 to 11 or produced by the process according to any one of claims 1 to 5 for production of a spray liquor.
14. 14. The use of the homogeneous granular material according to any one of claims 6 to 11 or produced by the process according to any one of claims 1 to 5 for regulation of the growth of plants.