AU1031499A - Solid formulation of a plant protection agent - Google Patents

Description

Solid preparation of a crop protection agent 5 The present invention relates to a solid preparation of a crop protection agent, obtainable by preparing a melt comprising 1-80 % by weight of an active compound usable in crop protection or a combination of such active 10 compounds 20-99 % by weight of at least one thermoplastic binder having a melting point or glass temperature of more than 70 0 C 0-20 % by weight of additives, 15 the sum of all the ingredients being 100% by weight, and subsequent briquetting by dividing the thermoplastic melt into drops in a first step and solidifying the drops by cooling in a 20 second step. The present invention furthermore relates to a process for preparing a solid preparation of a crop protection agent, which comprises melting at least one active compound, at least one 25 thermoplastic binder having a melting point or glass temperature of more than 70 0 C and, if appropriate, customary additives to a thermoplastic mixture, dividing the mixture into drops and solidifying these drops by cooling in a second step. 30 The present invention furthermore relates to a method which comprises using a solid preparation of a crop protection agent in solid or dissolved form for controlling phytopathogenic fungi, unwanted vegetation, unwanted infestations by insects or mites and/or for regulating the growth of plants and allowing it to act 35 on plants, their habitat or on seed. Active-compound-containing preparations prepared by melt extrusion are generally known. The extrusion of active-compound-containing melts of water-soluble polymers, 40 preferably of vinylpyrrolidone copolymers, is described in EP-A 240 904 and EP-A 240 906. Solid preparations of crop protection agents having a sustained release of active compound are mentioned in EP-A 596 203. 45 2 WO 92/15197 describes the preparation of water-dispersible, rapidly releasing crop protection granules. The crop protection agent, together with water-soluble fillers, for example urea, sugar alcohols, "heat-activated-binders" (ethoxylated 5 alkylphenols or ethylene oxide/propylene oxide block copolymers) and various auxiliaries (anionic surfactants, dispersants, fillers, etc.), is extruded at 50-130 0 C, for example through a sieve, for forming. 10 WO 93/25074 discloses water-dispersible crop protection granules which contain, in addition to the active component and various additives, in particular polyethylene glycols and surfactants which contain ethylene oxide groups. 15 The coextrusion of crop protection agents with polyvinylpyrrolidone, subsequent cooling, crushing and grinding, is described in WO 94/08455. The ground extrudate is sieved and, if appropriate, tabletted. 20 WO 94/23579 describes the use of such solid concentrates for preparing aqueous dispersions of pyrethroid insecticides. WO 94/08455 describes the melt extrusion of crop protection 25 agents having polyvinylpyrrolidone as binder, however, the discharged melt is not subjected to a subsequent shaping step. The cold melt is crushed, ground and sieved. This process is complicated, cost-intensive, leads to the generation of dust and yields non-uniform fragmented granules which are not 30 abrasion-resistant. WO 93/25074 mentions the possibility of a formulation by means of a Rotoformer@. The binder used in all examples is polyethylene glycol. Preparation of the formulations as described, using the 35 active compounds diurone - similar to WO 93/25074, page 26, Example 14, - and kresoxim-methyl (IUPAC name: methyl methoxyimino-a-(o-tolyloxy)-o-tolylacetate) basically never resulted in any "solid solutions", ie. the active compound was not distributed in molecular-disperse form in the matrix. 40 Formulations which were prepared as described are cloudy, in most cases soft powder agglomerates which, in contrast to the formulations according to the invention, only disperse slowly and incompletely in water. 45 -n 3 Furthermore, it is known that pharmaceutically active compounds can be processed in combination with polymers by melt extrusion to give various solid forms (EP-A 0358 105, EP-A 0240 904). Described is the continuous shaping by means of a calender and 5 hot-cut pelletization. Melts of low viscosity, which may be obtained for example from formulations having a high content of active compound or from formulations with cheap sugars, etc., can only be processed with difficulties by the known processes, since agglutination occurs. Furthermore, only a limited heat transfer 10 area per amount of product is available in the known processes, which may lead to problems during scale up. Briquetting of melts of high viscosity with the aid of a Rotoformer@ is known. Briquettes are solid shaped articles which 15 may be formed when a material of high viscosity, while passing one or more openings, is divided into small drop-like amounts which are subsequently cooled to solid shaped articles, for example on a moving transport surface. This process is part of the prior art and is sold for example by Sandvik Process Systems 20 GmbH, Stuttgart, under the name Rotoformer@ (US 4,279,579). Briquetting of melts having a high content of active compound and low viscosity poses a problem, since these melts do not 25 sufficiently solidify during the shaping to solid preparations of crop protection agents. It is an object of the present invention to provide a homogeneous, agglutination-free solid formulation of crop 30 protection agents which is readily and finely dispersible and has high storage stability. We have found that this object is achieved by the composition described at the outset. 35 Suitable active compounds are generally those active compounds which do not decompose under the processing conditions during the preparation of the melt. 40 The amount of the active compound components in the complete preparation may vary within wide limits, depending on activity, release rate and dispersibility. Thus, the content of active compound may be in the range of 1-80% by weight, preferably 45 20-80% by weight, based on the complete preparation. The only precondition is that the preparation can still be processed jthermoplastically.

4 The active compound is advantageously present in the form of a "solid solution", ie. in molecular disperse form in the matrix of the binder. 5 In general, suitable binders are polymeric binders or binders of low molecular weight which can be processed thermoplastically without decomposition and which, in combination with the active compound and other additives, do not give solid forms which are prone to cold flow. According to experience, these are substances 10 which have a melting point (mp) or glass temperature (Tg) of more than 70 0 C, for example from 80 0 C to about 200 0 C (even higher in the case of plasticizing active compounds or additives). 15 The glass temperatures (Tg) of selected binders are compiled below: thermoplastic binder Tg ( 0 C) Polyvinylpyrrolidone having a K value 175, decomp. 20 of 30 LuviskolR K 30, BASF Polyvinylpyrrolidone having a K value 96, decomp. of 12 Kollidon@ 12 PF, BASF N-Vinylpyrrolidone/vinyl acetate copo- 100-105, decomp. 25 lymer, mass ratio VP/VA = 60/40, having a K value of 30 Luviskol@ VA 64, BASF To obtain forms which are solid and storage-stable at room 30 temperature, the melting point or the glass temperature of the thermoplastic binder should generally be above 70 0 C, preferably >80 0 C and particularly preferably >90 0 C. This is particularly true for cases where active compound and binder partly or completely form a solid solution, since the glass temperature or 35 the melting point is lowered considerably in these cases. This behavior becomes particularly evident with low-melting active compounds. The binder for water-dispersible instant-release granules should 40 advantageously be water-soluble or water-dispersible. Moreover, active compound and binder should generally be processible homogeneously, ie. phase separation in the liquid state should not occur. Ideally, this also applies to the cooled solid phase (solid solution). Thus, the binder should on the one hand be 45 water-soluble or swellable in a neutral aqueous solution, and on O-1 VC,~ 5 the other hand be capable of dissolving hydrophobic active compounds. Examples of suitable binders are: 5 Polyvinylpyrrolidone (PVP), copolymers of N-vinylpyrrolidone (NVP) and vinyl esters, especially vinyl acetate, copolymers of vinyl acetate and crotonic acid, partially hydrolyzed polyvinyl 10 acetate, polyvinyl alcohol, poly(hydroxyalkyl acrylates) ( for example Ci- or C 2 -alkyl), poly(hydroxyalkyl methacrylates) (for example Ci- or C 2 -alkyl), polyacrylates and polymethacrylates (Eudragit types), copolymers of methyl methacrylate and acrylic acid, cellulose esters, cellulose ethers, especially 15 methylcellulose and ethylcellulose, hydroxyalkylcelluloses, especially hydroxypropylcellulose, hydroxyalkylalkylcelluloses, especially hydroxypropylethylcellulose, cellulose phthalates, especially cellulose acetate phthalate and hydroxypropylmethylcellulose phthalate, and mannans, especially 20 galactomannans. The K values (according to H. Fikentscher, Cellulose-Chemie 13 (1932), pages 58 to 64 and 71 and 74.) of the polymers are in the range from 10 to 100, preferably 12 to 70, in particular 12 to 35, and for PVP > 17, in particular 20 to 35. 25 Preferred polymeric binders are polyvinylpyrrolidone (PVP), copolymers of N-vinylpyrrolidone (NVP) and vinyl esters, in particular vinyl acetate, copolymers of vinyl acetate and crotonic acid, partially hydrolyzed polyvinyl acetate, polyvinyl alcohol, poly(hydroxyalkyl acrylates) (Ci- or C 2 -alkyl), 30 poly(hydroxyalkyl methacrylates) (Ci- or C 2 -alkyl), polyacrylates and polymethacrylates (Eudragit types), copolymers of methyl methacrylate and acrylic acid. Particularly preferred polymeric binders are one or more 35 polyvinylpyrrolidones and/or one or more copolymers of N-vinylpyrrolidone. In the complete mixture of all the components, the polymeric binder should generally soften or melt in the range from 200 to 40 1800 C, preferably from 600 to 1300 C. The glass transition temperature of the mixture will therefore usually be below 1800 C, preferably below 1300 C. It is reduced if necessary by customary plasticizing auxiliaries. XVCJN The amount of plasticizer is at the most 20, generally from 0.5 -7 o 15, preferably from 0.5 to 5, % by weight, based on the total 0 co eight of the mixture in order to produce storage-stable solid CN ~* ~ N\P 6 formulations of crop protection agents which show no cold flow. Examples of such plasticizers are: long-chain alcohols, ethylene glycol, propylene glycol, glycerol, trimethylolpropane, triethylene glycol, butanediols, pentanols such as 5 pentaerythritol, hexanols, polyethylene glycols, polypropylene glycols, polyethylene/propylene glycols, silicones, aromatic carboxylic esters (eg. dialkyl phthalates, trimellitic esters, benzoic esters, terephthalic esters) or aliphatic dicarboxylic esters (eg. dialkyl adipates, sebacic esters, azelaic esters, 10 citric esters and tartaric esters), fatty acid esters such as glycerol mono-, di- or triacetate, fatty acid glycerides or sodium diethyl sulfosuccinate. Preferably however, the mixture does not contain any plasticizer. 15 For an efficient biological action of the preparation according to the invention, the addition of surfactants is sometimes useful. Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example 20 lignosulfonic acid, phenolsulfonic acid, naphthalinesulfonic acid and dibutylnaphthalinesulfonic acid, and of fatty acids, alkylsulfonates and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols or fatty alcohol glycol ethers, condensation products of sulfonated naphthaline and its derivatives with formaldehyde, condensation products of naphthaline or of naphthalinesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol [sic] ethers, 30 ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol [sic] or tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene [sic], lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors, methylcellulose, fatty alcohol ethoxylates, oxoalcohol ethoxylates, fatty amide ethoxylates, fatty amine ethoxylates, alkylpolyglycosides, propyleneoxide/ ethylene oxide block polymers, fatty acid ethoxylates, polycarboxylates based on maleic acid and/or acrylic 40 acid, ethylenediamine ethoxylates and propoxylates, aminated fatty alcohol ethoxylates, fatty alcohol ethoxylate sulfates and mixed ethylenediamine ethoxylate propoxylates. Suitable additives are fillers or auxiliaries which speed up the 45 release (disintegrants, wick materials), substances which improve the dispersibility or stabilize the dispersion (for example anionic surfactants) or also auxiliaries used in extrusions, such 0A 7 as lubricants or flow regulators. Colorants, such as azo dyes, organic or inorganic pigments or colorants of natural origin, inorganic pigments being employed in a concentration of from 0.001 to 10, preferably 0.5 to 3, % by weight, based on the total 5 weight of the formulation, may be added to the mixture to prepare the formulation, likewise stabilizers, such as antioxidants, light stabilizers, hydroperoxide destroyers, radical scavengers. Additionally, wetting agents, preservatives, adsorbants, mold 10 release agents and propellants may be added (cf. for example R. Voigt, Lehrbuch der Pharmazeutischen Technologie, VCH-Verlag, Weinheim, p. 178-185, 1987). The only precondition for the suitability of auxiliaries is a sufficient temperature stability. The present invention also embraces the process for preparing a solid preparation of a crop protection agent, wherein at least 20 one active compound, at least one thermoplastic binder having a glass transition temperature above 70 0 C and, if appropriate, customary additives are melted to a plastic mixture, and the melt is briquetted by dividing the melt into drops in a first step, and solidifying these drops by cooling in a second step. 25 Suitable binders are the binders mentioned above, in particular polyvinylpyrrolidones and/or N-vinylpyrrolidone copolymers. Advantageously, the thermoplastic melt is divided into drops 30 using a rotating screen roll, and the drops are then removed from the screen roll by a moving conveyor belt and subsequently solidified. The invention particularly preferably embraces a process for preparing a solid preparation of a crop protection agent wherein the briquetting is carried out with the aid of a Rotoformer@. Melts of low viscosity which solidify particularly rapidly on 40 leaving the extruder or are only slightly sticky may alternatively be comminuted into drops by means of rotating blades and then completely cooled and solidified. The process steps of mixing and melting can be carried out in the 45 known manner, as described for example in EP-A-240 904, EP-A-337 256 and EP-A-358 105.

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8 It is possible to mix the components first and then to melt and homogenize them. However, in particular when sensitive active compounds are used, it has been found to be preferable first to melt and premix the polymeric binder, if appropriate together 5 with customary additives, stirred vessels, stirrers, solid mixers, etc., being operated, if appropriate, alternately, and then to mix in homogeneously the sensitive active compound(s) in "intensive mixers" in still plastic phase at very short residence times. Active compound(s), binders and, if appropriate, additives 10 can be employed in solid form, as a resin, as a solution or a dispersion. The melting and mixing take place in an apparatus customary for these purposes. Particularly suitable are extruders or heatable 15 containers with stirrers, for example kneaders. When required, the number of revolutions in the kneader can be controlled by the temperature, ie. the kneader is operated at low speed in the mixing stage, and the number of revolutions are then increased during melting. 20 A mixing apparatus which can be used is also that employed for mixing in plastics technology. Suitable types of apparatus are described, for example, in "Mixing and Compounding of Polymers", edited by Ica Manas-Zloczower,Zehev Tadmor, Carl Hanser-Verlag, Munich, ISBN No.:1 - 56990-156-2. Particularly suitable mixing apparatus comprises extruders and dynamic and static mixtures, and stirred vessels, single-shaft stirrers with stripper mechanisms, especially paste mixers, multishaft stirrers, 30 especially PDSM mixers, solid mixers and, preferably, mixer/kneader reactors (for example ORP, CRP, AP, DTB supplied by List, or Reactotherm@ supplied by Krauss-Maffei or Ko-Kneter@ supplied by Buss), trough mixers and internal mixers or rotor/stator systems (for example Dispax@ supplied by IKA). 35 The mixing apparatus is charged continuously or batchwise in a conventional way. Powdered components can be introduced in a free feed, for example via a weigh feeder. Plastic materials can be fed in directly from an extruder or via a gear pump, which is 40 particularly advantageous if the viscosities and pressures are high. Liquid media can be metered in by a suitable pump unit. Mixing and/or melting-can also be carried out in parallel or alternately in two or more apparatus in batchwise operation, so 45 that a continuous operation of the in-line shaping apparatus is possible. 11 Vc- i1 9 The mixture obtained by mixing and melting the binder, the active compound and, if appropriate, the additive or the additives ranges from pasty to viscous (thermoplastic) and is thus extrudable. The glass transition temperature of the mixture is 5 below the decomposition temperature of all the components which are present in the mixture. According to the invention, the still plastic mixture is initially extruded as a continuous strand, for example using a 10 suitable extrusion die. During the extrusion, solvents and residual moisture which may still be present can be removed by means of a vacuum pump. If required, the extruder may contain mixing, kneading and recycling elements. The form of the extrusion die depends on the desired shape. Examples of suitable 15 dies include round hole dies or coextrusion dies, such as dies having a circular ring/slot-shaped die cross section. Coextrusion dies are used for preparing open or closed shapes having at least two layers. One of the layers contains an active compound, the other layer may be free of active compound or may, if 20 appropriate, contain another active compound. Further details are to be found in WO-A 97/15293. However, preference is given to using round hole dies, where the 25 still plastic mixture is formed into a strand having a circular cross section and discharged into the Rotoformer@ or a similar apparatus suitable for preparing briquettes. The viscosity of the melt to be processed in the Rotoformer@ at 30 the processing temperature employed of 100-2000 C is usually 20 - 20,000 mPas x sec, preferably 20 - 5000 mPas x sec. The heat of the melt is carried off for example via a cooling conveyor by direct cooling. The extrudate which has been cooled in this way is generally non-sticky and solid at room temperature. 35 PVP and NVP copolymers have relatively high melting points or relatively high glass temperatures. Surprisingly, owing to the high active compound concentration, these polymers of high melting point become so soft that, as a melt of low viscosity, 40 they can be divided into drops which solidify, after cooling, to homogenous, storage-stable shaped articles (briquettes) that do not stick. Particular preference is given to mixtures of active compound and 45 PVP or N-vinylpyrrolidone copolymers. At least in some cases solid solutions are formed, the products are solid, low-dust and V l have good wettability. Owing to the homogenous, mostly 1x; 10 molecular-disperse distribution of the active compound in the polymer matrix, the active compound is rapidly'and finely dispersed when the formulation is dissolved in water, additionally, a stable dispersion is formed. 5 The present invention further relates to the use of one or more binders from the group consisting of the polyvinylpyrrolidones or the N-vinylpyrrolidone copolymers or a mixture of one or more polyvinylpyrrolidones with one or more N-vinylpyrrolidone 10 copolymers for preparing a solid preparation of a crop protection agent according to the invention. The present invention furthermore relates to the use of the solid 15 preparation of a crop protection agent according to the invention for controlling phytopathogenic fungi, unwanted vegetation, infestation by insects or mites and/or for regulating plant growth, by allowing the preparation of the crop protection agent to act in solid or dissolved form on plants, their habitat or on 20 seed. The process according to the invention is suitable, for example, for processing crop protection agents having herbicidal, fungicidal, insecticidal, acaricidal and growth-regulating 25 action. In the list of herbicides below, possible active compounds are indicated, but the list is not limited to these. 30 Herbicides from the class of the 1,3,4-thiadiazoles, such as buthidazole, cyprazole; amides, such as allidochlor (CDAA), benzoylprop-ethyl, 35 bromobutide, chlorothiamid, dimepiperate, dimethenamid, diphenamid, etobenzanid (benzchlomet), flamprop-methyl, fosamin, isoxaben, monalide; naptalame, pronamid (propyzamid), propanil; 40 aminophosphoric acids, such as bilanafos (bialaphos), buminafos, glufosinate-ammonium, glyphosate, sulfosate; aminotriazoles, such as amitrol; 45 11 anilides, such as anilofos, mefenacet; aryloxyalkanoic acids, such as 2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop-P, dichlorprop-P (2,4-DP-P), fenoprop 5 (2,4,5-TP), fluoroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamide, napropanilide, triclopyr; benzoic acids, such as chloramben, dicamba; 10 benzothiadiazinones, such as bentazone; bleachers, such as clomazone (dimethazone), diflufenican, fluorochloridone, flupoxam, fluridone, pyrazolate, sulcotrione 15 (chloro-mesulone); carbamates, such as asulam, barban, butylate, carbetamide, chlorbufam, chlorpropham, cycloate, desmedipham, di-allate, EPTC, esprocarb, molinate, orbencarb, pebulate, phenisopham, 20 phenmedipham, propham, prosulfocarb, pyributicarb, sulf-allate (CDEC), terbucarb, thiobencarb (benthiocarb), tiocarbazil, tri-allate, vernolate; 25 quinolinecarboxylic acids, such as quinclorac, quinmerac; chloroacetanilides, such as acetochlor, alachlor, butachlor, butenachlor, diethatyl-ethyl, dimethachlor, metazachlor, metolachlor, pretilachlor, propachlor, prynachlor, terbuchlor, 30 thenylchlor, xylachlor; cyclohexenones, such as alloxydim, caloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim, tralkoxydim, 2-{1-[2-(4-chlorophenoxy)propyloxyimino]butyl}-3-hydroxy-5-(2H 35 tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one; dichloropropionic acids, such as dalapon; 40 dihydrobenzofurans, such as ethofumesate; dihydrofuran-1-ones, such as flurtamone; dinitroanilines, such as benefin, butralin, dinitramin, 45 ethalfluralin, fluchloralin, isopropalin, nitralin, oryzalin, pendimethalin, prodiamine, profluralin, trifluralin; 12 dinitrophenols, such as bromofenoxim, dinoseb, dinoseb-acetate, dinoterb, DNOC; diphenyl ethers, such as acifluorfen-sodium, aclonifen, bifenox, 5 chlornitrofen (CNP), difenoxuron, ethoxyfen, fluorodifen, fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen; dipyridylenes, such as cyperquat, difenzoquat-methylsulfate, diquat, paraquat-dichloride; ureas, such as benzthiazuron, buturon, chlorbromuron, chloroxuron, chlortoluron, cumyluron, dibenzyluron, cycluron, 15 dimefuron, diuron, dymron, ethidimuron, fenuron, fluormeturon, isoproturon, isouron, karbutilat, linuron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, monuron, neburon, siduron, tebuthiuron, trimeturon; 20 imidazoles, such as isocarbamide; imidazolinones, such as imazamethapyr, imazapyr, imazaquin, imazethabenz-methyl (imazame),imazethapyr; 25 oxadiazoles, such as methazole, oxadiargyl, oxadiazone; oxiranes, such as tridiphane; 30 phenols, such as bromoxynil, ioxynil; phenoxyphenoxypropionic esters, such as clodinafop, cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, fenthiaprop-ethyl, fluazifop-butyl, 35 fluazifop-p-butyl, haloxyfop-ethoxyethyl, haloxyfop-methyl, haloxyfop-p-methyl, isoxapyrifop, propaquizafop, quizalofop-ethyl, quizalofop-p-ethyl, quizalofop-tefuryl; 40 phenylacetic acids, such as chlorfenac (fenac); phenylpropionic acids, such as chlorophenprop-methyl; 45 13 protoporphyrinogen IX oxydase inhibitors, such as benzofenap, cinidon-ethyl, flumiclorac-pentyl, flumioxazin, flumipropyn, flupropacil, fluthiacet-methyl, pyrazoxyfen, sulfentrazone, thidiazimine; 5 pyrazoles, such as nipyraclofen; pyridazines, such as chloridazon, maleic hydrazide, norflurazon, 10 pyridate; pyridinecarboxylic acids, such as clopyralid, dithiopyr, picloram, thiazopyr; 15 pyrimidyl ethers, such as pyrithiobac-acid, pyrithiobac-sodium, KIH-2023, KIH-6127; sulfonamides, such as flumetsulam, metosulam; 20 sulfonylureas, such as amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron methyl, ethoxysulfuron, flazasulfuron, halosulfuron-methyl, 25 imazosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl; 30 triazines, such as ametryn, atrazine, aziprotryn, cyanazine, cyprazine, desmetryn, dimethamethryn, dipropetryn, eglinazine-ethyl, hexazinon, procyazine, prometon, prometryn, propazin, secbumeton, simazine, simetryn, terbumeton, terbutryn, terbuthylazine, trietazine; 35 triazinones, such as ethiozin, metamitron, metribuzin; triazolecarboxamides, such as triazofenamid; 40 uracils, such as bromacil, lenacil, terbacil; various, such as benazolin, benfuresate, bensulide, benzofluor, butamifos, cafenstrole, chlorthal-dimethyl (DCPA), cinmethylin, 45 dichlobenil, endothal, fluorbentranil, mefluidide, perfluidone, piperophos.

14 In the list of compounds having growth-regulating action below, possible active compounds of this group are indicated, but the list is not limited to these. 5 Compounds having growth-regulating action, such as 1-naphthylacetamide, 1-naphthylacetic acid, 2-naphthyloxyacetic acid, 3-CPA, 4-CPA, ancymidol, anthraquinone, BAP, butifos; 10 tribufos, butralin, chlorflurenol, chlormequat, clofencet, cyclanilide, daminozide, dicamba, dikegulac sodium, dimethipin, chlorfenethol, etacelasil, ethephon, ethychlozate, fenoprop, 2,4,5-TP, fluoridamid, flurprimidol, flutriafol, gibberellic acid, gibberillin, guazatin, imazalil, indolylbutyric acid, 15 indolylacetic acid, karetazan, kinetin, lactidichlor-ethyl, maleic hydrazide, mefluidide, mepiquat-chloride, naptalam, paclobutrazole, prohexadione calcium, quinmerac, sintofen, tetcyclacis, thidiazuroh, triiodobezoic acid, triapenthenol, triazethan, tribufos, trinexapacethyl, uniconazole. 20 In the list of fungicides below possible active comounds are indicated, but the list is not limited to these. Fungicides of the class 25 sulfur, dithiocarbamates and their derivatives, such as iron(III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, 30 tetramethylthiuram disulfides [sic], ammonia complex of zinc (N,N-ethylenebisdithiocarbamate), ammonia complex of zinc (N,N'-propylenebisdithiocarbamate), zinc (N,N'-propylenebisdithiocarbamate), N,N'-polypropylenebis(thiocarbamoyl)disulfide; 35 nitro derivatives, such as dinitro(1-methylheptyl)phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate, 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl 40 5-nitroisophthalate; heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, 0,0-diethyl phthalimidophosphonothioate, 45 5-amino-1-[bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4 triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo[4,5-b]quinoxaline, methyl 15 1-(butylcarbamoyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 2-(furyl-(2))benzimidazole, 2-(thiazolyl-(4))benzimidazole, N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide, 5 N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfuric diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole, 10 1,4-dichloro-2,5-dimethoxybenzene, 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, pyridine 2-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4 15 dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide, 2,4,5-trimethylfuran-3-carboxanilide, N-cyclohexyl-2,5-dimethylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide, 20 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine 2,2,2-trichloroethyl acetal, piperazine-1,4-diyl-bis-1-(2,2,2 trichloroethyl)formamide, 1-(3,4-dichloroanilino)-1 formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecylmorpholine or its salts, 25 2,6-dimethyl-N-cyclododecylmorpholine or its salts, N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis 2,6-dimethylmorpholine, N-[3-(p-tert-butylphenyl)-2-methyl propyl]piperidine, 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-di oxolan-2-ylethyl]-1H-1,2,4-triazole, 1-[2-(2,4-dichloro 30 phenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole, N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolyl urea, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1 yl)-2-butanone, 1-(4-chlorophenoxy)-3,3-dimethyl-1 (lH-1,2,4-triazol-1-yl)-2-butanol, (2RS, 3RS)-1-[3-(2-chloro 35 phenyl)-2-(4-fluorophenyl)oxiran-2-ylmethyl]-1H-1,2,4 triazole, a-(2-chlorophenyl)-a-(4-chlorophenyl)-5-pyrimidine methanol, 5-butyl-2-dimethylamino-4-hydroxy-6 methylpyrimidine, bis(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene, 1,2-bis-(3 40 methoxycarbonyl-2-thioureido)benzene, anilinopyrimidines, such as N-(4,6-dimethylpyrimidin-2 yl)aniline, N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]aniline, N-(4-methyl-6-cyclopropylpyrimidin-2-yl)aniline, 45 16 phenylpyrroles, such as 4-(2,2-difluoro-1,3-benzodioxol-4 yl)pyrrole-3-carbonitrile, cinnamamides, such as 3-(4-chlorophenyl)-3-(3,4-dimethoxy 5 phenyl)acryloylmorpholine, and a variety of fungicides, such as dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2 10 hydroxyethyl]glutarimide, hexachlorobenzene, methyl N-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate, DL-N-(2, 6-dimethylphenyl ) -N-(2 '-methoxyacetyl ) alanine methyl ester, N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2 aminobutyrolactone, DL-N-(2,6-dimethylphenyl)-N 15 (phenylacetyl)alanine methyl ester, 5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2, 4-dioxo-1,3 oxazolidine, 3-[3,5-dichlorophenyl(-5-methyl-5-methoxy methyl]-1,3-oxazolidine-2,4-dione [sic], 3-(3,5-dichloro phenyl)-1-isopropylcarbamoylhydantoin, N-(3,5-dichloro 20 phenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide, 2 -cyano-[ N- (ethylaminocarbonyl) -2-methoximino ] acetamide, 1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole, 2,4-difluoro-a-(lH-1,2,4-triazolyl-1-methyl)benzhydryl alcohol, N-(3-chloro-2,6-dinitro-4-trifluoromethyl 25 phenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine, 1-((bis-(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4 triazole; strobilurins, such as methyl E-methoximino-[a-(o-tolyloxy) 30 o-tolyl]acetate, methyl E-2-{2-[6-(2-cyanophenoxy) pyridimin-4-yloxy]-phenyl}-3-methoxyacrylate, N-methyl E-methoximino- [a- (2 -phenoxyphenyl) ] acetamide, methyl-E-methoximino-[a-(2,5-dimethylphenoxy)-o tolyl]acetamide. 35 Additionally, fungicidally active compounds of the formula IA containing a nucleus Q and IB containing a nucleus T, respectively, from the class of the strobilurins are to be mentioned, 40 RX T .. RY 45 Xn R" Xn R" IA IB 17 where ==. is a single or a double bond and the nucleus, the index and the substituents have the following meanings: Q is cyclopentenyl, cyclohexenyl, phenyl, pyrrolyl, thienyl, furyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, thiadiazolyl, triazolyl, pyridinyl, 2-pyridonyl, pyrimidinyl and triazinyl; 10 T is phenyl, oxazolyl, thiazolyl, thiadiazolyl, oxadiazolyl, pyridinyl, pyrimidinyl and triazinyl; Y is =C- or -N-; 15 R' is -C[CO 2

CH

3

]=CHOCH

3 , -C[CO 2

CH

3

]=NOCH

3 , -C[CONHCH 3

]=NOCH

3 ,

-C[CO

2

CH

3

]=CHCH

3 , -C[CO 2

CH

3

]=CHCH

2

CH

3 , -C[COCH 3

]=NOCH

3 ,

-C[COCH

2

CH

3

]=NOCH

3 , -N(OCH 3

)-CO

2

CH

3 , -N(CH 3

)-CO

2

CH

3 ,

-N(CH

2

CH

3

)-CO

2

CH

3 ; 20 R" is a C-organic radical which is attached directly or via an oxy, mercapto, amino or alkylamino group; for example unsubstituted or substituted aryloxy, substituted hetaryloxy, substituted aryloxymethylene, substituted 25 hetaryloxymethylene, substituted arylethenylene, substituted hetarylethenylene, and the like, see WO 96/32015, pages 6 and 7, where aryloxy is, for example, a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, for example phenyl, naphthyl and 30 anthracenyl, which is linked to the skeleton via an oxygen atom (-0-); and where hetaryloxy is, for example, a 5- or 6-membered heterocycle (heterocyclyl) containing, in addition to 35 carbon ring members, one to three nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms. With respect to the cyclic (saturated, unsaturated or 40 aromatic) groups, the term "unsubstituted or substituted" is meant to express that these groups may be partially or fully halogenated and/or may carry one to four (in particular one to three) of the following radicals: 45 - cyano, nitro, hydroxyl, amino, carboxyl, LdN aminocarbonyl, alkyl, haloalkyl, alkenyl, \W haloalkenyl, alkenyloxy, haloalkenyloxy, alkynyl, 18 haloalkynyl, alkynyloxy, haloalkynyloxy, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, 5 dialkylaminocarbonyl, alkylcarbonylamino, alkoxycarbonylamino, alkylcarbonyl-N-alkylamino and alkylcarbonyl-N-alkylamino, where the alkyl groups in these radicals preferably contain 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms, and the 10 alkenyl or alkynyl groups mentioned in these radicals contain 2 to 8, preferably 2 to 6, in particular 2 to 4 carbon atoms; together with a group X and the ring Q or T to which they 15 are attached, an unsubstituted or substituted bicyclic, partially or fully unsaturated system which may contain one or more heteroatoms from the group consisting of oxygen, sulfur and nitrogen, in addition to carbon ring members; 20 Rx is -OC[CO 2

CH

3

]=CHOCH

3 , -OC[CO 2

CH

3

]=CHCH

3 ,

-OC[CO

2

CH

3

]=CHCH

2

CH

3 , -SC[CO 2

CH

3

]=CHOCH

3 , -SC [CO 2

CH

3

]I=CHCH

3 , -SC [CO 2

CH

3

]I=CHCH

2

CH

3 , 25

-N(CH

3

)C[CO

2

CH

3

]=CHOCH

3 , -N(CH 3

)C[CO

2

CH

3

]=NOCH

3 ,

-CH

2

C[CO

2

CH

3

]=CHOCH

3 , -CH 2

C[CO

2

CH

3

]=NOCH

3 ,

-CH

2

C[CONHCH

3

]=NOCH

3 ; 30 RY -0-, -S-, =CH-, -HC=,-N= or =N-; n is 0, 1, 2 or 3, it being possible for the radicals X to 35 be different if n is greater than 1; X is cyano, nitro, halogen, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, Ci-C 4 -alkylthio; 40 in the case that n > 1, a C 3

-C

5 -alkylene,

C

3

-C

5 -alkenylene, oxy-C 2

-C

4 -alkylene, oxy-Ci-C 3 -alkyleneoxy, oxy-C 2

-C

4 -alkenylene, oxy-C 2

-C

4 -alkenyleneoxy or butadienediyl group which is attached to two adjacent carbon atoms of the phenyl ring, where these chains may for their part carry one to three of the following radicals: halogen, Ci-C 4 -alkyl,

O

19 Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy or Ci-C 4 -alkylthio. Structures of the compounds IA and IB are disclosed in detail in 5 WO 96/32015, pages 3 to 18. When preparing the mixtures, preference is given to employing the active compounds IA and IB, which may be admixed, if required, with further active compounds against pests (for example insects, arachnids or nematodes) or harmful fungi, or else herbicidal or growth-regulating active compounds or fertilizers. They are especially important for controlling a large number of 15 fungi in a variety of crop plants, such as cotton, vegetable species (for example cucumbers, beans and cucurbits), barley, grass, oats, coffee, maize, fruit species, rice, rye, soya, grapevine, wheat, ornamentals, sugar cane, and a variety of seeds. 20 They are particularly suitable for controlling the following plant diseases: - Alternaria species in vegetables and fruit, 25 - Botrytis cinerea (gray mold) in strawberries, vegetables, ornamentals and grapevines, Cercospora arachidicola in groundnuts, e Erysiphe cichoracearum and Sphaerotheca fuliginea in 30 cucurbits, * Erysiphe graminis (powdery mildew) in cereals, - Fusarium and Verticillium species in a variety of plants, 0 Helminthosporium species in cereals, 35 e Mycosphaerella species in bananas, * Phytophthora infestans in potatoes and tomatoes, 0 Plasmopara viticola in grapevines, e Podosphaera leucotricha in apples, 40 * Pseudocercosporella herpotrichoides in wheat and barley, * Pseudocercosporella species in hops and cucumbers, e Pseudoperonospora- species in hops and cucumbers, e Puccinia species in cereals, * Pyricularia oryzae in rice, Rhizoctonia species in cotton, rice and lawn, 0 U n1 '0N 20 Septoria nodorum in wheat, * Uncinula necator in grapevines, * Ustilago species in cereals and sugarcane, and 5 - Venturia inaequalis (scab) in apples. The application rates of the abovementioned preferred compounds are, when used for protecting crop plants, from 2 to 0.1 kg/ha, preferably from 1.25 to 0.2 kg/ha, in particular from 0.75 to 10 0.3 kg/ha, depending on the desired effect. For the compounds IA and IB, the application rates are from 1 to 0.01 kg/ha, preferably from 0.5 to 0.02 kg/ha, in particular from 0.25 to 0.03 kg/ha. 15 For seed treatment, the application rates of the mixture are generally from 0.1 to 100 g/100 kg of seed, preferably from 0.5 to 50 g/100 kg of seed, in particular from 1 to 10 g/100 kg of 20 seed. In general, the formulations comprise from 1 to 80, preferably from 20 to 80, particularly preferably from 50 to 80, % by weight of one of the compounds IA and IB, or of the mixture of the 25 compounds IA and IB. The active compounds are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to 1 H NMR spectrum or HPLC). 30 The compounds IA, IB or mixtures thereof, or the corresponding formulations, are applied by treating the harmful plants, their habitat or the materials, plants, seeds, soils, areas or rooms to be protected against fungal attack with a fungicidally effective 35 amount of the mixture, or of the compounds IA or IB in the case of separate application. The treatment may be carried out before or after infection by the harmful fungi. 40 The processes according to the invention permit the preparation of a solid preparation of a crop protection agent which is generally free of organic solvents. Owing to the preparation process, the resulting briquettes have very homogeneous particle size, are transparent, substantially spherical and have a smooth, abrasion-free surface structure which does not tend to Vd 45 agglutinate. The extrusion process and the briquetting process are dust-free, since the solidified extrudate does not have to be ground in order to obtain a uniform particle size, and additional

~V

21 apparatus for reducing active-compound-containing dusts are therefore not required. Compared to polyethylene glycol-containing formulations, the 5 formulations according to the invention have the following advantages: They give abrasion-resistant, form-stable and non-sticky briquettes which can be quickly and finely dispersed in water. 10 The last-mentioned properties are a necessary precondition for the application of the active compounds in agriculture. When making up the spray liquor, the active compound should disperse rapidly and finely to ensure as uniform as possible a 15 distribution of the active compounds on the field. In addition to application by spraying, the formulations according to the invention can also be used for application by broadcasting. 20 The process according to the invention has the advantage that in particular melts of low viscosity, which cause problems with the prior art for extrusion, can be processed without problems in a briquetting process. 25 Using the process according to the invention, it is possible to prepare solid preparations of a crop protection agent having particularly accurate dimensions. The process is inexpensive, permits the preparation of a very high number of pieces per time 30 unit and avoids waste. Below, the process according to the invention is illustrated by examples. 35 General procedure The amounts of active compound, polymers and, if appropriate, additives (for example nonionic surfactants) stated in the 40 examples were introduced mixed or else separately into a co-rotating, tightly meshing twin-screw extruder ZSK 30 (supplied by Werner & Pfleiderer GmbH, Stuttgart, Germany) and extruded over 12 temperature zones. C r\-V 5f 22 The table below gives details of the temperature gradient (OC) in the extruder (zones 1 - 12) and Rotoformer@ (roll and conveyor) of Examples 1 and 2: 5 Zone Zone Zone Zone Roll Con 1 2 3 4-12 veyor Temperature 20-100 100 120 140-180 150 25

(

0 C) L 10 The speed of the screws can be varied in the range from 100-300 rpm, at from 20 to 100 0 C in the feed zone (zone 1) and from 100 to 180 0 C in the melting zones (zone 2 - 12). The throughput was 10-12 kg/h and the residence time 1-2 min. The 15 active compound, the polymer and the additives were transported to the extruder inlet via weigh feeders, fed in and melted. Lutensol@AT 25 (C 1 6

-C

1 8 fatty alcohol having 25 ethylene oxide units,BASF) was, if required, added in liquid form and incorporated using mixer and kneading elements. Additionally, 20 there were the possibility of degassing in several extruder zones. The melt which was discharged at the end of the extruder via a die was introduced into the Rotoformer roll by means of a gear pump. The rotating heated roll has a screen mantle, and the molten extrudate is discharged through the perforation (d = 1 mm) 25 of the screen mantle onto a cooled conveyor. From there, the product was then transferred into the container in question by means of a scrape. The resulting briquettes have a diameter of about 1-2 mm. The throughput is 10-12 kg/h. 30 The Rotoformer@ (type 50.221, supplied by Sandvik Process Systems GmbH, Stuttgart, Germany) consists of a roll having 3720 holes (d=lmm) and a capacity of about 2 kg of melt which is mounted about 3 mm over a cooling conveyor of a band width of 400 mm and a band length of 4 m. The temperature of the roll was maintained at 140-180 0 C, the conveyor temperature was adjusted to 20 0 C by means of water cooling and the conveyor speed was 30 m/min. Example 1 40 Various solid preparations of crop protection agents of different composition A - D were prepared as described in the general procedure. The active compound in the formulations was kresoxim-methyl (IUPAC name: methyl lyd 5 methoxyimino-a-(o-tolyloxy)-o-tolylacetate), the binder was 23 Luviskol@ K 30, Luviskol@ VA 64 or, as additive, Lutensol® AT 25. The amounts that were metered in are shown in the table below. 5 Formu- Kresoxim- Luviskol@ Luviskol@ Lutensol@ lation methyl K 30 VA 64 AT 25 [% by weight] [% by [% by [% by weight] weight] weight] 10 A 50 50 - B 50 45 5 C 50 45 - 5 D 50 45 4.5 0.5 15 After melt extrusion and subsequent briquetting in the Rotoformer@, the formulations A to D give transparent, hard and form-stable spherical briquettes having a smooth surface. The active compound content of the briquettes in question was 20 examined by HPLC. After 3 months of storage at 25 0 C in a cylindrical 25 kg container (diameter: 30 cm), the briquettes remain form-stable. On storage at 45 0 C for three days, all the briquettes remain form-stable, flowing ("cold flow") does not occur. 25 The densities of the briquettes were determined using a Pyknometer and the solvent pentane. The bulk densities were determined in a measuring cylinder. 30 Formulation Density [g/ml] Bulk density [g/ml] A 1.226 755 35 B 1.222 734 C 1.247 759 D 1.223 723 To determine the particle size distribution, a sieve analysis was 40 carried out (Lit.: "Ullmanns Encyclopddie der technischen Chemie" 4th Edition, Volume 5, Analysen- und MeBverfahren, VCH Weinheim, 1980, p. 726-738.) 45

IIC

U

24 Mesh size Formulation Formulation Formulation Formulation [mm] A B C D [percentage [percentage [percentage [percentage by mass] by mass] by mass] by mass] 5 > 3.0 0 0 0 0 2.0-3.0 5.18 0.96 2.29 4.36 1.6-2.0 90.11 74.19 85.57 88.49 1.25-1.6 4.71 22.60 11.75 7.15 10 1.0-1.25 0 2.25 0.39 0 0.5-1.0 0 0 0 0 <0.5 0 0 0 0 The preparation by Rotoformer@ results in very uniform 15 formulations. The weighed arithmetic means result from the mean mesh sizes (d: mean equivalent diameter, w: percentage by mass): 20 d = 2 wi di Formulation Formulation Formulation Formulation A B C D 25 d [mm] 1.82 1.71 1.77 1.78 Example 2 Preparations from WO 93/25074, pages 26 and 27, Example 14 and 30 16, containing the binder polyethylene glycol (PEG) 8000 were prepared in a comparative experiment in the formulations E (active compound kresoxim-methyl) and F (active compound diuron) and compared in terms of their dispersibility with the formulations A to D according to the invention containing the binder polyvinylpyrrolidone Luviskol@ K30. In a Petri dish, 5 g of active compound were added to 5 g of molten binder PEG 8000, and the temperature of the mixture was 40 kept at 900 - 110 0 C. With the aid of a Pasteur pipette, drops of a diameter of 1 to 2 mm were transferred onto a superior chromium alloy steel plate and cooled to room temperature. By this method, a number of briquettes sufficient for carrying out dispersibility experiments were prepared. 45

O

25 The dispersibility was examined as follows: 1.0 g of a sieve fraction (1.6-2 mm) of the formulation in question were introduced with stirring (magnetic stirrer Ikamag 5 RET-G, supplied by Janke & Kunkel GmbH & Co. KG., Staufen, Germany; Teflon stirrer 1 = 4 cm) into a 1 1 glass vessel of a diameter of 10 cm filled with 1000 ml of tap water (T = 20 0 C) at a stirrer speed of 800 rpm (0.1% strength dispersion). After 10 min, the dispersion is filtered off through 300 p and 160 p 10 sieves and the sieve residue is determined in % by weight based on the starting material (1.0 g). Formulation kresoxim- Luviskol@ Luviskol@ Lutensol@ methyl K 30 VA 64 AT 25 15 [% by [% by [% by [% by weight] weight] weight] weight] A 50 50 - B 50 45 5 20 C 50 45 - 5 D 50 45 4.5 0.5 E 50 - 50 F - 50 50 25 Formulation Sieve residue 300 m Sieve residue 160 p [%] [%] A 0 0 30 B 1 1 C 6 8 D 0 0 E 46 47 F 60 61 35 The formulations E and F contain the binder polyethylene glycol PEG 8000. The briquettes prepared according to WO 93/25074 are cloudy powder agglomerates which contain the active compound in crystalline form. Furthermore, the briquettes of formulation E 40 are sticky at room temperature, ie. they form agglutinates and do not flow. The formulations A - D contain the binder polyvinylpyrrolidone and give transparent, hard, non-sticky and form-stable spherical d briquettes having a smooth surface. The active compound content of the briquettes in question was examined by HPLC. The active )ompound is present in molecular-disperse form and can be quickly

NZ

26 and finely dispersed in water. The sieve residues of formulations A - D after 10 minutes of stirring are negligable (0-8%), while the briquettes of formulations E and F disperse very slowly and have a high proportion of coarse particles (47-61%). 5 10 15 20 25 30 35 40 45

Claims (2)

1. A solid preparation of a crop protection agent, obtainable by preparing a melt comprising 1-80 % by weight of'an active compound usable in crop protection or a combination of such 10 active compounds

20-99 % by weight of at least one thermoplastic binder having a melting point or glass temperature of more than 70 0 C 0-20 % by weight of additives, 15 the sum of all the ingredients being 100% by weight, and subsequent briquetting by dividing the thermoplastic melt into drops in a first step and solidifying the drops by 20 cooling in a second step. 2. A solid preparation of a crop protection agent as claimed in claim 1, obtainable by melt extrusion and subsequent briquetting. 25 3. A solid preparation of a crop protection agent as claimed in claim 1 or 2, where the thermoplastic melt is divided into drops with the aid of a rotating screen roll and the drops are subsequently cooled to solid shaped articles on a moving 30 transport surface. 4. A solid preparation of a crop protection agent as claimed in any of claims 1 to 3, comprising as binder one or more polyvinylpyrrolidones. 35 5. A solid preparation of a crop protection agent as claimed in any of claims 1 to 3, comprising as binder one or more N-vinylpyrrolidone copolymers. 40 6. A solid preparation of a crop protection agent as claimed in any of claims 1 to 3, comprising as binder a mixture of one or more polyvinylpyrrolidones and one or more N-vinylpyrrolidone copolymers. 45 28 7. A solid preparation of a crop protection agent as claimed in any of claims 1 to 6, comprising at least one compound having fungicidal, herbicidal, insecticidal, acaricidal or growth-regulating action, or a mixture of active compounds 5 from the group consisting of these compounds. 8. A solid preparation of a crop protection agent as claimed in claim 7, comprising as active compound at least one fungicidal compound of the formula IA containing a nucleus Q 10 or IB containing a nucleus T from the class of the strobilurins RX 15 T .. RY Xn - xn R" IA IB 20 where == is a single or a double bond and the nucleus, the index and the substituents have the following meanings: Q is cyclopentenyl, cyclohexenyl, phenyl, pyrrolyl, thienyl, furyl, pyrazolyl, imidazolyl, oxazolyl, 25 isoxazolyl, thiazolyl, thiadiazolyl, triazolyl, pyridinyl, 2-pyridonyl, pyrimidinyl and triazinyl; T is phenyl, oxazolyl, thiazolyl, thiadiazolyl, oxadiazolyl, pyridinyl, pyrimidinyl and triazinyl; 30 Y is =C- or -N-; R' is -C[CO 2 CH 3 ]=CHOCH 3 , -C[CO 2 CH 3 ]=NOCH 3 , -C[CONHCH 3 ]=NOCH 3 , 35 -C[CO 2 CH 3 ]=CHCH 3 , -C[CO 2 CH 3 ]=CHCH 2 CH 3 , -C[COCH 3 ]=NOCH 3 , -C[COCH 2 CH 3 ]=NOCH 3 , -N(OCH 3 )-CO 2 CH 3 , -N(CH 3 )-CO 2 CH 3 , -N(CH 2 CH 3 )-CO 2 CH 3 ; R" is a C-organic radical which is attached directly or via 40 an oxy, mercapto, amino or alkylamino group; together with a group X and the ring Q or T to which they are attached, an unsubstituted or substituted bicyclic, partially or fully unsaturated system which may contain 45 one or more heteroatoms from the group consisting of 29 oxygen, sulfur and nitrogen, in addition to carbon ring members; RX is -OC[CO 2 CH 3 ]=CHOCH 3 , -OC[CO 2 CH 3 ]=CHCH 3 , 5 -OC[CO 2 CH 3 ]=CHCH 2 CH 3 , -SC[CO 2 CH 3 ]=CHOCH 3 , -SC[CO 2 CH 3 ]=CHCH 3 , -SC[CO 2 CH 3 ]=CHCH 2 CH 3 , -N(CH 3 )C[CO 2 CH 3 ]=CHOCH 3 , -N(CH 3 )C[CO 2 CH 3 ]=NOCH 3 , -CH 2 C[CO 2 CH 3 ]=CHOCH 3 , -CH 2 C[CO 2 CH 3 ]=NOCH 3 , -CH 2 C[CONHCH 3 ]=NOCH 3 ; 10 RY -0-, -S-, =CH-, -HC=,-N= or =N-; 15 n is 0, 1, 2 or 3, it being possible for the radicals X to be different if n is greater than 1; 20 X is cyano, nitro, halogen, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, Ci-C 4 -alkylthio; in the case that n > 1, a C 3 -C 5 -alkylene, C 3 -C 5 -alkenylene, oxy-C 2 -C 4 -alkylene, 25 oxy-Ci-C 3 -alkyleneoxy, oxy-C 2 -C 4 -alkenylene, oxy-C 2 -C 4 -alkenyleneoxy or butadienediyl group which is attached to two adjacent carbon atoms of the phenyl ring, where these chains may for their part carry one to three of the following radicals: halogen, Ci-C 4 -alkyl, 30 Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy or Ci-C 4 -alkylthio. 9. A process for preparing a solid preparation of a crop 35 protection agent as claimed in one or more of claims 1 to 8, which comprises melting at least one active compound, at least one thermoplastic binder having a melting point or glass transition temperature of more than 70 0 C and, if appropriate, customary additives to a plastic mixture and 40 briquetting the melt by dividing it into drops in a first step and solidifying these drops by cooling in a second step. 10. A process for preparing a solid preparation of a crop protection agent as claimed in claim 9, wherein at least one 45 thermoplastic binder from the group consisting of the 30 polyvinylpyrrolidones or the N-vinylpyrrolidone copolymers is employed. 11. A process for preparing a solid preparation of a crop 5 protection agent as claimed in claim 9 or 10, wherein the preparation of the melt is carried out in an extruder. 12. A process for preparing a solid preparation of a crop 10 protection agent as claimed in any of claims 9 to 11, wherein the thermoplastic melt is divided into drops with the aid of a rotating screen roll and subsequently solidified. 13. A process for preparing a solid preparation of a crop 15 protection agent as claimed in one of more of claims 1 to 8, wherein one or more binders from the group consisting of the polyvinylpyrrolidones or the N-vinylpyrrolidone copolymers or a mixture of one or more polyvinylpyrrolidones with one or more N-vinylpyrrolidone copolymers is employed. 20 14. A method for controlling phytopathogenic fungi, unwanted vegetation, unwanted infestation by insects or mites and/or for regulating the growth of plants, which comprises employing a solid preparation of a crop protection agent as 25 claimed in one or more of claims 1 to 8 in solid or dissolved form and allowing it to act on plants, their habitat or on seed. 15. A method for controlling insects or wood-destroying fungi, 30 which comprises employing a solid preparation of a crop protection agent as claimed in one or more of claims 1 to 8 in dissolved form and allowing it to act on insects, their habitat or on wood. 35 40 45