AU2010277784B2 - Granulate containing a carboxylic growth regulator and a solid acidifier - Google Patents

Abstract

The present invention relates to a granulate comprising a carboxylic growth regulator and a solid acidifier. The invention further relates to a method for producing the granulate by extrusion or fluidized bed granulation. The invention further relates to a use of the granulate for producing an aqueous spray mixture, in which the granulate is brought into contact with water, and the use of the granulate for regulating the growth of plants.

Description

1 Granulate containing a carboxylic growth regulator and a solid acidifier The present invention relates to granules comprising a carboxyl-containing growth regulator and a solid acidifier. The invention furthermore relates to a process for the 5 preparation of the granules by extrusion or fluidized-bed granulation. The invention also relates to a use of the granules for the preparation of an aqueous spray mixture by bringing the granules into contact with water, and to a use of the granules for regulating the growth of plants. The present invention comprises combinations of preferred features with other preferred features. 10 Carboxyl-containing growth regulators such as prohexadione salts (e.g. prohexadione calcium) are known growth regulators and are commercially available in a variety of agrochemical formulations. Usually, the spray mixture is made up by treating the prohexadione salt in the spray tank with water (for example tap water or spring water) 15 and is then brought to a slightly acidic pH by adding citric acid. Rademacher and Kober, Europ. J. Hort. Sci. 2003, 68(3), 101-107 (Efficient use of prohexadione-Ca in pome fruits) disclose an aqueous composition comprising 0.25% by weight of prohexadione-calcium and citric acid or phosphoric acid. 20 The pending European patent application EP 08165281.0 of 9.26.2008 discloses the use of a combination of acylcyclohexanedionecarboxylic acids and acylcyclohexane dionedicarboxylic esters for improving the development of Gramineae. Acidification of the spray mixture is said to be advantageous for promoting the uptake of 25 acylcyclohexanedionecarboxylic acids into plants. Stover et al., Proceedings 31st PGRSA (Plant Growth Regulation Society of America) Annual Meeting, 2004, page 86, disclose a spray mixture comprising 500 ppm of prohexadione-calcium, which spray mixture has been adjusted to pH 3.5 with citric 30 acid. Lovatt and Salazar-Garcia, Proceedings 33rd PGRSA Annual Meeting, 2006, pages 98-107, disclose a spray mixture comprising 125 mg/I prohexadione-calcium, which spray mixture has been adjusted to a pH of 5.5 using citric acid. 35 Petgen, Das deutsche Weinmagazin 2009, 4, 26-30 discloses the acidification of a spray mixture using citric acid (0.1% strength) to a pH of 4.0 to 5.5. The addition of citric acid is said to improve the solubility in water and to cause a more rapid uptake of the active substance. 40 The disadvantage of the known formulations of carboxyl-containing growth regulators such as prohexadione salts is that the agricultural practitioner must make up the spray 2 mixture, which requires a great deal of labor and time. He needs extra devices for measuring the pH, extra storage space for citric acid and ha to handle the citric acid, which is classified as "irritant". As the result of the complicated preparation, the makeup operation is subject to error. It was an object of the present invention to find a formulation of carboxyl-containing growth regulators such as prohexadione salts, and a preparation process therefor, which formulation already comprises an acidifier. The formulation should be simple to handle by the user and should be storage-stable. It was further desirable that the formulation should comprise large amounts of carboxyl-containing growth regulators such as prohexadione salts and/or of acidifiers. Moreover, it was desirable that a solution or suspension with high biological activity can be prepared from the formulation by dilution with water, even hard water. It was intended that the formulation should be capable of being implemented on an industrial scale, with inexpensive and nontoxic starting materials. The object was achieved by granules comprising prohexadione-calcium and a solid acidifier, wherein the acidifier is a hydrogen sulphate or a hydrogen phosphate. The granules take the form of a composition which is solid at 201C. The individual granules can be spherical in terms of shape, with corners, edges and/or depressions being possible. Such shapes are typically generated in fluidized-bed granulation. The granules may also be cylindrical in shape, as generated for example in extrusion. Carboxyl-containing growth regulators are growth regulators which comprise at least one carboxyl groups. The carboxyl-containing growth regulators may be present in the form of the free acid (-CO2H) or in the form of the carboxylate salt (-C02 ). Preferably, the carboxyl-containing growth regulators are present in the form of the carboxylate salt. Suitable carboxyl-containing growth regulator are growth regulators from the classes of the auxins, ethylene inhibitors, gibberellins and growth inhibitors which comprise at least one carboxyl groups.

2a Preferred carboxyl-containing growth regulator are present in the form of a free acid or of a salt of abscisic acid, aviglycine, cyclanilide, dikegulac, gibberellins A 1 , A 3 , A 4 ,

A

7 , indole-3-acetic acid, 4-chloroindole-3-acetic acid, indole-3-butyric acid, 1 naphthalene-acetic acid, 2-naphthoxyacetic acid, 4-chlorophenoxyacetic acid, 2,4 dichlorophenxy-acetic acid, 2-(3-chlorophenoxy)propionic acid, 2-(2,4 dichlorophenoxy)propionic acid, or in the form of the growth regulator of the formula (1).

3 0 HOOC CO-R (I) 0 where R is C-C 1 o-alkyl or C3-CIo-cycloalkyl. Suitable carboxylate salts are salts of the cations of the alkali metals, preferably of 5 lithium, sodium and potassium, of the alkaline earth metals, for example of calcium and magnesium, and of the transition metals, preferably of manganese, copper, zinc and iron, furthermore ammonium (NH 4 *) and substituted ammonium, where one to four hydrogen atoms may be substituted by organic groups. Preferred carboxylate salts are, in particular, the sodium, potassium, calcium and ammonium salts. 10 Particularly preferably the granules comprise a growth regulator of the formula (1), 0 HOOC CO-R (1) 0 15 where R represents Ci-Cio-alkyl or C3-C1-cycloalkyl, in the form of a free acid or of a salt. Preferably, R represents C-C 4 -alkyl or C3-C-cycloalkyl, and in particular ethyl or cyclopropyl. Preferably, the granules comprise a salt of a growth regulator of the formula (1). 20 The compounds of the formula (I) may be present not only in the trione form (triketo form) L.a, but also in the tautomeric keto-enol forms L.b and L.c: o OH 0 OH HOOC CO-R * HOOC CO-R HOOC R o0 0 L.a l.b L.c 25 The salts of the growth regulators of the formula (1) may be not only the salts of the monoanions, but also the salts of the dianions of these compounds. The monoanions may be present not only as carboxylate anions Id, but also as enolate anions I.e and If,: 30 4 o o0 9 ooc CO-R HOOC Co-R ++ HOOC 0 e R o 0 0 I.d I.e l.f Preferred cations in the salts of the growth regulators of the formula I are the ions of 5 the alkali metals, preferably of lithium, sodium and potassium, of the alkaline earth metals, preferably of calcium and magnesium, and of the transition metals, preferably of manganese, copper, zinc and iron, furthermore ammonium (NH 4 +) and substituted ammonium, where one to four hydrogen atoms are replaced by CrC-4-alkyl, hydroxy CrC 4 -alkyl, C-C4-alkoxy-C-C 4 -alkyl, hydroxy-CrC4-alkoxy-C-C 4 -alkyl, phenyl or 10 benzyl, preferably ammonium, methylammonium, isopropylammonium, dimethyl ammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyeth 1-oxy)eth-1-ylammonium, di(2-hydroxyeth-1-yl)ammonium, benzyltrimethylammonium, benzyltriethylammonium, furthermore phosphonium ions, sulfonium ions, preferably 15 tri(C-C4-alkyl)sulfonium such as trimethylsulfonium, and sulfoxonium ions, preferably tri(C1C4-alkyl)sulfoxonium. Other preferred cations are chlormequat [(2-chloroethyl) trimethylammonium], mepiquat (N,N-dimethylpiperidinium) and N,N-dimethyl morpholinium. Especially preferred cations are the alkali metal cations, the alkaline earth metal cations and the ammonium cation (NH 4 +). In particular, it is the calcium salt. 20 Especially preferred carboxyl-containing growth regulators are prohexadione (R = ethyl) and trinexapac (R = cyclopropyl), in particular prohexadione. Prohexadione and trinexapac can, as described above, be present in the form of the free acid or of the salt. Prohexadione and trinexapac are preferably present in the form of the salt, in 25 particular of the calcium salt. The granules may comprise from 0.01 to 80% by weight, preferably from 0.1 to 50% by weight, especially preferably from 1 to 25% by weight and in particular from 3 to 15% by weight of carboxyl-containing growth regulators. 30 The acidifier is a solid chemical. The melting point is in most cases at least 500C, preferably at least 100*C and in particular at least 150*C. In a further preferred embodiment, the acidifier is soluble in water at 20*C to an extent of at least 50 g/Il, especially preferably to an extent of at least 150 g/I and in particular to an extent of at 35 least 300 g/Il. The preferred solid acidifier is a carboxylic acid with two to 20 carbon atoms, a hydrogen sulfate or a hydrogen phosphate. Mixtures of the abovementioned acidifiers are also possible. In a further preferred embodiment, the acidifier is a carboxylic acid 5 having two to six carbon atoms (especially oxalic acid), a hydrogen sulfate or a hydrogen phosphate. In a further preferred embodiment, the acidifier is a hydrogen sulfate or a hydrogen phosphate. 5 The carboxylic acid may be a linear, branched or cyclic carboxylic acid with two to 20 carbon atoms. In most cases, the carboxylic acid comprises at least one carboxyl group (-COOH), for example one, two or three. The carboxylic acid comprises two to 20 carbon atoms, preferably two to 12, in particular two to 8 carbon atoms. Besides carboxyl groups, it may feature further functional groups such as alcohol groups. In 10 most cases, the carboxylic acid has at least one carboxyl group with 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 with two to 20 carbon atoms are saturated and unsaturated Ca-C 2 0 -fatty acids, alkanedicarboxylic acids (such as oxalic acid, malonic 15 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 acid (such as phthalic acid, isophthalic acid, terephthalic acid, benzoic acid, salicylic acid), and 20 unsaturated dicarboxylic acids (such as fumaric acid, maleic acid). Preferred carboxylic acids with two to 20 carbon atoms are Ca-C 2 -fatty acids, alkanedicarboxylic acids and hydroxy-functionalized carboxylic acids, in particular alkanedicarboxylic acids and hydroxy-functionalized carboxylic acids. 25 Especially preferred carboxylic acids are citric acid and oxalic acid. In particular, the carboxylic acid is oxalic acid (melting point >157*C, solubility in water 1000 g/I). In a further embodiment, the carboxylic acid is in particular citric acid (melting point 153 0 C). Hydrates of citric acid, such as the monohydrate, are also known and are to be covered in the present context by the term citric acid. 30 Suitable hydrogen sulfates are salts comprising the anion HSO 4 -, for example alkali metal salts or ammonium salts. Especially preferred hydrogen sulfate is sodium hydrogen sulfate or ammonium hydrogen sulfate (melting point 120 0 C, solubility in water 1000 g/l), in particular sodium hydrogen sulfate (melting point >315*C, solubility 35 in water 1000 g/l). Suitable hydrogen phosphates are salts such as alkali or alkaline-earth metal salts comprising the anion H 2

PO

4 or the anion HP0 4 2 -. Preferred are alkali or alkaline-earth metal salts comprising the anion H 2 PO4- (dihydrogen phosphates). Especially preferred 40 hydrogen phosphate is sodium dihydrogen phosphate, potassium dihydrogen phosphate or calcium dihydrogen phosphate.

6 The granules may comprise from 0.5 to 50% by weight, preferably from 2 to 30% by weight and in particular from 5 to 25% by weight of acidifier. The granules may comprise an inorganic sulfate. The inorganic sulfate is preferably 5 soluble in water to an extent of at least 1 g/l, preferably to an extent of at least 100 g/l, at 20 0 C. Suitable inorganic sulfates are sulfates of metal ions or of quaternary nitrogen compounds (such as ammonium). The inorganic sulfate is preferably ammonium sulfate (solubility in water 754 g/i). The granules may comprise from 5 to 75% by weight, preferably from 25 to 70 and in particular from 40 to 65% by weight of inorganic 10 sulfate. The granules may comprise a binder. Binders are generally known. Suitable examples are saccharides and synthetic polymers, preferably saccharides. The binder is particularly preferably a disaccharide, maltodextrin, cellulose ether, 15 polyvinylpyrrolidone, polyvinyl acetate or polyvinyl alcohol. The binder is especially preferably a disaccharide or a maltodextrin. Examples of binders which comprise a saccharide are mono-, di-, oligo- and polysaccharides, and their mixtures. Examples of suitable monosaccharides are 20 sorbitol, mannitol and glucose. Examples of suitable disaccharides are lactose and sucrose. Examples of suitable oligosaccharides are starch hydrolyzates with a DE (dextrose equivalent) value of from 2 to 20 (known as maltodextrins). Examples of suitable polysaccharides are starch (wheat starch, cornstarch, potato starch, rice starch), starch derivatives, cellulose acetate phthalate, hydroxylmethylcel lu lose 25 phthalate, microcrystalline cellulose, sodium-carboxymethylcellulose, methylcellulose, cellulose ethers such as hydroxypropylcellulose, hydroxypropylmethylcel lu lose, methylhydroxyethylcellu lose, methyl hydroxypropylcel lu lose, hydroxyethylcel lu lose. Preferred saccharides are disaccharides, oligosaccharides and cellulose ethers and their mixtures. Starch hydrolysates are especially preferred. 30 Examples of binders which comprise a synthetic polymer are polyolefins such as polyethylene, polypropylene, polybutylene and polyisobutynylene; vinyl polymers such as polyvinyl chloride, polyvinyl pyrrolidone, polyvinylinylcaprolactam, polyvinyl acetate, polyvinyl alcohol, polystyrene, polyacrylonitrile, polyacrylates, polymethacrylates; 35 polyacetals such as polyoxymethylene; polyesters with at least partially aliphatic ester groups such as polyhydroxybutyric acid, polyhydroxyvaleric acid, polybutylene succinates, polyalkylene terephthalates such as polyalkylene adipate terephthalates such as polybutylene adipate terephthalates; polyester amides; polyether amides; polyamides; polyester amides; polycaprolactams; polyimides; polyethers; polyether 40 ketones; polyurethanes and polycarbonates; and copolymers of ethylene/vinyl acetate, ethylene/(meth)acrylates, styrene/acrylonitrile, styrene/butadiene, styrene/butadiene/acrylonitrile, olefin/maleic anhydride. Preferred synthetic polymers 7 are vinyl polymers, in particular polyvinylpyrrolidone, polyvinyl acetate and polyvinyl alcohol. The granules may comprise from.0.1 to 30% by weight, preferably from 0.5 to 15% by 5 weight and in particular from 2 to 8% by weight of binder. The granules may comprise a nonionic or anionic surfactant. This means that it may comprise at least one nonionic surfactant or at least one anionic surfactant or a mixture of at least one nonionic surfactant and at least one anionic surfactant. The nonionic or 10 anionic surfactant is preferably an alkoxylate, a block polymer or a sulfonate; especially preferably an alkoxylate which has been alkoxylated with ethylene oxide, a block polymer comprising polyethylene oxide and polypropylene oxide blocks, or an alkali metal salt, alkaline-earth metal salt or ammonium salt of a sulfonate; and in particular a block polymer comprising polyethylene oxide and polypropylene oxide blocks, or an 15 alkali metal salt, alkaline-earth metal salt or ammonium salt of sulfonates of naphthalenes, alkylnaphthalenes and of condensed naphthalenes or alkylaryls. Suitable nonionic surfactants are alkoxylates, N-alkylated fatty acid amides, amine oxides, esters, block polymers or sugar-based surfactants. Examples of alkoxylates are 20 compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated. It is possible to use ethylene oxide and/or propylene oxide, preferably ethylene oxide, for the alkoxylation. Examples of N-alkylated fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples 25 of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Suitable block polymers are block polymers of the A-B or of the A-B-A type (molar mass for example from 500 to 5000 g/mol) comprising polyethylene oxide and polypropylene oxide blocks or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Preferred nonionic surfactants 30 are block polymers, preferably block polymers comprising polyethylene oxide and polypropylene oxide blocks. Suitable anionic surfactants are alkali metal, alkaline-earth metal or ammonium salts of sulfonates, sulfates, phosphates or carboxylates. Examples of sulfonates are 35 alkylarylsulfonates (such as lignin), diphenylsulfonates, alpha-olefinsulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of condensed naphthalenes (for example with formaldehyde) or alkylaryls, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids 40 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 8 anionic surfactants are alkali metal, alkaline-earth metal or ammonium salts of sulfonates, specifically alkali metal, alkaline-earth metal or ammonium salts of sulfonates of naphthalenes, of alkylnaphthalenes, and of condensed naphthalenes or alkylaryls. 5 The granules may comprise from 0.1 to 35% by weight, preferably from 0.5 to 25% by weight and in particular from 3 to 18% by weight of nonionic or anionic surfactant, with all nonionic and anionic surfactants being added up. 10 The granules may comprise a complexing agent. A complexing agent is understood as meaning organic compounds which form complexes in water with calcium and magnesium ions. Examples of suitable complexing agents are EDTA (ethylenediaminetetraacetic acid), NTA (nitrilotriacetic acid), EDDHA (ethylenediam ined i(ortho-hydroxyphenyl)acetic acid), DTPA 15 (diethylenetriaminepentaacetic acid), HEDTA (hydroxyethylenediaminetriacetic acid), citric acid, gluconic acid, isoascorbic acid, sodium isoascorbate, tartaric acid, iminodisuccinate tetrasodium salt, triethanolamine, and the alkali metal or alkaline earth metal salts of the abovementioned acids. Preferred complexing agents are EDTA and their alkali metal salts. The granules may comprise from 0.001 to 10% by weight, 20 preferably from 0.01 to 2% by weight and in particular from 0.05 to 0.5% by weight of complexing agent. The granules may comprise a solid carrier. This means that it may comprise at least one solid carrier. Examples of carriers which may be mentioned are: a) inorganic 25 compounds: mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, attapulgites, montmorillonites, mica, vermiculites, synthetic silicas, amorphous silicas and synthetic calcium silicates, or mixtures of these; b) organic compounds: ground plastics, fertilizers such as 30 ammonium phosphate, ammonium nitrate, thiourea and urea, products of vegetable origin such as cereal meals, tree bark meals, wood meal and nutshell meal, cellulose powder. The solid carriers may also be employed as aggregate formers, for example silicas. Aggregate formers are therefore solid carriers for the purposes of the present invention. 35 The carrier is preferably an inorganic carrier, especially preferably a silicate, such as precipitated silica, aluminum silicates and calcium silicates. The mean particle size of the silica d50 (determined via laser diffraction) may be in the range of from 0.1 to 100 pm, preferably from 0.5 to 20 pm and in particular 1 to 10 pm. The specific surface 40 area may be in the range of from 1 to 500 m 2 /g, preferably 10 to 100 m 2 /g (determined by means of areameter analogously to ISO 5794-1, Annex D).

The granules may comprise from 0.1 to 35% by weight, preferably from 0.5 to 25% by weight and in particular from 2 to 17% by weight of solid carrier. The granules may comprise further formulation auxiliaries, the choice of the auxiliaries 5 usually depending on the specific use form. Examples of suitable formulation auxiliaries are solvents, surface-active substances (such as surfactants, protective colloids, dispersants, wetters and adhesives), organic and inorganic thickeners, bactericides, antifreezes, antifoams, optionally colorants and stickers (for example for the treatment of seed). 10 Suitable surface-active substances, for example in the form of surfactant, dispersant or wetter, are the alkali metal, alkaline-earth metal, ammonium salts of aromatic sulfonic acids, for example of lignosulfonic acid (Borresperse* types, Borregaard, Norway), phenolsulfonic acid, naphthalenesulfonic acid (Morwet* types, Akzo Nobel, USA) and 15 dibutylnaphthalenesulfonic acid (Nekal* types, BASF, Germany), and 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, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, 20 polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl 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, 25 denatured proteins, polysaccharides (for example methylcellulose), hydrophobically modified starches, polyvinyl alcohol (Mowiol* types, Clariant, Switzerland), polycarboxylates (Sokalan* types, BASF, Germany), polyalkoxylates, polyvinylamine (Lupamin* types, BASF, Germany), polyethyleneimine (Lupasol* types, BASF, Germany), polyvinylpyrrolidone and their copolymers. Lignosulfonates are preferred. 30 Examples of adjuvants are organically modified polysiloxanes, such as BreakThru S 240*; alcohol alkoxylates, such as Atplus*245, Atplus*MBA 1303, Plurafa&LF and LutensolO ON ; EO/PO block polymers, for example Pluronic® RPE 2035 and Genapol* B; alcohol ethoxylates, for example Lutensol® XP 80; and sodium dioctylsulfosuccinate, 35 for example Leophen® RA. Examples of thickeners (i.e. compounds which impart a modified flow behavior to the composition, i.e. high viscosity at rest and low viscosity in the agitated state) are polysaccharides and organic and inorganic layered minerals such as xanthan gum 40 (Kelzan®, CP Kelco), Rhodopol* 23 (Rhodia) or Veegum® (R.T. Vanderbilt) or Attaclay* (Engelhard Corp.).

10 Examples of antifoams are silicone emulsions (such as, for example, Silikon* SRE, Wacker, Germany or Rhodorsil*, Rhodia, France), long-chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures of these. 5 The granules may optionally comprise further pesticides, such as one or two pesticides. The granules preferably comprise a further growth regulator. The granules especially preferably comprise mepiquat chloride as further growth regulator. In a further embodiment, the granules are free from pesticides other than growth regulators. Preferably, the granules comprise from 1 to 70% by weight, preferably from 15 to 60% 10 by weight and in particular from 25 to 40% by weight of a further growth regulator, such as mepiquat chloride. The term pesticides refers to at least one active substance selected from the group of the fungicides, insecticides, nematicides, herbicides, safeners and/or further growth 15 regulators. Preferred pesticides are fungicides, insecticides, herbicides and growth regulators. Especially preferred pesticides are growth regulators. Mixtures of pesticides of two or more of the abovementioned classes may also be used. The skilled worker is familiar with such pesticides, which can be found, for example, in the Pesticide Manual, 15th Ed. (2009), The British Crop Protection Council, London. The following list of 20 pesticides is intended to illustrate, but not to restrict, the possible combinations: A) Strobilurins: Azoxystrobin, dimoxystrobin, coumoxystrobin, coumethoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, 25 pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, trifloxystrobin, methyl 2-[2-(2,5-dimethylphenyl-oxymethyl)phenyl}-3-methoxy acrylate, N-methyl-2-(2-(3 (2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxy iminoacetamide; B) Carboxamides: 30 - 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-methylthiazole-5-carboxanilide, N-(4'-trifl uoromethylthiobi phenyl-2-yl) 35 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 acid morpholides: dimethomorph, flumorph, pyrimorph; - Benzamides: flumetover, fluopicolide, fluopyram, zoxamide; - Other carboxamides: carpropamid, diclocymet, mandipropamid, oxytetracyclin, 40 silthiofam, N-( 6 -methoxypyridin-3-yl)cyclopropanecarboxamide; C) Azoles: - Triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, 11 diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, 5 triadimenol, triticonazole, uniconazole; - Imidazoles: cyazofamid, imazalil, imazalil sulfate, pefurazoate, prochloraz, triflumizole; - Benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole; - Others: ethaboxam, etridiazole, hymexazole, 2-(4-chloropheny)-N-[4-(3,4-dimethoxy 10 phenyl)isoxazol-5-yI]-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-methyl phenyl)-2,3-di methylisoxazolid in-3-yl]pyridine; - Pyrimidines: bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, mepanipyrim, 15 nitrapyrin, nuarimol, pyrimethanil; - Piperazines: triforine; - Pyrroles: fludioxonil, fenpiclonil; - Morpholines: aldimorph, dodemorph, dodemorph acetate, fenpropimorph, tridemorph; 20 - Piperidines: fenpropidin; - Dicarboximides: fluoroimide, iprodione, procyrnidone, vinclozolin; - Nonaromatic 5-membered heterocyclic rings: famoxadon, fenamidon, flutianil, octhilinone, probenazole, S-allyl 5-amino-2-isopropyl-3-oxo-4-ortho-tolyi-2,3 dihydropyrazole-1-thiocarboxylate; 25 - Others: acibenzolar-S-methyl, amisulbrom, anilazine, blasticidin-S, captafol, captan, quinomethionate, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat methylsulfate, fenoxanil, folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quin oxyfen, triazoxide, tricyclazole, 2 -butoxy-6-iodo-3-propylchromen-4-one, 5-chloro 1 -(4,6-dimethoxypyrim idi n-2-yl)-2-methyl- 1 H-benzim idazole, 5-chloro-7-(4-methyl 30 piperidin-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 dithiocarbarmates: ferbam, mancozeb, maneb, metam, methasulfocarb, metiram, propineb, thirarn, zineb, ziram; 35 - Carbamates: diethofencarb, benthiavalicarb, iprovalicarb, proparnocarb, propamocarb hydrochloride, valiphenal, 4-fluoropheny N-(1-(1-(4 cyanophenyl)ethanesulfonyl) but-2-yl)carbamate; F) Other fungicides - Guanidines: dodine, dodine free base, guazatine, guazatine acetate, iminoctadine, 40 iminoctadine triacetate, iminoctadine tris(albesilate); - Antibiotics: kasugamycin, kasugamycin hydrochloride hydrate, polyoxines, streptomycin, validamycin A; 12 - Nitrophenyl derivatives: binapacryl, dicloran, dinobuton, dinocap, nitrothal-isopropyl, tecnazene; - Organometallic compounds: fentin salts such as, for example, fentin acetate, fentin chloride, fentin hydroxide; 5 - Sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane; - Organophosphorus compounds: edifenphos, fosetyl, fosetyl aluminum, iprobenfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl; - Organochlorine compounds: chlorthalonil, dichlofluanid, dichlorphen, flusulfamide, hexachlorobenzene, pencycuron, pentachlorophenol and its salts, fthalide, 10 quintozen, thiophanate-methyl, tolylfluanid, N-(4-chloro-2-nitrophenyl)-N-ethyl 4-methylbenzenesulfonamide; - Inorganic active substances: phosphorous acid and its salts, Bordeaux mixture, copper salts such as, for example, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; 15 - Biological fungicides, plant strengtheners: Ampelomyces quisqualis (for example the product AQ 10* from Intrachem Bio GmbH & Co. KG, Germany), Aspergillus flavus (for example the product AFLAGUARD* from Syngenta, Switzerland), Aureobasidium pullulans (for example the product BOTECTOR* from bio-ferm GmbH, Germany), Bacillus pumilus (e.g. Strain NRRL No. B-30087 in SONATA® and BALLAD® Plus 20 from AgraQuest Inc., USA), Bacillus subtilis (e.g. Strain NRRL No. B-21661 in RHAPSODY, SERENADED MAX and SERENADED ASO from AgraQuest Inc., USA), Bacillus subtilis var. amyloliquefaciens FZB24 (for example the product TAEGRO® from Novozyme Biologicals, Inc., USA), Candida oleophila 1-82 (for example the product ASPIRE® from Ecogen Inc., USA), Candida saitoana (e.g. the 25 products BIOCURE* (in admixture with lysozyme) and BIOCOAT® from Micro Flo Company, USA (BASF SE) and Arysta), chitosan (e.g. ARMOUR-ZEN from BotriZen Ltd., New Zealand), Clonostachys rosea f. catenulata, also referred to as Gliocladium catenulatum (e.g. Strain J1446: PRESTOP® from Verdera, Finland), Coniothyrium minitans (for example the product CONTANS® from Prophyta, Germany), 30 Cryphonectria parasitica (for example the product Endothia parasitica from CNICM, France), Cryptococcus albidus (for example the product YIELD PLUS® from Anchor Bio-Technologies, South Africa), Fusarium oxysporum (e.g. the products BIOFOX® from S.1.A.P.A., Italy, and FUSACLEAN® from Natural Plant Protection, France), Metschnikowia fructicola (for example the product SHEMER* from Agrogreen, 35 Israel), Microdochium dimerum (for example the product ANTIBOT® from Agrauxine, France), Phlebiopsis gigantea (for example the product ROTSOP® from Verdera, Finland), Pseudozyma flocculosa (for example the product SPORODEX® from Plant Products Co. Ltd., Canada), Pythium oligandrum DV74 (for example the product POLYVERSUM® from Remeslo SSRO, Biopreparaty, Czech Republic), Reynoutria 40 sachlinensis (for example the product REGALIA® from Marrone Biolnnovations, USA), Talaromyces flavus V117b (for example the product PROTUS* from Prophyta, Germany), Trichoderma asperellum SKT-1 (for example the product ECO-HOPE® 13 from Kumiai Chemical Industry Co., Ltd., Japan), T. atroviride LC52 (for example the product SENTINEL* from Agrimm Technologies Ltd, New Zealand), T. harzianum T 22 (for example the product PLANTSHIELD® from BioWorks Inc., USA), T. harzianum TH 35 (for example the product ROOT PRO* from Mycontrol Ltd., Israel), 5 T. harzianum T-39 (e.g. the products TRICHODEX* and TRICHODERMA 2000@ from Mycontrol Ltd., Israel and Makhteshim Ltd., Israel), T. harzianum and T. viride (for example the product TRICHOPEL from Agrimm Technologies Ltd, New Zealand), T. harzianum ICCO12 and T. viride ICC080 (for example the product REMEDIER® WP from Isagro Ricerca, Italy), T. polysporum and T. harzianum (for 10 example the product BINAB® from BINAB Bio-Innovation AB, Sweden), T. stromaticum (for example the product TRICOVAB® from C.E.P.L.A.C., Brazil), T. virens GL-21 (for example the product SOILGARD® from Certis LLC, USA), T. viride (for example the products TRIECO® from Ecosense Labs. (India) Pvt. Ltd., India and BIO-CURE® F from T. Stanes & Co. Ltd., India), T. viride TV1 (for example the 15 product T. viride TV1 from Agribiotec srl, Italy), Ulocladium oudemansii HRU3 (for example the product BOTRY-ZEN® from Botry-Zen Ltd, New Zealand); - Others: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamine, metrafenon, pyriofenon, mildiomycin, oxine-copper, prohexadione-calcium, spiroxamin, tolylfluanid, N-(cyclopropylmethoxyimino-(6-difluoromethoxy-2,3-difluorophenyl) 20 methyl)-2-phenylacetamide, N'-(4-(4-chloro-3-trifluoromethylphenoxy)-2,5-dimethyl phenyl)-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 -methylformam id ine, N'-(5-difluoromethyl-2 methyl- 4

-(

3 -trimethylsiianylpropoxy)phenyl)-N-ethyl-N-methylformamidine, methyl 25 (1,2,3,4-tetrahydronapthalen-1 -yl)-2-{1 -[2-(5-methyl-3-trifluoromethylpyrazol- 1 yl)acetyl]piperidin-4-yl}thiazole-4-carboxylate, N-methyl-(R)-1,2,3,4-tetrahydro naphthalen-1 -yl-2-{ 1 -[2-(5-methyl-3-trifl uoromethylpyrazol- I -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-y methoxyacetate, N-methyl-2-{1-[2-(5 30 methyl-3-trifl uorom ethyl-1 H-pyrazol-1-yl)acetyl]piperidin-4-yl}-N-[(I R)-1,2,3,4-tetra hydronaphthalen-1 -yi]-4-thiazolecarboxamide; G) Growth regulators Abscisic acid, amidochlor, ancymidole, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, 35 dikegulac, dimethipin, 2,6-dimethyipuridine, ethephon, flumetralin, flurprimidole, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), metconazole, naphthaleneacetic acid, N-6-benzyladenine, paclobutrazole, prohydrojasmone, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-triiodobenzoic acid, trinexapac-ethyl and uniconazole; 40 H) Herbicides - Acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, 14 pretilachlor, propachlor, thenychlor; - amino acid analogs: bilanafos, glyphosate, glufosinate, sulfosate; - aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl; 5 - bipyridyls: diquat, paraquat; - Carbamates and thiocarbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate; - Cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, 10 tepraloxydim, tralkoxydim; - Dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin; - Diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen; 15 - Hydroxybenzonitriles: bromoxynil, dichlobenil, ioxynil; - Imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr; - Phenoxyacetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichloroprop, MCPA, MCPA-thioethyl, MCPB, mecoprop; 20 - 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, fluce 25 tosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosul furon, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, tria sulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1-((2-chloro 6-propylimidazo[1,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl)urea; 30 - Triazines: ametryne, atrazine, cyanazine, dimethametryne, ethiozine, hexazinone, metamitron, metribuzine, prometryne, simazine, terbuthylazine, terbutryne, triaziflam; - Ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, methabenzthiazurontebuthiuron; - Other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-methyl, 35 diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfon, pyroxsulam; - Others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarbazone, benfluresate, benzofenap, bentazone, benzobicyclon, bromacil, 40 bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethyl, chlorthal, cinmethylin, clomazone, cumyluron, cyprosulfamid, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid, 15 fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, fluorochloridon, flurtamon, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methylarsenic acid, naptalam, oxadiargyl, oxadiazone, oxaziclomefon, pentoxazone, pinoxadene, pyraclonil, pyraflufen-ethyl, pyrasulfotol, 5 pyrazoxyfen, pyrazolynate, quinoclamin, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, 4-hydroxy-3-[2-(2 methoxyethoxymethyl)-6-trifl uorom ethylpyrid in-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-pyrim idi n-1 -yl) phenoxy]pyrid in-2-yloxy)acetate, methyl 6-amino-5-chloro-2 10 cyclopropylpyrimidine-4-carboxylate, 6-ch loro-3-(2-cyclopropyl-6-methyl phenoxy)pyridazin-4-ol, 4-amino-3-chloro-6-(4-chlorophenyl)-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-dimethyl amino-2-fluorophenyl)pyridine-2-carboxylate; 15 I) insecticides - 0 rgano(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, 20 paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pi rimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon; - Carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, 25 propoxur, thiodicarb, triazamate; - Pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalo thrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluva 30 linate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin, - Insect growth inhibitors: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, 35 tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramate; - Nicotin receptors agonists/antagonists: clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1-(2-chloro-thiazol-5-ylmethyl) 2-nitrimino-3,5-dimethyl-[1,3,5]triazinane; 40 - GABA antagonists: endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, 5-amino-1-(2,6-dichloro4-methylphenyl)-4-sulfinamoyl-I H-pyrazole-3-thio carboxamide; 16 - Macrocyclic lactones: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram; - Mitochondrial electron transport chain inhibitor (METI) I acaricides: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim; 5 - METI 11 and III substances: acequinocyl, fluacyprim, hydramethylnon; - Uncouplers: chlorfenapyr; - Inhibitors of oxidative phosphorylation: cyhexatin, diafenthiuron, fenbutatin oxide, propargite; - Insect molting exhibitors: cryomazine; 10 - Inhibitors of mixed-function oxidases: piperonyl butoxide; - Sodium channel blockers: indoxacarb, metaflumizone; - Others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozin, sulfur, thiocyclam, flubendiamide, chlorantraniliprole, cyazypyr (HGW86); cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron and 15 pyrifluquinazone. Very suitable examples of further growth regulators are abscisic acid, ancymidol, aviglycine, 6-benzylaminopurine, brassinolides, chlormequat chloride, choline chloride, cyclanilide, diflufenzopyr, dikegulac, ethephon, flurprimidol, forchlorfenuron, 20 gibberellins A,, A 3 , A 4 , A 7 , inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidid, mepiquat chloride, metconazole, 1 -methylcyclopropene, naphthaleneacetic acid, paciobutrazole, prohydrojasmone, tebuconazole, thidiazuron, triapenthenol, 2,3,5-triiodobenzoic acid, trinexapac-ethyl and uniconazole. The growth regulator is preferably mepiquat chloride, chlormequat chloride or ethephone, in particular 25 mepiquat chloride. The granules may comprise up to 70% by weight, preferably up to 55% by weight and in particular up to 40% by weight of further growth regulator. In a preferred embodiment, the granules comprise from 0.1 to 70% by weight, preferably from 1 to 50 and in particular from 10 to 40% by weight of further growth regulator. 30 In one embodiment, the granules may comprise from 0.1 to 50% by weight of carboxyl containing growth regulator and from 0.5 to 45% by weight of solid acidifier. Preferably, the granules comprise from 0.5 to 30% by weight of carboxyl-containing growth regulator and from 2 to 30% of solid acidifier. Especially preferably, the granules comprise from 0.5 to 30% by weight of a growth regulator of the formula (I) in the form 35 of a free acid or of a salt, and from 2 to 30% by weight of a carboxylic acid having two to 20 carbon atoms, a hydrogen sulfate or a hydrogen phosphate. The abovementioned granules may comprise further formulation auxiliaries, complexing agents, inorganic sulfate, binders, surfactant or solid carrier, so that the total of all components of the granules amounts to 100% by weight. 40 In a further embodiment, the granules may comprise from 0.1 to 45% by weight of carboxyl-containing growth regulator, from 0.5 to 35% by weight of solid acidifier and 17 from 0.1 to 20% by weight of binder. Preferably, the granules comprise from 0.5 to 30% by weight of carboxyl-containing growth regulator, from 2 to 30% by weight of solid acidifier and from 0.5 to 15% by weight of binder. Especially preferably, the granules comprise from 0.5 to 30% by weight of a growth regulator of the formula (1) in the form 5 of a free acid or of a salt, from 2 to 30% by weight of a carboxylic acid having two to 20 carbon atoms, a hydrogen sulfate or a hydrogen phosphate, and from 0.5 to 15% by weight of disaccharide or maltodextrin. The abovementioned granules can comprise further formulation auxiliaries, complexing agents, inorganic sulfate, surfactant or solid carrier, so that the total of all components of the granules amounts to 100%. 10 In a further embodiment, the granules may comprise at least 0.1% by weight of carboxyl-containing growth regulator, at least 0.5% by weight of solid acidifier, at least 0.1% by weight of binder and at least 5% by weight of inorganic sulfate. Preferably, the granules comprise at least 0.1 % by weight of carboxyl-containing growth regulator, at 15 least 2% by weight of solid acidifier, at least 1.0% by weight of binder and at least 20% by weight of inorganic sulfate. The abovementioned granules can comprise further formulation auxiliaries, complexing agents, surfactant or solid carrier, so that the total of all components of the granules amounts to 100% by weight. 20 The present invention also relates to a process for the preparation of the granules according to the invention by extrusion or fluidized-bed granulation. The extrusion process can be carried out as follows: in general, it is customary to meter a physical mixture of carboxyl-containing growth regulator together with solid acidifier, 25 further pesticides and formulation auxiliaries freely, for example via a weigh feeder, into an extruder, where the mixture is warmed. In general, the components are mixed in a manner known per se in kneaders or extruders, preferably in single- or twin-screw extruders, in a temperature range of between 50 and 200 0 C, preferably between 20 and 150*C. The extruder may comprise mixing, kneading and return elements, as 30 required. Any solvents present and residual moisture may optionally be stripped off during the extrusion by means of gas outlet ports or vacuum pumps. Moreover, components in liquid or else in solid form may be introduced via pumps or conveying means arranged laterally. The shape of the extrusion die depends on the shape desired. The emerging extrudate may be shaped by extrusion granulation of the fully or 35 partially cooled extrudates, by hot-cutting of the extrudate at the extruder head using a granulator with rotating knives, by underwater granulation directly at the exit point of the extrusion from the die, or by another method conventionally used method. The resulting solid shapes may be processed further to give shaped articles, for example by injection molding. In a preferred embodiment, shaping of the emerging melt is by 40 extrusion granulation. The fluidized-bed granulation process may be carried out as follows: fluidized-bed 18 granulation is a well-studied process for the preparation of granules. Suitable systems and operating procedures have been described for example by Rosch and Probst, Verfahrenstechnik 1975 (9), 59-64 or in EP 0 799 569. A fluidized-bed granulator usually comprises a fluidizing chamber with a sieve plate consisting of a perforated 5 metal sheet. Here, heatable fluidizing gas at a certain entry temperature and flow rate flows through the sieve plate into the fluidizing chamber. Liquids or dispersions may be sprayed into the fluidizing chamber by means of a nozzle. Powders may be introduced into the granulator by suction. In the method comprising the fluidized-bed granulation, the most frequently used procedure is to introduced an aqueous composition 10 comprising some of the components into a fluidized-bed chamber. In most cases, introduction is effected by spraying the composition into a fluidized bed. In this context, the composition is, in most cases, sprayed via one or more nozzles, for example one-, two- or three-substance nozzles. It is preferred that the dispersion is dried via two substance nozzles using an inert gas, such as pressurized air or nitrogen, at a 15 pressure of from 1.2 to 5.0 bar and a bed temperature of from 15 to 100 C. Usually, the nozzle is arranged at a distance from the sieve plate which corresponds to 1.5 to 10 times, in particular 2 to 8 times, the thickness of the packing of the fluidized bed at rest. If the nozzle is too close above the fluidized bed, or if the nozzle enters the fluidized bed, severe aggregation takes place and the fluidized bed collapses. If the distance of 20 the nozzle to the fluidized bed is unduly large, the finely divided particles have time to dry, so that, in general, a powder but no granules will be obtained, but at least a product with a high proportion of dust. The process according to the invention may be carried out continuously or batchwise, preferably batchwise. Usually, heatable fluidizing gas, such as air, flows through the sieve plate into the fluidized-bed chamber. The 25 entry temperature of the fluidizing gas will in most cases amount to from 50 to 2200C, preferably from 70 to 150*C and in particular from 90 to 120*C. In a further embodiment, the entry temperature is below 1300C, preferably below 1200C, in particular below 1150C. The amount of fluidizing gas per square meter of incident flow surface area of the fluidized bed may amount to from 3000 to 20 000 m 3 /h, preferably 30 from 6000 to 18 000 m 3 /h and in particular from 9000 to 14 000 m 3 /h. The process may be carried out with a fluidized-bed filling of from 50 to 2000 kg/m 2 area of the incident flow surface, preferably from 100 to 1000 kg/im 2 . By fluidized-bed filling is understood, in continuous operation, the "holdup", and in the batch method the batch size, i.e. the amount of filling at the end of the granulation process. The fines which leave the 35 fluidized bed with the waste gas are separated out in the customary manner. They may be recirculated into the fluidized bed as seeds for the formation of granules. Both an internal and an external return of the fines is possible. All apparatuses conventionally employed for such purposes may be used for separating out the fines and for returning them. The finished granules are discharged via one or more suitable devices. All 40 conventionally used devices are suitable for this purpose, for example a countercurrent gravity separator, zigzag separator or discharge via a flap.

19 The present invention furthermore relates to the use of the granules according to the invention for the preparation of the spray mixture by bringing the granules into contact with water. The spray mixture may be an aqueous solution or an aqueous suspension, depending on the solubility and concentration of the individual granule components. 5 The spray mixture is usually the ready-to-use composition which can be applied using state-of-the-art application equipment. To prepare the spray mixture, the granules are usually mixed with an excess of water. During this process, the granules are advantageously dispersed or dissolved rapidly and completely in water. The aqueous spray suspension may comprise up to 5.0 kg, preferably from 0.25 to 2.5 kg of granules 10 in 100 to 1000 1 of water. Substances which are suitable for dilution in addition to water are also mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic 15 hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone. 20 In particular when using very hard and/or alkaline water, it may be advantageous to add further amounts of inorganic sulfates (for example ammonium sulfate) and/or acidifier to the solution or suspension made up for spraying in order to achieve a pH of from 3.5 to 6.5, preferably from 4.0 to 5.5. Thus, an addition of from 0.01 to 2% by weight, preferably from 0.1 to 0.5% by weight, of inorganic sulfate may be helpful. 25 The spray mixture is usually applied by spraying or atomizing. Various types of oils, and wetters, adjuvants, herbicides, bactericides, fungicides or insecticides, may be added immediately prior to application in the form of a tank mix. These substances can be admixed to the spray mixture in a weight ratio of tank mix: granules of 1:100 to 30 100:1, preferably 1:10 to 10:1. The pesticide concentration of the tank mix may be varied within substantial ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1 %. When used in plant protection, the application rates are between 0.01 and 2.0 kg of active substance per ha, depending on the nature of the desired effect. 35 The present invention furthermore relates to the use of the granules according to the invention for regulating the growth of plants. Virtually all developmental stages of a plant may be covered. Examples of plants are cereals, beet, fruit, legumes, soy, oilseed rape, mustard, olives, sunflowers, sorghum and millet, barley, oats, rye, 40 coconut, cucurbits, cotton, peanuts, potatoes, tomatoes, rice, Solanaceae, beans, citrus fruit, vegetable plants, maize, sugar cane, oil palm, tobacco, coffee, tea, bananas, avocado, fruit trees (such as plum, peach, cherry, apple, pear, mirabelle), 20 grape vines (such as white-wine grape varieties and red-wine grape varieties, for example MOller-Thurgau, Bacchus, Riesling, Scheurebe, Silvaner and/or Dornfelder, Lemberger, Tempranillo and Trollinger as red-wine grape varieties), hops, grass, soft fruit (for example strawberries, raspberries, currants or gooseberries), natural latex 5 plants, ornamentals, forestry plants or turf grasses (such as Kentucky Bluegrass, annual and perennial ryegrass, tall fescue, red fescue, white bentgrass, annual bluegrass, Zoysia, Bermuda grass, centipede grass, St. Augustine grass). Plants which can be used are also those which are tolerant to attack by insects, viruses, bacteria or fungi or to the application of herbicide as the result of breeding, including recombinant 10 methods. Preferred plants are fruit trees (in particular apple, pear and sweet cherry), Gramineae (in particular wheat, triticale, barley, oats and rye, but also maize, rice, sugarcane and turf grasses). 15 Examples a) to g) hereinbelow illustrate various inventive uses of the granules according to the invention: a) Thus, for example, it is possible to severely inhibit the vegetative growth of the 20 plants, which manifests itself in particular in reduced elongation. Accordingly, the growth of the treated plants is stunted; moreover, the leaves are darker in color. An advantageous feature in practice is found to be a reduced intensity of the growth of grasses on verges, in hedges, on canal embankments and on turfed areas such as parks, sports grounds and orchards, ornamental lawns and airfields, so that grass 25 cutting, which is laborious and expensive, can be reduced. b) Also of economic interest is increasing the standing ability of crops which are prone to lodging, such as cereals, maize and sunflowers. The resultant shortening and strengthening of the stem reduces or eliminates the danger of "lodging" (breaking) of 30 plants under adverse weather conditions before harvesting. Another important aspect is the use of growth regulators for inhibiting the elongation and for modifying the course of maturation in cotton. This makes possible move efficient mechanical harvesting of this crop plant. In fruit trees and other trees, pruning costs can be saved by means of the growth regulators. At the same time, biennial bearing of fruit trees may be 35 interrupted by growth regulators. By using growth regulators, it is also possible to increase the lateral branching of the plants. This is of interest when, for example, more intense tillering is desired in cereal plants. c) Also, winter hardiness can be increased considerably by means of growth regulators, 40 for example in winter cereals and winter rape. Here, firstly elongation and the development of unduly vigorous foliar or plant biomass (which is therefore particularly sensitive to frost) are inhibited. Secondly, the vegetative development of the young 21 plants after sowing and before the onset of winter frosts is slowed down despite advantageous growth conditions. Thus, the risk of frost damage of such plants, which tend to premature breakdown of floral inhibition and to switchover to the generative phase, is eliminated. In winter cereals, it is advantageous for the stands to be well into 5 the tillering phase in autumn due to treatment with growth regulators, but to enter the cold season without unduly vigorous growth. This can prevent increased sensitivity to frost and - owing to the relatively low amount of foliar biomass or plant biomass - attack by a variety of diseases (for example fungal disease). Moreover, inhibiting the vegetative growth makes possible denser planting of the soil in a number of crop 10 plants, so that higher yields based on the acreage may be achieved. d) Higher yields both in terms of plant parts and in terms of plant constituents can be achieved by means of growth regulators. Thus, for example, it is also possible to induce the growth of larger amounts of buds, flowers, leaves, fruits, seed kernels, roots 15 and tubers, to increase the sugar content in sugar beet, sugarcane and citrus fruits, to increase the protein content in cereals or soybeans, or to stimulate increased latex flow in rubber trees. In this context, the active substances may cause increased yields by engaging in the plant metabolism or by promoting or inhibiting the vegetative and/or generative growth. Finally, plant growth regulators can also bring about shortened or 20 extended developmental stages or else an acceleration or delay in maturity of the harvested plant parts pre- or post-harvest. e) Of economic interest is, for example, the facilitation of harvesting, which is made possible by concentrating, over time, the dehiscence or reduced adhesion to the tree in 25 the case of citrus fruits, olives or in other varieties and cultivars of pome fruit, stone fruit and hard-shelled fruit. The same mechanism, that is to say the promotion of the development of abscission tissue between the fruit or leaf portion and the shoot portion of the plant is also essential for a thoroughly controlled defoliation of useful plants such as, for example, cotton. 30 f) Moreover, growth regulators may reduce the water consumption of plants. This is particularly important in the case of cropped areas which require artificial irrigation, which requires great financial input, for example in arid or semi-arid zones. Owing to the use of growth regulators, the irrigation intensity can be reduced, and farm 35 economics improved. The effect of growth regulators may bring about better exploitation of the available water since, inter alia, the degree of stomatal opening is reduced, a thicker epidermis and cuticula are formed, root penetration into the soil is improved, the transpiring leaf surface area is reduced, or the microclimate in the crop stand is advantageously affected by more compact growth. 40 g) A physiological resistance to pathogens and harmful insects may also be achieved by means of growth regulators by altering metabolic processes and/or altering the 22 cytological structure. An advantage of the present invention is that the process can be carried out on an industrial scale using standard apparatuses. It permits the combination of carboxyl 5 containing growth regulators, such as prohexadione-calcium, with acidifiers in a single formulation. Furthermore, nontoxic starting materials are used. The granules prepared by the process according to the invention are highly storage-stable and may comprise large amounts of acidifiers. Upon dilution with water, spray suspensions are formed rapidly, even upon dilution with hard water. Previous homogenization of the granules 10 before the dilution step is not necessary. Also, the use of modern washing-in airlocks is possible without previously making the granules into a "paste". When removing some of the granules from the commercial packaging, they can be metered in in a simple manner because they are free-flowing (dry flowable). The granules have a potent bioregulatory activity. 15 In contrast to previous formulations, the following advantages in particular result: - As a rule, the admixture of adjuvants (for example ammonium sulfate or acidifier) is no longer required, which means simpler operation, improved user safety and fewer potential sources of error when making up the spray mixture. - The solubility of carboxyl-containing growth regulators such as prohexadione-Ca, is 20 improved. Now, the active substance is present in its active form (the free acid) immediately after making up the spray suspension. - In the presence of an acidifier (slightly acidic pH of the suspension), prohexadione is present in undissociated form (apolar) and can thus be taken up more rapidly by plant cells. The result is, in particular under unfavorable application conditions (for 25 example rapid drying-on of the spray mixture in warm and dry weather), an increased efficiency of the active substance. Moreover, rain fastness is achieved considerably more rapidly. The examples which follow are intended to illustrate the invention, without limiting it. 30 Examples Example 1: Preparation of the granules In a fluidized-bed granulator (for example Glatt GmbH, GPCG series), granules A to D 35 were prepared batchwise, as follows: first, an aqueous active-substance mixture was prepared from prohexadione-calcium, kaolin, silicate (mean particle size d50 9 pm, specific surface area 35 m 2 /g), antifoam (silicone-based), sucrose, maltodextrin, nonionic surfactant, anionic surfactant, and, optionally, acidifier (citric acid monohydrate, oxalic acid, sodium hydrogen sulfate) and/or EDTA-Na4. Then, this 40 active substance mixture was processed by wet-grinding methods to give an active substance suspension which was kept homogenous in a separate vessel, with stirring. Then, sieved ammonium sulfate (fraction 300-1000 pm) was introduced into the 23 fluidized-bed granulator as the fluidized bed. Using a two-substance nozzle (diameter 3.5 mm, nozzle pressure 3 bar), the active substance suspension was sprayed onto the ammonium sulfate in the fluidized bed. The spray rate of 4 1/min (spraying time 195 min) and the nozzle position were chosen such that no secondary agglomeration 5 occurred. The amount of fluidizing gas was approximately 12 000 m 3 /h with an entry temperature of 110*C and an exit temperature of 50"C. The water evaporation rate was 30-40 g/m 3 . Using the above process, granules A to D with the composition as shown in Table 1 were prepared. The granules were storage-stable and easy to package. 10 Table 1: Composition of the granules (ai data in % by weight) Granules A Granules B Granules C Granules D Prohexadione-calcium 10 10 10 10 Nonionic surfactant 10 10 10 10 Kaolin 3 3 3 3 Sucrose 4 4 4 4 Maltodextrin 2 2 2 2 Silica gel 8.8 8.8 8.8 8.8 Anionic surfactant 3 3 3 3 Antifoam 0.4 0.4 0.4 0.4 Sodium hydrogen sulfate - - 10 20 Oxalic acid 10 - Citric acid monohydrate - 10.9 - EDTA-Na 4 - 0.1 0.1 0.1 Ammonium sulfate 48.8 47.8 48.7 38.7 Example 2: Chemical and physical properties 15 Storage stability Granules A to D were subjected to a standardized storage test at elevated temperature (FAO Standard CIPAC (Collaborative International Pesticides Analytical Council) MT46.3 "Accelerated storage procedure") and stored for two weeks at 54 0 C. Before and after these accelerated storage tests, the chemical and physical properties were 20 tested. Physical stability (CIPAC MT 174 dispersion test "DISPERSIBILITY OF WATER DISPERSIBLE GRANULES"): Samples of in each case 2 g of granules A and B were placed into 100 ml of CIPAC water D before and after storage, fully dispersed and left to stand for 2 h. The sediment which formed in this spray mixture was read off at 25 < 0.05 ml. Further physical results are detailed in Table 2.

24 '- E E E =LEm c a) o C) ,t No 0 oD (* wfo 0 Of ca 2 . o S0 0 - - NOr 2 o0k n o (9 > r COio E to o r1 0 *0) coo CDw C 6< (a D w 0 ) ELLE o- > 0 o " 0 >U)c 0 H,= LV Wi-

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ooO O CDC 0 -0-... 5 09 ' o>0 - c> CD 6 Q- (D- -. 2 D -- -o >- O z4 En T:D -D0 ) 0" fl aD)q: - ( C) CoD to-Lo 0 Co o -*- .2 -o 6 d0 -CrN y ' (D r r- cu c a) - .)0 e= IL z I.

m D) CD ii ~ - ~ 0<0 * E( H C e _ o- -o -o co O E E o 0 U.) 5D 5 a) > 0o . 0 0 2 -DO r C 0 o cj 0 m < -- 6 oH Iw O 0 o C S _ 0 - In E ) Ef- l 1- M Lo C)w-0 w0 0) C, c: go gL D 0 (D U)~~cc c)*-D_ 0 w .0 C? m V 0 0 :V 0 ~ n v m LD o C') -jL L' -o o.9 L CDi C) (0 EO 0 - (DE a) r-uU aD a) m c HH< Coa-Q(D -CL LA > 24a Comprises/comprising and grammatical variations thereof when used in this specification are to be taken to specify the presence of stated features, integers, steps or components or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

Claims (15)

1. Granules comprising prohexadione-calcium and a solid acidifier, wherein the acidifier is a hydrogen sulfate or a hydrogen phosphate.

2. The granules according to claim 1, which comprise from 0.5 to 50% by 5 weight of acidifier.

3. The granules according to claim 1 or 2, which comprise from 5 to 25% by weight of acidifier.

4. The granules according to any one of claims 1 to 3, which comprise a binder. 10

5. The granules according to claim 4, wherein the binder is a saccharide.

6. The granules according to any one of claims 1 to 5, which comprise a nonionic or anionic surfactant.

7. The granules according to any one of claims 1 to 6, which comprise an inorganic sulfate. 15

8. The granules according to any one of claims 1 to 7, which comprise a complexing agent.

9. The granules according to any one of claims 1 to 8, which comprise a solid carrier.

10. The granules according to any one of claims I to 9, which comprise a 20 further growth regulator.

11. The granules according to claim 10, wherein the further growth regulator is mepiquat chloride, 26

12. The granules according to claim 11, which comprise from 25 to 40% by weight of mepiquat chloride.

13. A process for the preparation of the granules according to any one of claims 1 to 12 by extrusion or fluidized-bed granulation. 5

14. The use of the granules according to any one of claims 1 to 12 for the preparation of an aqueous spray mixture, by bringing the granules into contact with water.

15. The use of the granules according to any one of claims 1 to 12 for regulating the growth of plants. 10 BASF SE WATERMARK PATENT & TRADE MARK ATTORNEYS P35568AUOO