WO1999021419A1

WO1999021419A1 - Solid formulation of a plant protection agent

Info

Publication number: WO1999021419A1
Application number: PCT/EP1998/006682
Authority: WO
Inventors: Andreas Ernst; Matthias Bratz; Andreas Kleinke; Thomas Kessler
Original assignee: Basf Aktiengesellschaft
Priority date: 1997-10-29
Filing date: 1998-10-21
Publication date: 1999-05-06
Also published as: EP1026946A1; AU749945B2; CA2307836A1; AR013991A1; JP2001520977A; AU1031499A; IL135664A0

Abstract

The invention relates to a solid formulation of a plant protection agent. Said formulation is obtained by producing a melt containing 1-80 wt. % of an active agent or a combination of active agents which can be used for plant protection; 20-99 wt. % of at least one thermoplastic binder with a melting or glass transition temperature of more than 70° C, and 0-20 wt. % additives, the sum of all of these constituents equalling 100 wt. %, and then pelleting said melt by reducing it to drops in a first stage and setting the drops by means of cooling in a second stage.

Description

Solid preparation of a plant protection product

description

The present invention relates to a solid preparation of a crop protection agent obtainable by producing a melt comprising

1-80% by weight of an active ingredient which can be used in crop protection or a combination of such active ingredients 20-99% by weight of at least one thermoplastic binder with a melting or glass transition temperature of more than 70 ° C. 0-20% by weight of additives,

the sum of all the ingredients being equal to 100% by weight and subsequent pastillation, by dividing the thermoplastic melt into drops in a first step and solidifying them in a second step by cooling.

The invention further relates to a process for the production of a solid preparation of a crop protection agent, characterized in that at least one active ingredient, at least one thermoplastic binder having a melting or glass transition temperature of more than 70 ° C. and, if appropriate, customary additives are melted to form a thermoplastic mixture, the melt into droplets and these parts solidified cool in a second step by Ab ^¬.

The invention further provides a process, characterized denotes ge ^¬ that a solid formulation of a crop ^¬ protection means for controlling phytopathogenic fungi, uner ^¬ wünschtem vegetation, undesired attack by insects or mites and / or for regulating the growth of plants in solid or dissolved form and used on plants, their habitat or on seeds.

Active ingredient-containing preparations Herge by melt extrusion ^¬ sets are generally known. The extrusion of active substance-containing melts of water-soluble polymers, preferably of copolymers of vinyl pyrrolidone, is described in EP-A 240 904 and EP-A 240 906. EP-A 596 203 mentions solid preparations of crop protection agents with a delayed active ingredient release. WO 92/15197 describes the production of water-dispersible, quick-release crop protection granules. The crop protection active ingredient is used for shaping together with water-soluble fillers, for example urea, sugar alcohols, so-called "heat-activated binders" (ethoxylated alkylphenols or ethylene oxide / propylene oxide block copolymers) and various auxiliaries (anionic surfactants, disintegrants, fillers, etc.) 50-130 ° C extruded through a sieve, for example.

WO 93/25074 discloses water-dispersible crop protection granules which, in addition to the active component and various additives, contain in particular polyethylene glycols and surfactants containing ethylene oxide groups.

WO 94/08455 describes the co-extrusion of crop protection agents with polyvinylpyrrolidone, followed by cooling, breaking and grinding. The ground extrudate is sieved and, if necessary, tableted.

WO 94/23579 describes the use of such solid concentrates for the production of aqueous dispersions of pyrethroid insecticides.

WO 94/08455 describes the melt extrusion of crop protection active ingredients with polyvinylpyrrolidone as a binder, but the emerging melt is not subjected to any subsequent shaping step. The cooled melt is broken, ground and sieved. This process is complex, cost-intensive, leads to dust formation and results in non-abrasion-resistant, non-uniform broken granules.

WO 93/25074 mentions the possibility of assembly using Rotoformer ^® . Polyethylene glycol is used as a binder in all examples. In principle, the recipes for the recipes with the active ingredients diuron - analogous to WO 93/25074, page 26, example 14 - and kresoxim-methyl (IUPAC name: methyl methoxyimino-α- (o-tolyloxy) -o-tolylacetate) resulted no "solid solutions", ie did not contain the active substance in a molecularly dispersed manner in the matrix. The formulations below are cloudy, mostly soft powder agglomerates which, compared to the formulations according to the invention, can be dispersed only slowly and incompletely in water.

It is also known that pharmaceutical extracts can be processed into various solid forms by melt extrusion in conjunction with polymers (EP-A 0358 105, EP-A 0240 904). The continuous shaping by means of lander and hot tee. Low-viscosity melts, as can be obtained, for example, in formulations containing high levels of active ingredients or formulations with inexpensive sugars, etc., are difficult to process with the known processes, since sticking occurs. Furthermore, only a limited heat transfer area per product quantity is available in the known methods, which can cause problems with scale-up.

The pastilization of highly viscous melts with the help of a rotoforming machine is known. Pastilles are solid moldings that can be created by dividing a highly viscous mass into droplet-like quantities as they pass through one or more openings, which are then cooled, for example, on a moving transport surface to form solid moldings. This process is state of the art and is sold, for example, by Sandvik Process Systems GmbH, Stuttgart, as Rotoformer ^® (US 4,279,579).

A problem is the pastilling of high-viscosity, low-viscosity melts, since these do not harden sufficiently when they are shaped into solid preparations of pesticides.

The object of the present invention was to provide a homogeneous, non-sticky, fast and fine-particle dispersing crop protection solid formulation which should have a long shelf life.

The object was achieved by the composition described at the beginning.

In general, active substances are considered that do not decompose under the processing conditions during the production of the melt.

The amount of active ingredient components in the overall preparation can vary within wide limits depending on the effectiveness, the rate of release and the dispersibility. The active ingredient content can thus be in the range from 1-80% by weight, preferably from 20-80% by weight, based on the preparation as a whole. The only condi ^¬ supply is that the preparation is still melt-processable. The active ingredient is advantageously in the form of a "solid solution", ie molecularly dispersed in the matrix of the binder.

In principle, suitable binders are polymeric or low molecular weight binders which can be processed without decomposition and which, together with the active ingredient and other additives, result in solid forms which do not tend to flow cold. Experience has shown that these are substances that have a melting (mp) or glass transition temperature (Tg) of more than 70 ° C, for example 80 ° C to about 200 ° C (also higher for softening active ingredients or additives).

The glass temperatures (Tg) of selected binders are listed below:

In order to obtain solid, storage-stable forms at room temperature, the melting point or the glass transition temperature of the thermoplastic binder should generally be above 70 ° C., preferably> .80 ° C. and particularly preferably> 90 ° C. Above all, when the active ingredient and binder partially or completely form a solid solution, because in these cases the glass transition temperature or melting point is significantly reduced. This behavior is particularly evident with low-melting active ingredients.

In the case of water-dispersible instant-release granules, the binder should advantageously be water-soluble or water-dispersible. In addition, the active ingredient and binder should usually be able to be processed homogeneously, i.e. there should be no phase separation in the liquid state. Ideally, this also applies to the cooled solid phase (solid solution). The binder should therefore be water-soluble or swellable in an aqueous, neutral solution and also have the ability to dissolve hydrophobic active substances.

Examples of suitable binders are: Polyvinylpyrrolidone (PVP), copolymers of N-vinylpyrrolidone (NVP) and vinyl esters, in particular vinyl acetate, copolymers of vinyl acetate and crotonic acid, partially saponified polyvinyl acetate, polyvinyl alcohol, polyhydroxyalkyl acrylates (for example Ci- or C ₂ -alkyl), polyhydroxyalkyl methacrylates ( C ₂ alkyl), polyacrylates and polymethacrylates (Eudragit types), copolymers of methyl methacrylate and acrylic acid, cellulose esters, cellulose ethers, in particular methyl cellulose and ethyl cellulose, hydroxyalkyl celluloses, in particular hydroxypropyl cellulose, hydroxyalkyl alkyl celluloses, in particular hydroxypropyl ethyl cellulose, Cellulose phthalates, especially cellulose acetate phthalate and hydroxypropylmethyl cellulose phthalate, and mannans, especially 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, for PVP> 17, in particular 20 to 35.

Preferred polymeric binders are polyvinylpyrrolidone (PVP), copolymers of N-vinylpyrrolidone (NVP) and Vinylestern, in particular vinyl acetate, copolymers of vinyl acetate and crotonic ^¬ acid, partially hydrolyzed polyvinyl acetate, polyvinyl alcohol, polyhydroxyalkyl (Cj_- or C ₂ alkyl), polyhydroxyalkyl methacrylates (Cχ- or C -alkyl), polyacrylates and polymethacrylates (Eudragit types), copolymers of methyl methacrylate and acrylic acid.

Particularly preferred polymeric binders are one or more polyvinylpyrrolidones and / or one or more copolymers of N-vinylpyrrolidone.

The polymeric binder should generally soften or melt in the total mixture of all components in the range from 20 ° to 180 ° C., preferably 60 ° to 130 ° C. The glass transition temperature of the mixture will therefore usually be below 180 ° C, preferably below 130 ° C.

If necessary, it is reduced by the usual softening agents. The amount of plasticizer is at most 20, in general 0.5 to 15, preferably 0.5 to 5% by weight, based on the total weight of the mixture, so that storage-stable plant protection product formulations are formed which do not show a cold flow. Examples of such plasticizers are: long-chain alcohols, ethylene glycol, propylene glycol, glycerol, trimethylolpropane, triethylene glycol, butanediols, pentanols, such as pentaerythritol, hexanols, polyethylene glycols, polypropylene glycols, polyethylene propylene glycols, silicones, aromatic carboxylic acid esters, eg trimellitic acid esters (eg dialkyl acid phthalates) esters, terephthalic acid esters) or aliphatic dicarboxylic acid esters (eg dialkyl adipates, sebacic acid esters, azelaic acid esters, citric and tartaric acid esters), fatty acid esters such as glycerol mono-, glycerol di- or glycerol triacetate, fatty acid glycerides or sodium diethyl sulfosuccinate.

However, the mixture preferably contains no plasticizer.

The addition of surfactants Sub ^¬ is partially attached punching preparation for efficient biological effect of the supply according to the invention. The surface-active substances are the alkali, alkaline earth and ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalene sulfonic acid, and of fatty acid, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and Salts of sulfated hexa-, hepta- and octadecanols or fatty alcohol - glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl, or nonyl phenol or tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol ester, lignin sulfite liquor, methyl cellulose ethoxylate, fatty alcohol amide ethoxylates, fatty amine ethoxylates, alkyl polyglycosides, propylene oxide / ethylene oxide block polymers, fatty acid ethoxylates, polycarboxylates based on maleic acid and / or acrylic acid, ethylenediamine ethoxylates and propoxylates, aminated fatty alcohol ethoxylates, fatty alcohol ethoxylate sulfoxylates and mixed ethylenediaminate diamines.

As the additives, fillers or excipients are contemplated, which accelerate the release (disintegrants, wick substances), substances which improve the dispersibility or the dispersion stabilization (eg, anionic surfactants) or extrude sion technical aids such as lubricants or Fließregu ^¬ liermittel. Dyes, such as azo dyes, organic or inorganic pigments or dyes of natural origin, inorganic pigments being used in a concentration of 0.001 to 10, preferably 0.5 to 3% by weight, based on the total weight of the formulation, can be used in the mixture stabilizers such as antioxidants, light stabilizers, hydroperoxide destroyers, radical scavengers are added to prepare the formulation. Wetting agents, preservatives, adsorption agents, mold release agents and blowing agents can also be added (see, for example, R. Voigt, Textbook of Pharmaceutical Technology, VCH-Verlag, Weinheim, pp. 178-185, 1987).

The only requirement for the suitability of auxiliaries is sufficient temperature stability.

The invention also encompasses a process for producing a solid preparation of a crop protection agent, which is characterized in that at least one active ingredient, at least one thermoplastic binder having a glass transition temperature above 70 ° C. and, if appropriate, customary additives are melted into a plastic mixture and the Pastillized melt by dividing the melt into drops in a first step and solidifying it in a second step by cooling.

Suitable binders are those mentioned above, in particular polyvinylpyrrolidones and / or copolymers of N-vinylpyrrolidone.

The thermoplastic melt is advantageously divided into drops using a rotating screen roller, which are removed from the screen roller by a moving conveyor belt and then solidified.

The invention particularly preferably comprises a method for producing a solid preparation of a crop protection agent, characterized in that the pastillation is carried out with the aid of a Rotoformers ^® .

Low-viscosity melts, which are characterized in that they harden particularly quickly when they leave the extruder or are only slightly sticky, can alternatively be broken into drops by rotating knives and then completely cooled and hardened.

The process steps of mixing and melting can be carried out in a known manner, as described for example in EP-A-240 904, EP-A-337 256 and EP-A-358 105.

The components can first be mixed and then melted and homogenized. However, especially when using sensitive active ingredients, it has proven to be preferred to first melt and premix the polymeric binder, if appropriate together with customary additives, the stirred kettles, agitators, solid-state mixers etc. optionally in the Be operated alternately, and then mix in the sensitive active ingredient (s) in "intensive mixers" in the plastic phase with very short residence times. Active ingredient (s), binders and any additives can be used in solid form, as a resin, as a solution or dispersion.

The melting and mixing takes place in a device which is customary for this purpose. Extruders or heatable containers with stirrers, e.g. Kneader. Depending on requirements, the speed in the kneader can be set temperature-controlled, i.e. you can work at low speed in the mixing stage and then increase the speed when melting.

Devices which are used in plastics technology for mixing can also be used as a mixing apparatus. Suitable devices 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. Be ^¬ Sonders suitable mixing apparatuses are extruders and dynamic and static mixers, and stirred vessels, single-shaft stirrers with stripper mechanisms, especially so-called Pastenrührwerke, multishaft stirrers, especially PDSM mixers, Feststoffmi- shear and preferably mixing kneader reactors (for example ORP, CRP, AP, DTB from List or Reactotherm ^® from Krauss-Maffei or Ko-Kneter ^® from Buss), double-bowl kneaders (trough mixers) and stamp kneaders (internal mixers) or rotor / stator systems (eg Dispax from IKA).

The mixing device can be fed continuously or discontinuously in the usual way. Powdery components can be introduced in the free inlet, eg using a differential dosing scale. Plastic masses can be fed in directly from an extruder or fed in via a gear pump, which is particularly advantageous for high viscosities and high pressures. Liquid media can be metered in by a geeigne ^¬ tes pump unit.

The mixing and / or melting can also take place in two or more discontinuously operating devices in parallel or alternately, in order to be able to operate the downstream shaping device continuously.

The mixture obtained by mixing and melting the binder, the active ingredient and optionally the additive or additives is pasty to viscous (thermoplastic) and therefore also extrudable. The glass transition temperature of the Gemi It is below the decomposition temperature of all components contained in the mixture.

According to the invention, the plastic mixture is first extruded into a continuous strand using, for example, a suitable extrusion tool. Any solvents and residual moisture that may be present can be drawn off during the extrusion by means of a vacuum pump. The extruder can contain mixing, kneading and return elements as required. The shape of the extrusion tool depends on the desired shape. For example, round hole tools or coextrusion tools, such as tools with an annular-gap-shaped exit cross section, are suitable. Coextrusion tools are used to produce at least two-layer, open or closed forms. One of the layers contains an active ingredient, the other layer can be free of active ingredient or optionally contain another active ingredient. Further information can be found in WO-A 97/15293.

However, round-hole nozzles are preferably used, the plastic mixture being formed as a strand with a circular cross section and discharged into the rotoformer or into an analog apparatus suitable for the production of pastilles.

The viscosity of the melt to be processed in the Rotoformer ^® is usually between 20 and 20,000 mPas x sec, advantageously between 20 and 5,000 mPas x sec at the processing temperature of 100-200 ° C. The heat contained in the melt is, for example, by means of a cooling belt Direct cooling dissipated. The extrudate cooled in this way is generally tack-free and solid at room temperature.

PVP and NVP copolymers have relatively high melting points and relatively high glass transition temperatures. These high-melting polymers surprisingly become so soft due to the high concentration of active ingredient that they can be broken down into drops as a low-viscosity melt, and after cooling they solidify to form homogeneous, storage-stable, non-adhesive moldings (lozenges).

Mixtures of active ingredient and PVP or copolymers of N-vinylpyrrolidone are particularly preferred. At least partially solid solutions are formed, the products are solid, low in dust and show good wettability. Due to the homogeneous, mostly molecularly disperse distribution of the active ingredient in the polymer matrix, the active ingredient is dissolved when the formulation is dissolved. Distribution in water quickly and finely, it also results in a stable dispersion.

Another object of the invention is the use of one or more binders from the group of polyvinylpyrrolidones or copolymers of N-vinylpyrrolidone or a mixture of one or more polyvinylpyrrolidones with one or more copolymers of N-vinylpyrrolidone for the preparation of a solid preparation according to the invention Pesticide.

The invention furthermore relates to the use of the solid preparation of a crop protection agent according to the invention for controlling phytopathogenic fungi, undesirable plant growth, insect or mite infestation and / or for regulating the growth of plants, the preparation of the crop protection agent in solid or dissolved form on plants, whose habitat or seeds can act.

The process according to the invention is suitable, for example, for the processing of crop protection active compounds having a herbicidal, fungicidal, insecticidal, acaricidal and growth-regulating action.

The following list of herbicides shows possible active ingredients, but should not be limited to these.

Herbicides from the class of 1, 3, 4-thiadiazoles, such as buthidazoles, cyprazoles

Amides, such as allidochlor (CDAA), benzoylprop-ethyl, bromobutide,

Chlorothiamide, Dimepiperate, Dimethenamid, Diphenamid, Etobenzanid (Benzchlomet), Flamprop-methyl, Fosamin, Isoxaben, Monalide,

Naptalame, pronamide (propyzamide), propanil

Aminophosphoric acids, such as bilanafos, (bialaphos), buminafos, glufosinate-ammonium, glyphosate, sulfosate

Aminotriazoles such as amitrole

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 (2,4,5-TP), Fluoroxypyr, MCPA, MCPB, Mecoprop, Mecoprop-P, Napropamide, Napropanilide, Triclopyr Benzoic acids, such as chloramben, dicamba

Benzothiadiazinones, such as bentazone

Bleachers such as Clomazone (Dimethazone), Diflufenican, Fluorochloridone, Flupoxam, Fluridone, Pyrazolate, Sulcotrione (Chloromesulone)

Carbamates, such as Asulam, Barban, Butylate, Carbetamid, Chlorbufam, Chlorpropham, Cycloate, Desmedipham, Diallate, EPTC, Esprocarb, Molinate, Orbencarb, Pebulate, Phenisopham, Phenmedipham, Propham, Prosulfocarb, Pyributicarb, Sulfallerbate (CDEC), Thiobencarb (Benthiocarb), Thiocarbazil, Triallate, Vernolate

Quinolinic acids such as Quinclorac, Quinmerac

Chloroacetanilides, such as acetochlor, alachlor, butachlor, butenochlor, diethyl ethyl, dimethachlor, metazachlor, metolachlor, pretilachlor, propachlor, prynachlor, terbuchlor, thenylchlor, xylachlor

Cyclohexenones, such as alloxydim, caloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim, tralkoxydim, 2- {1- [2- (4-chlorophenoxy) copyloxyimino] butyl} '3-hydroxy-5- (2H-tetrahydrothiopyran-3- yl) - 2-cyclohexen-l-one

Dichloropropionic acids, such as Dalapon

Dihydrobenzofurans such as ethofumesate

Dihydrofuran-3-one, such as Flurtamone

Dinitroaniline such as benefin, butralin, dinitramine, ethalfluralin, fluchloralin, isopropalin, nitralin, oryzalin, pendimethalin, prodiamine, profluralin, trifluralin

Dinitrophenols, such as bromofenoxim, dinoseb, dinoseb acetate, dinoterb, DNOC

Diphenyl ethers, such as acifluorfen-sodium, aclonifen, bifenox, chloronitrofen (CNP), difenoxuron, ethoxyfen, fluorodifen, fluoroglyc-oven-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen

Dipyridylenes such as cyperquat, difenzoquat methyl sulfate, diquat, paraquat dichloride Ureas, such as benzthiazuron, buturon, chlorobromuron, chloroxuron, chlorotoluron, cumyluron, dibenzyluron, cycluron, dimefuron,

Diuron, Dymron, Ethidimuron, Fenuron, Fluorometuron, Isoproturon,

Isouron, carbutilate, linuron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, monuron, neburon, siduron, tebuthiuron,

Trimeturon

Imidazoles such as isocarbamide

Imidazolinones, such as imazamethapyr, imazapyr, imazaquin, imazethazenzomethyl (imazame), imazethapyr

Oxadiazoles, such as methazoles, oxadiargyl, oxadiazon

Oxiranes, such as tridiphanes

Phenols, such as bromoxynil, ioxynil

Phenoxyphenoxypropionic acid esters, such as clodinafop, cyhalofop-butyl, ciclofop-methyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, fenthia-propethyl, fluazifop-butyl, fluazifop-p-butyl, haloxyfop-ethoxy-ethyl, haloxyfop-methyl, haloxyfop-p -methyl, isoxapyrifop, propa- quizafop, quizalofop-ethyl, quizalofop-p-ethyl, quizalofop-tefuryl

Phenylacetic acids, such as chlorfenac (fenac)

Phenylpropionic acids, such as chlorophenprop-methyl

Protoporphyrinogen-IX oxidase inhibitors, such as benzofenap, cinidon-ethyl, flumiclorac-pentyl, flumioxazin, flumipropyn, flupropacil, fluthiacet-methyl, pyrazoxyfen, sulfentrazone, thidiazimin pyrazoles, such as nipyraclofen

Pyridazines, such as chloridazon, maleic hydrazide, norflurazon, pyridates

Pyridinecarboxylic acids, such as clopyralide, dithiopyr, picloram, thiazo-pyr

Pyrimidyl ethers such as pyrithiobacic acid, pyrithiobac-sodium, KIH-2023, KIH-6127

Sulfonamides such as flumetsulam, metosulam Sulfonylureas, such as amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, cyclosulfuramuron, ethametsulfuron methyl, ethoxyεulfuron, flazasulfuron, halosulfuron-methyl, imazosulfuron-methyl, prozetsulfuron-methyl, mets ethyl, rimsul-furon, sulfometuron-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl

Triazines such as Ametryn, Atrazin, Aziprotryn, Cyanazine, Cyprazine, Desmetryn, Dimethamethryn, Dipropetryn, Eglinazin-ethyl, Hexazi-non, Procyazine, Prometon, Prometryn, Propazin, Secbumeton, Simazin, Simetryn, Terbumeton, Terbutryn, Trerbzinyn, Terbutrin, Terbutryn, Terbutryn

Triazinones, such as ethiozine, metamitron, metribuzin

Triazole carboxamides such as triazofenamide

Uracile such as Bromacil, Lenacil, Terbacil

Various such as benazolin, benfuresate, bensulide, benzofluor, butamifos, cafenstrole, chlorothal-dimethyl (DCPA), cinmethylin, dichlobenil, endothall, fluorobentranil, mefluidide, perfluidone, piperophos.

The following list of compounds with growth regulatory activity shows possible active substances from this group, but is not intended to be limited to these.

Compounds with growth regulatory activity, such as

1-naphthylacetamide, 1-naphthylacetic acid, 2-naphthyloxyacetic acid, 3-CPA, 4-CPA, ancymidol, anthraquinone, BAP, butifos; Tribufos, Butralin, Chlorflurenol, Chlormequat, Clofencet, Cyclanilide, Daminozide, Dicamba, Dikegulac sodium, Dimethipin, Chlorfenethethol, Etacelasil, Ethephon, Ethylchlozate, Fenoprop, 2,4,5-TP, Fluoridamid, Flurriafidol, Flutriafidol , Gibberellic acid, Gibberillin, Guazatin, Imazalil, Indolylbutyric acid, Indolylacetic acid, Karetazan, Kinetin, Lactidichloro-ethyl, Maleic hydrazide, Mefluidide, Mepiquat-chloride, Naptalam, Paclobutrazole, Prohexadacetium Sodium, Quininmercione, Acid, Calcium Quinine Thidiazuron,

Triiodobezoicacid, triapenthenol, triazethane, tribufos, trinexapacethyl, uniconazole.

The following list of fungicides shows possible active ingredients, but should not be limited to these. Fungicides from the class

Sulfur, dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese-zinc-ethylenediamine-bis-dithiocarbamate, tetramethylthiurium -diamide-dithi-di-amide-dithi-di-carbamate ), ammonia-Kom plex ^¬ 'bisdithiocarbamate -propylene), zinc (N, N' of zinc (N, N -Pro- pylenbis dithiocarbamate), N, N '-polypropylene-bis (thio- carbamoyl) disulfide;

Nitroderivatives, such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4, 6-dinitrophenyl-3, 3-dimethylacrylate, 2-sec-butyl-4, 6-dinitrophenyl-isopropyl carbonate, 5-nitro -isophthalic acid - di-isopropyl ester;

heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2, 4-dichloro-6- (o-chloroanilino) -s-triazine, 0, O-diethyl-phthalimidophosphonothioate, 5-amino-l- [bis - (dimethylamino) - phosphinyl] -3-phenyl-l, 2, 4-triazole, 2, 3-dicyano-l, 4-dithioanthraquinone, 2-thio-l, 3-dithiolo [4, 5-b] quinoxaline, l- (butyl-carbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) -benzimidazole, N- (1, 1, 2, 2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio-phthalimide,

N-dichlorofluoromethylthio-N ', N' -dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-rhodanomethylthiobenzothiazole, 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-di-hydro-5-carboxanilido 6-methyl-l, 4-oxathiin, 2, 3-dihydro-5-carboxanilido-6-methyl-l, 4-oxathiin-4, 4-dioxide, 2-methyl-5, 6-di-hydro- 4H-pyran-3-carboxylic acid anilide, 2-methyl-furan-3-carboxylic acid anilide, 2, 5-dimethyl-furan-3-carboxylic acid anilide, 2,4,5-trimethyl-furan-3-carboxylic acid anilide, 2, 5-dimethyl-furan-3-carboxylic acid-cyclohexylamide, N-cyclohexyl-N-methoxy-2, 5-dimethyl-furan-3-carboxamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid acid anilide, N-formyl-N-morpholine-2, 2, 2-trichloroethyl acetal, piperazin-1, 4-diylbis-l- (2, 2, 2-trichloroethyl) -formamide, 1- (3, 4-dichloroanilino ) -1- formylamino-2, 2, 2-trichloroethane, 2, 6-dimethyl-N-tridecyl- morpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts, N- [3- (p-tert. - Butylphenyl) -2-methylpropyl] cis-2, 6-dimethylmorpholine, N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine, 1- [2- (2, 4- Dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) -4-n-propyl -l, 3-dioxolan-2-yl- ethyl] -HH-l, 2,4-triazole, N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N '-imidazol-yl-urea, 1- (4-chlorophenoxy ) -3,3-dimethyl-1- (1H-1,2,4-triazol-l-yl) -2-butanone, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H -1, 2, 4-triazol-l-yl) -2-butanol, (2RS, 3RS) -1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) oxiran-2-ylmethyl ] -1H-1,2,4-triazole, a- (2-chlorophenyl) -a- (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethyl-amino-4-hydroxy- 6-methyl-pyrimidine, bis- (p-chlorophenyl) -3-pyri-dinmethanol, 1, 2-bis (3-ethoxycarbonyl-2-thioureido) benzene, 1, 2-bis (3-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-cyclopropyl-pyrimidin-2-yl] aniline,

Phenylpyrroles, such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile,

Cinnamic acid amides, such as 3- (4-chlorophenyl) -3- (3, 4-dimethoxyphenyl) acrylic morpholide,

as well as various fungicides, such as dodecylguanidine acetate,

3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide,

Hexachlorobenzene, DL-methyl-N- (2,6-dimethyl-phenyl) -N-furoyl (2) -alaninate, DL-N- (2,6-dimethyl-phenyl) -N- (2'-methoxyace - tyl) -alanine-methyl ester, N- (2, 6-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone, DL-N- (2, 6-dimethylphenyl) -N- (phenylacetyl) ) -alanine methyl ester, 5-methyl-5-vinyl-3- (3, 5-dichlorophenyl) -2, 4-dioxo-l, 3-oxazolidine, 3- [3, 5-dichlorophenyl (-5-methyl- 5-methoxymethyl] -1, 3-oxazolidine-2,4-dione, 3- (3, 5-dichlorophenyl) -1-isopropylcarbamoylhydantoin, N- (3, 5-dichlorophenyl) -1, 2-dimethylcyclopropane-1 , 2-dicarboximide, 2-cyano- [N- (ethylamino carbonyl) -2-methoximino] acetamide, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4 -triazole, 2, 4-difluoro-a- (1H-1, 2, 4-tri-azolyl-1-methyl) -benzhydryl alcohol, N- (3-chloro-2, 6-dinitro-4-tri ^■ fluoromethyl- phenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1- ((bis- (4-fluorophenyl) methylsilyl) ethyl) -1H-1,2,4-triazole.

Strobilurins such as methyl-E-methoxyimino- [α- (o-tolyloxy) -o-tolyl] acetate, methyl-E-2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yl - oxy] -phenyl} -3-methoxyacrylate, methyl-E-methoxyimino- [α- (2-phen-oxyphenyl)] -acetamide, methyl-E-methoxyimino- [α- (2, 5-dimethyl-phenoxy) -o -tolyl] -acetamide, From the class of the strobilurins are moreover more fungicidally ^¬ same compounds of formulas IA or IB Q a nucleus to name a nucleus containing T containing

where - represents a single or double bond and the nucleus of the index and the substituents have the following Be ^¬ importance:

Q cyclopentenyl, cyclohexenyl, phenyl, pyrrolyl, thienyl, furyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, thiadiazolyl, triazolyl, pyridinyl, 2-pyridonyl, pyrimidinyl and triazinyl;

T phenyl, oxazolyl, thiazolyl, thiadiazolyl, oxadiazolyl, pyridinyl, pyrimidinyl and triazinyl.

Y = C- or -N-;

R '-C [C0 ₂ CH _3] = CHOCH _3, -C [C0 ₂ CH _3] = NOCH _3, -C [CONHCH _3] = NOCH _3, -C [C0 ₂ CH _3] = CHCH _3, -C [C0 ₂ CH ₃ ] = CHCH ₂ CH ₃ , -C [COCH ₃ ] = NOCH ₃ , -C [COCH ₂ CH ₃ ] = NOCH ₃ , -N (OCH ₃ ) -C0 ₂ CH ₃ , -N (CH ₃ ) -C0 ₂ CH ₃ , -N (CH ₂ CH ₃ ) -C0 ₂ CH ₃ ;

R "is a C-organic radical, which directly or via an oxy, mercapto, amino, or alkylamino group is bound, for example, optionally substituted aryloxy, substi ^¬ tuiertes hetaryloxy, substituted aryloxymethylene, substituted hetaryloxymethylene, substituted Arylethe- Nylen , substituted hetarylethenylene, inter alia, 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 anthracenyl, which has an oxygen atom (—0—) to the

Scaffold is bound;

where hetaryloxy, for example a 5- or 6-membered heterocycle (heterocyclyl), contains, in addition to carbon ring members, one to three nitrogen atoms and / or one Oxygen or sulfur atom or one or two oxygen and / or sulfur atoms;

The addition "possibly subst." with regard to the cyclic (saturated, unsaturated or aromatic) groups is intended to express that these groups can be partially or completely halogenated and / or can carry one to four (in particular one to three) of the following radicals:

Cyano, nitro, hydroxy, amino, carboxyl, aminocarbonyl, alkyl, haloalkyl, alkenyl, haloalkenyl, alkenyloxy, haloalkenyloxy, alkynyl, haloalkynyl, alkynyloxy, haloalkynyloxy, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylamino, dialkylamino, alkylcarbonyl, Alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonylamino, alkoxycarbonylamino, alkylcarbonyl -N-alkylamino and alkylcarbonyl -N-alkylamino, the alkyl groups in these radicals preferably 1 to 6

Contain carbon atoms, in particular 1 to 4 carbon atoms, and the 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 are attached, an optionally substituted bicyclic, partially or completely unsaturated system which, in addition to carbon ring members, can contain one or more heteroatoms from the group consisting of oxygen, sulfur and nitrogen;

R ^x -OC [C0 ₂ CH ₃ ] = CHOCH ₃ , -0C [C0 ₂ CH ₃ ] = CHCH ₃ , -OC [C0 ₂ CH ₃ ] = CHCH ₂ CH ₃ , -SC [C0CH ₃ ] = CHOCH ₃ ,

-SC [C0 ₂ CH ₃ ] = CHCH ₃ , -SC [C0 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 [C0 ₂ CH ₃ ] = CHOCH ₃ , -CH ₂ C [C0 ₂ CH ₃ ] = N0CH ₃ ,

-CH ₂ C [CONHCH ₃ ] = STILL ₃ ;

Λ R ^y -0-, -S-, = CH-, -HC =, - N = or = N-; n is 0, 1, 2 or 3, where the radicals X can be different if n is greater than 1;

X cyano, nitro, halogen, -C-C ₄ alkyl, -C-C -haloalkyl, -C-C ₄ ~ alkoxy, -C-C ₄ -haloalkoxy, -C-C ₄ alkylthio;

for the case that n> 1, a C ₃ -Cs alkylene, C -C ₅ alkenylene, 0xy-C -C ₄ alkylene, oxy-Cι- bonded to two adjacent C atoms of the phenyl ring C ₃ -alkylene-oxy-, oxy-C -C ₄ -alkenylene-, oxy-C ₂ -C ₄ -alkenyleneoxy- or

Cι Cι-C-C ₄ haloalkyl, C _x -C ₄ -alkoxy, C halogen, _C4 alkyl, _Cι-4 -haloalkoxy or C _4: butadienediyl, wherein these chains in turn may carry from one to three of the following radicals -Alkylthio,

Structures of compounds IA and IB are disclosed in detail in WO 96/32015, pages 3 to 18.

When providing the mixtures, preference is given to using the active ingredients IA or IB, to which, depending on the need, further active ingredients can be admixed against pests (e.g. insects, arachnids or nematodes) or harmful fungi or else herbicidal or growth-regulating active ingredients or fertilizers.

They are particularly important for combating a large number of fungi on various crops such as cotton, vegetables (e.g. cucumbers, beans and squashes), barley, grass, oats, coffee, corn, fruit plants, rice, rye, soy, wine, wheat, ornamental plants , Sugar cane and a variety of seeds.

They are especially suitable for controlling the following plant health ^¬ units:

Alteraaria species on vegetables and fruits,

Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and grapevines ^¬,

Cercospora arachidicola on peanuts,

Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants,

Erysiphe graminis (powdery mildew) on cereals, Fusari um and Verticillium species on various plants, Helmin thospori um species on cereals, Mycosphaerella species on bananas,

Phytophthora infes tans on potatoes and tomatoes, Plasmopara vi ticola on vines, Podosphaera leucotricha on apples, Pseudocercosporella herpotrichoides on wheat and barley, Pseudocercosporella species on hops and cucumbers,

Pseudoperonospora species on hops and cucumbers,

Puccinia species on cereals,

Pyricularia oryzae on rice,

Rhizocfconia species on cotton, rice and lawn,

Septoria nodorum on wheat,

Uncinula neca tor on vines,

C / sfcilago species on cereals and sugar cane, as well

Venturia inaequalis (scab) on apples.

The application rates of the preferred compounds mentioned, when used to protect crop plants, are from 2 to 0.1 kg / ha, preferably 1.25 to 0.2 kg / ha, in particular 0.75 to 0, depending on the type of effect desired. 3 kg / ha.

The application rates for the compounds IA and IB are 1 to 0.01 kg / ha, preferably 0.5 to 0.02 kg / ha, in particular 0.25 to 0.03 kg / ha.

In the case of seed treatment, application rates of mixture of 0.1 to 100 g / 100 kg of seed, preferably 0.5 to 50 g / 100 kg of seed, in particular 1 to 10 g / 100 kg of seed, are generally used.

The formulations in general contain 1 to 80, preferably ^¬, 20 to 80, particularly preferably 50 to 80 wt .-% of one of the compounds IA or IB or the mixture of the compounds IA or IB.

The active ingredients are placed in a purity of 90% to 100%, preferably 95% to 100% (according to NMR or HPLC ⁱ H-spectrum) a ^¬.

The compounds IA, IB or their mixtures or the corresponding formulations are used by mixing the harmful fungi, their habitat or the materials, plants, seeds, soils, areas or spaces to be protected against fungal attack with a fungicidally effective amount of the mixture or of compounds IA and IB treated separately. The treatment can take place before or after the infestation by the harmful fungi.

The methods according to the invention allow the preparation of a solid preparation of a crop protection agent which is generally free of organic solvents. Due to the manufacturing process, the pastilles are very homogeneous in particle size, transparent, almost spherical and have a smooth, abrasion-free and non-sticky surface structure. door. The extrusion process and the pastillation process are dust-free, since the hardened extrudate does not have to be ground in order to achieve a uniform particle size and therefore no additional apparatus precautions are necessary to contain dusts containing active substances.

The formulations according to the invention have the following advantages over formulations based on polyethylene glycol: they give abrasion-resistant, dimensionally stable and non-sticky pastils which can be dispersed quickly and finely in water.

The last-mentioned properties are a necessary prerequisite for the agricultural application of the active ingredients. When preparing the spray liquor, the active ingredient should be dispersed quickly and in fine particles so that the active ingredients are distributed as evenly as possible in the field.

In addition to spray application, the formulations according to the invention can also be used for scatter application.

The process according to the invention has the advantage that, in particular, low-viscosity melts, which cause problems with the prior art known for extrusion, can be processed without problems using a pastillation process.

With the method according to the invention it is possible to produce particularly precisely dimensioned solid preparations of a crop protection ^agent . The process is inexpensive, allows very large quantities to be achieved per unit of time and avoids waste.

The method according to the invention is explained below using ^examples .

General implementation

The amounts of active ingredient, polymers and optionally additives (e.g. nonionic surfactants) specified in the examples were mixed or introduced separately into a co-rotating, tightly intermeshing twin-screw extruder ZSK 30 (Werner & Pfleiderer GmbH, Stuttgart) and extruded over 12 temperature zones.

The following table provides information on the temperature profile (° C) in E Exxttrruuddeerr ((ZZoonnee 11 - 1122)) and Rotoformer ^® (roller and belt) of Examples 1 and 2:

The speed of the screws can be varied in the range of 100-300 rpm, at temperatures between 20 and 100 ° C in the conveying zone (zone 1) and 100-180 ° C in the melting zones (zones 2 - 12). The throughput was 10-12 kg / h and the residence time was 1-2 min. The active ingredient, the polymer and the additives were fed, conveyed and melted on metering scales at the extruder inlet. Lutensol ^® AT 25 (Ciε-Ciβ fatty alcohol with 25 ethylene oxide units), BASF was optionally fed in liquid and incorporated with mixing and kneading elements. It was also possible to degas in several extruder zones. The melt emerging at the end of the extruder through a nozzle was introduced into the rotoforming roll by means of a gear pump. The rotating, heated roller has a screen jacket, from the perforation (d = 1 mm) of which the molten extrudate is applied to a cooled conveyor belt. From there, the product reaches the respective container shape via a stripping device. The resulting pastilles have a diameter of approximately 1-2 mm. The throughput is 10-12 kg / h.

The Rotoformer ^® (type 50.221, Sandvik Process Systems GmbH, Stuttgart) consists of a roller with 3720 holes (d = lmm) and a capacity of about 2 kg of melt, which is at a distance of about 3 mm above a cooling belt with a width of 400 mm and 4 m tape length is attached. The temperature of the roller was kept at 140-180 ° C, the belt temperature was adjusted to 20 ° C by water cooling and the belt speed was 30 m / min.

example 1

Various solid preparations of plant protection products of different composition A - D were produced as described in the general procedure. The formulations contained kresoxim-methyl (IUPAC name: methyl methoxy-imino-α- (o-tolyloxy) -o-tolylacetate) as the active ingredient, Luviskol ^® K 30, Luviskol ^® VA 64 and Lutensol ^® AT 25 as additives.

The amounts added are shown in the table below.

After melt extrusion and subsequent pelletizing in Roto former ^® formulations A to D give transparent, surface-hard and dimensionally stable spherical pellets with a smooth upper ^¬. The active ingredient content of the respective lozenges was checked by HPLC. After 3 months of storage at 25 ° C in a cylindrical 25 kg container (diameter: 30 cm), the pastils remain dimensionally stable. When stored at 45 ° C for three days, all lozenges remain dimensionally stable and there is no melting ("cold flow").

The densities of the lozenges were determined using a pycnometer with the solvent pentane. The bulk densities were determined in the standing cylinder.

A sieve analysis was carried out to determine the particle size distribution. (Ref: "Ullmann's Encyclopedia of Industrial Che ^¬ mie" 4th edition, volume 5, analysis and measurement methods, VCH Weinheim, 1980, pp 726-738.)

The packaging with Rotoformer ^® results in very uniform formulations.

The weighted arithmetic mean result from the mean mesh sizes (d: mean equivalent diameter, w: mass fraction):

d = ∑ Wi di

Formulation Formulation Formulation Formulation A B C D d [mm] 1.82 1.71 1.77 1.78

Example 2

Recipes from WO 93/25074, pages 26 and 27, examples 14 and 16, which contain polyethylene glycol (PEG) 8000 as binders, were reproduced in a comparative test in the formulations E (active ingredient Kresoxim-methyl) and F (active ingredient Diuron) and in their dispersibility compared with the formulations A to D according to the invention with the polyvinylpyrrolidone Luviskol K30 as a binder.

5 g of active ingredient were added to 5 g of melted PEG 8000 binder in a petri dish, the temperature of the mixture being kept between 90 ° and 110 ° C. Using a Pasteur pipette, droplets with a diameter of 1 to 2 mm were transferred to a stainless steel plate and cooled to room temperature. With this method, a sufficient amount of pastilles was produced in order to be able to carry out experiments on dispersibility.

The dispersibility was determined as follows:

1.0 g of a sieve fraction (1.6-2 mm) of the respective formulation is placed in a 1 1 glass vessel with a diameter with stirring (Ikamag RET-G magnetic stirrer, Janke & Kunkel GmbH & Co.G., Staufen, Germany; 1 = 4 cm Teflon stirrer) 10 cm with 1000 ml of tap water (T = 20 ° C) at a stirring speed of 800 rpm (0.1% dispersion). After 10 min, the mixture is filtered through 300μ and 160μ sieves and the sieve residue is determined in% by weight based on the starting quantity (1.0 g).

Formulations E and F contain the binder polyethylene glycol PEG 8000. The pastilles recreated according to WO 93/25074 are cloudy powder agglomerates which contain the active ingredient in crystalline form. The pastilles from formulation E are also sticky at room temperature, i.e. they cake and are not free-flowing.

Formulations A - D contain polyvinylpyrrolidone as a binder and result in transparent, hard, non-tacky and dimensionally stable spherical pastilles with a smooth surface. The active ingredient content of the respective lozenges was checked by HPLC. The active ingredient is molecularly dispersed and can be dispersed quickly and finely in water. The sieve residues in formulations A - D are negligible after stirring for 10 minutes (0-8%), while the lozenges of formulations E and F disperse very slowly and have a high coarse fraction (47-61%).

Claims

1. Solid preparation of a pesticide obtainable 5 containing by making a melt

1-80 wt .-% of a usable in crop protection

Active ingredient or a combination of such active ingredients 10 20-99 wt .-% of at least one thermoplastic binder with a melting or glass temperature of more than 70 ° C.

0-20% by weight additives,

15 where the sum of all ingredients is equal to 100% by weight and subsequent pastillation by dividing the thermoplastic melt into drops in a first step and solidifying them in a second step by cooling.

20 2. Solid preparation of a plant protection product according to claim 1 obtainable by melt extrusion and subsequent pastillation.

3. Solid preparation of a crop protection agent according to claim 1 25 or 2, wherein the thermoplastic melt is divided into drops with the aid of a rotating sieve roller and these are then cooled to solid shaped bodies on a moving transport surface.

30 4. Solid preparation of a crop protection agent according to claim 1 to 3 containing one or more polyvinyl pyrrolidones as a binder.

5. Solid preparation of a crop protection agent according to claim 1 35 to 3 containing as a binder one or more copolymers of N-vinylpyrrolidone.

6. Solid preparation of a plant protection product according to claim 1 to 3 containing a mixture of or as a binder

40 several polyvinylpyrrolidones and one or more copolymers of N-vinylpyrrolidone.

7. Solid preparation of a plant protection product according to claim 1 to 6 containing at least one fungicidal, herbicidal, insectic

45 cid, acaricidal or growth-regulating compound or an active ingredient mixture from the group of these

Links .

8. Solid preparation of a plant protection product according to claim 7 containing as an active ingredient at least one fungicidal compound of the formula IA containing a nucleus Q or IB containing a nucleus T from the class of strobilurins

in which - stands for a single or double bond and the nucleus, index and substituents have the following meaning:

Q cyclopentenyl, cyclohexenyl, phenyl, pyrrolyl, thienyl, furyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl,

Thiazolyl, thiadiazolyl, triazolyl, pyridinyl, 2-pyridonyl, pyrimidinyl and triazinyl;

Y = C- or -N-;

R '-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 [C0 ₂ CH ₃ ] = CHCH ₂ CH ₃ , -C [COCH ₃ ] = N0CH ₃ ,

-C [COCH ₂ CH ₃ ] = NOCH ₃ , -N (0CH ₃ ) -C0 ₂ CH ₃ , -N (CH ₃ ) -C0 CH ₃ , -N (CH ₂ CH ₃ ) -C0 CH ₃ ;

R "is a C-organic radical which is bonded directly or via an oxy, mercapto, amino or alkylamino group;

together with a group X and the ring Q or T to which they are attached, an optionally substituted bicyclic, partially or completely unsaturated system which, in addition to carbon ring members, has one or more heteroatoms from the group consisting of oxygen, sulfur and nitrogen may contain f;

R -OC [CO ₂ CH ₃ ] = CHOCH ₃ , -OC [CO ₂ CH ₃ ] = CHCH ₃ ,

-OC [C0 ₂ CH ₃ ] = CHCH ₂ CH ₃ , -SC [C0 ₂ CH ₃ ] = CHOCH ₃ , -SC [C0 ₂ CH ₃ ] = CHCH ₃ , -SC [C0 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 ;

R ^y -O-, -S-, = CH-, -HC =, -N = or = N-

10 n is 0, 1, 2 or 3, where the radicals X are different NEN be Kgs ^¬ when n is greater than 1;

X cyano, nitro, halogen, Cχ-C ₄ alkyl, -C-C ₄ haloalkyl, C _x -C ₄ alkoxy, Cι-C ₄ haloalkoxy, Cι-C ₄ alkylthio;

15 for the case that n> 1, one bonded to two adjacent carbon atoms of the phenyl ring C -Cs alkylene, C -C ₅ alkenylene, oxy-C ₂ -C ₄ alkylene, oxy-Cχ -C ₃ -alkylene- oxy-, oxy-C ₂ -C ₄ -alkenylene-, oxy-C -C ₄ -alkenyleneoxy- or

20 butadienediyl, wherein these chains in turn may carry from one to three of the following radicals: halogen, Cι-C ₄ -alkyl, C ₄ haloalkyl, Cι-C ₄ -alkoxy, C ₄ -haloalkoxy or Cι-C ₄ -Alkylthio,

25 9. Process for the preparation of a solid preparation of a

Plant protection product according to one or more of claims 1 to 8, characterized in that at least one active ingredient, at least one thermoplastic binder with a melting or glass transition temperature of more than 70 °

30 C and, if necessary, conventional additives are melted into a plastic mixture and the melt is pelletized by dividing it into drops in a first step and solidifying them in a second step by cooling.

35 10. Process for the preparation of a solid preparation of a

Plant protection product according to Claim 9, characterized in that at least one thermoplastic binder from the group of the polyvinylpyrrolidones or the copolymers of N-vinylpyrrolidone is used.

40

11. Process for the preparation of a solid preparation of a

Plant protection agent according to claims 9 and 10, characterized in that the melt is produced in an extruder.

45

12. A method for producing a solid preparation of a crop protection agent according to claim 9 to 11, characterized in that the thermoplastic melt is divided into drops with the aid of a rotating sieve roller and then

5 solidified.

13. A method for producing a solid preparation of a crop protection agent according to one or more of claims 1 to 8, characterized in that one or more

10 uses binders from the group of polyvinylpyrrolidones or copolymers of N-vinylpyrrolidone or a mixture of one or more polyvinylpyrrolidones with one or more copolymers of N-vinylpyrrolidone.

15 14. A method for combating phytopathogenic fungi, undesirable plant growth, undesirable insect or mite infestation and / or for regulating the growth of plants, characterized in that a solid preparation of a plant protection product according to one or more of the claims

20 1 to 8 used in solid or dissolved form and on plants, their habitat or on seeds.

15. A method for controlling insects or wood-destroying fungi, characterized in that a solid prepara- 25 processing a crop protection product according to one or more of claims 1 begins to 8 in dissolved form and sects In ^¬, makes their habitat or on wood .

30

35

40

45 Solid preparation of a plant protection product

Summary

Solid preparation of a plant protection product obtainable by producing a melt containing

1-80% by weight of an active ingredient which can be used in crop protection or a combination of such active ingredients

20-99% by weight of at least one thermoplastic binder with a melting or glass temperature of more than 70 ° C. 0-20% by weight of additives,

the sum of all ingredients being equal to 100% by weight and subsequent pelletization, by dividing the melt into drops in a first step and solidifying them by cooling in a second step.