WO2000028816A1 - Plant protection agents in tablet form - Google Patents

Abstract

The invention relates to a solid preparation of a plant protection product which can be obtained by melt extrusion, subsequent cooling, crushing and/or milling, optionally grading and then pressing, tablet auxiliaries being added.

Description

Phytosanitary tablets

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 water-soluble thermoplastic binder with a melting or glass temperature of more than 70 ° C and a water solubility of more than 1.0 g per liter at 20 ° C

0-20% by weight additives,

where the sum of all ingredients is 100% by weight,

subsequent cooling, breaking and / or grinding,

Subsequent addition to the comminuted and optionally classified material (100 parts by weight) of

0-10 parts by weight of water-dispersible or water-insoluble tableting aids and

10-300 parts by weight of water-soluble tablet excipients,

then mixing the entire preparation and pressing into tablets.

Another object of the invention is a method for producing a solid preparation of a crop protection agent, characterized in that at least one active ingredient, at least one water-soluble thermoplastic binder with a melting or glass transition temperature of more than 70 ° C and, if appropriate, conventional additives to a plastic The mixture melts and the melt cools, breaks and / or grinds, if necessary classified, mixed with tablet excipients and compressed into tablets.

Another object of the invention is a method, characterized in that a solid preparation of a plant protection agent for combating phytopathogenic fungi, indispensable desired plant growth, undesirable insect or mite infestation and / or for regulating the growth of plants in solid or dissolved form and used on plants, their habitat or on seeds.

Active substance-containing preparations which are produced by melt extrusion 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.

WO 92/15197 describes the production of water-dispersible, quick-release crop protection granules. The crop protection agent is used together with water-soluble fillers e.g. 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.) for molding at 50-130 ° C, for example, extruded through a sieve .

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 and US 5,665,369 describe the co-extrusion of crop protection agents with polyvinylpyrrolidone, followed by cooling, breaking and grinding. The ground extrudate is sieved and, if necessary, tableted. The ground solid formulations obtained in this way are molecularly disperse distributions of the active compounds in the matrix PVP. Solid active ingredients can thus be processed into finely divided solid formulations without complex fine grinding processes. It is also possible to process liquid active ingredients and active ingredients with low melting points (<80 ° C), which cannot be formulated in a conventional manner (grinding the active ingredients with dispersing agents), to formulate solid formulations.

In the examples, various pyrethroids are melt extruded together with polyvinylpyrrolidone, discharged, cooled and ground. The sieve fraction around 250 μm is dispersed in water within a short time (80% of the active substance is released in less than 1 min). The resulting dispersion has a biological insecticidal activity comparable to that of conventional formulations. In addition, it is mentioned in US Pat. No. 5,665,369 that the sieve fraction was compressed into tablets with typical tableting substances, and that despite being assumed to be considerably larger Surface should release 80% of the active ingredient in less than 1 min, analogous to the original sieve fraction. Important parameters such as the size of the tablets, the type of tablet machine and especially the tablet auxiliaries used are not described. It is only mentioned that, for reasons of better handling, the ground extrudate can be compacted into tablets.

Typical tablet ingredients such as celluloses, starches and their derivatives (see textbook on pharmaceutical technology, Rudolf Voigt, 6th edition, VCH, Weinheim, Germany, 1987, p. 155 ff or Modern pharmaceutics, Gilbert S. Banker, 3 rd ed., Marcel Dekker Inc., New York, USA, pp. 333 ff), ie as auxiliary substances for direct tableting Without prior pretreatment of the tablet animal goods (e.g. wet granulation), they swell quickly in water (see use as tablet disintegrant), but only partially dissolve in water, if at all. In the case of spray tank applications, the use of such additives leads to adhesive, coarse sedimenting, sieves and nozzles clogging dispersions, which can be shown in the form of slurries of the substances mentioned in dispensing apparatus.

A problem is therefore the provision of a solid, dust-free, easy-to-handle and easy-to-dose, non-sticky and finely dispersed crop protection agent solid formulation which can be applied without problems and should also have a high storage stability.

Another problem is the simple and inexpensive direct tableting of active ingredients or active ingredient formulations with inexpensive, water-soluble excipients.

The object of the present invention was to provide such a formulation.

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

Surprisingly, it could be shown that substances such as ammonium sulfate, urea and effervescent propellants, which are unknown as auxiliaries in direct tableting (see Voigt BZ al, textbook of pharmaceutical technology; only very few substances are available for inexpensive and simple direct tableting of active ingredients or Active ingredient preparations suitable) can be easily compressed into tablets with polyvinylpyrrolidone crop protection extrudates. This and others Similar substances (tablet auxiliaries) are readily water-soluble and give clear solutions, ie they can be used without problems for spray tank applications. Presumably, polyvinylpyrrolidone is not only suitable for melt extrusion of active substances and in pure form as a tablet binder, but surprisingly also shows, as a highly concentrated extruded active substance, excellent binding properties for mixtures which cannot be directly tabletted a priori.

Active substances which do not decompose under the processing conditions during the production of the melt are generally suitable for the production of the melt. These can be both liquid and solid active substances. In addition, drug solutions are also considered.

Depending on the effectiveness, the amount of active ingredient components can

Release rate and dispersibility vary within wide limits. The active substance content in the melt can be in the range from 1-80% by weight, preferably from 20-80% by weight, based on the melt preparation. The only condition is that the preparation can still be processed thermoplastically.

The active ingredient is advantageously in the form of a "solid solution", i.e. molecularly dispersed in the matrix of the thermoplastic 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 stable, stable form 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 in the case of low-melting active ingredients or those which are liquid at room temperature.

The binder should 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 on the one hand and also have the ability to dissolve hydrophobic active ingredients on the other.

Examples of suitable binders are:

Polyvinylpyrrolidone (PVP), copolymers of N-vinylpyrrolidone (VP) and vinyl esters, especially 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 methacrylate ~ or C ₂ alkyl), polyacrylates and polymethacrylates (Eudragit types), copolymers of methyl methacrylate and acrylic acid, cellulose esters, cellulose ethers, especially methyl cellulose and ethyl cellulose, hydroxyalkyl celluloses, especially hydroxypropyl cellulose, hydroxyalkyl alkyl celluloses, in particular Hydroxypropyl ethyl cellulose, cellulose sephthalates, especially cellulose acetate phthalate and hydroxypropyl methyl 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 vinyl esters, in particular vinyl acetate, copolymers of vinyl acetate and crotonic acid, partially saponified polyvinyl acetate, polyvinyl alcohol, polyhydroxyalkylacrylates (Cχ-alkyl) or C ₂ -hydroxyalkyl, C ₂ -alkyl-C ₂ -alkyl-C ₂ -alkyl (-C ~ or C ₂ alkyl), polyacrylates and polymethacrylates (Eudragit types), poly-N-vinylcaprolactam and copolymers and 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 of the melt 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 conventional softening agents. The amount of plasticizer is at most 20, generally 0.5 to 15, preferably 0.5 to 5% by weight, based on the total weight of the melt, so that storage-stable plant protection product formulations are formed which do not show a cold flow. Examples of plasticizers of this type 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 dialkyl ester phthalates) (eg dialkyl ester phthalates) 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 diethylsulfosuccinate.

However, the mixture preferably contains no plasticizer.

The addition of surface-active substances is sometimes appropriate for an efficient biological effect of the preparation 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 dibutylnaphthalenesulfonic acid, and of fatty acid, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts sulfa - tated hexa-, hepta- and octadecanols or fatty alcohol glycol ether, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethyienoctylphenol ether, ethoxylated isooctyl, octyl, octyl, octyl, octyl, octyl 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 esters, lignin sulfite alcohol ethers, methyl taloethoxylate, methyl cellulose ethoxylate, methyl cellulose alcohol eamidethoxy latex, fatty amine ethoxylates, alkylpolyglycosides, 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 alcohols - 5-ethoxylated sulfate and mixed ethylenediaminophenamines.

Fillers or auxiliary substances that accelerate the release (disintegrants, wick substances), sub-

10 punches that improve the dispersibility or stabilize the dispersion (e.g. anionic surfactants) or also extrusion-technical aids such as lubricants or flow regulators. Dyes, such as azo dyes, organic or inorganic pigments or dyes of natural origin, where

15 organic pigments in a concentration of 0.001 to 10, preferably 0.5 to 3% by weight, based on the total weight of the melt, can be added to the mixture for the production of the melt, as can stabilizers, such as antioxidants, light stabilizers , Hydroperoxide destroyer, radio

20 calenders.

Wetting agents, preservatives, adsorbents, mold release agents and blowing agents can also be added (see e.g. R. Voigt, Textbook of Pharmaceutical Technology, VCH-Verlag, Weinheim, pp. 178-185, 25 1987).

The only prerequisite for the suitability of auxiliaries is adequate temperature stability during the production of the melt. 30

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.

35 The components can first be mixed and then melted and homogenized. In particular when using sensitive active ingredients, it has proven to be preferred to first melt and premix the polymeric binder, optionally together with conventional additives, the

40 stirred tanks, agitators, solid mixers etc. may be operated alternately, and then the sensitive active ingredient (s) in "intensive mixers" in the plastic phase should be mixed homogeneously with very short residence times. Active ingredient (s), binders and possibly additives can be in liquid and solid form as

45 resin, can be used 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, such as kneaders, are particularly suitable. Depending on requirements, the speed in the kneader can be set temperature-controlled, ie 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. Particularly suitable mixing devices are extruders and dynamic and static mixers, as well as stirred tanks, single-shaft agitators with stripping devices, in particular so-called paste agitators, multi-shaft agitators, in particular PDSM mixers, solid-state mixers and preferably mixing kneading reactors (e.g. 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), rotor / stator systems (eg Dispax ^® from IKA) or counter-rotating and co-rotating twin-screw kneaders (ZSK ) eg from Werner u. Pfleiderer, Stuttgart, Germany.

The mixing device can be fed continuously or discontinuously in the usual manner. Powdered components can be fed in free, e.g. be introduced via 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 using a suitable pump unit.

The mixing and / or melting can also take place in two or more discontinuously operating devices in parallel or alternately.

The mixture obtained by mixing and melting the binder, the active ingredient and optionally the additive or the additives is pasty to viscous (thermoplastic) and therefore also extrudable. The glass transition temperature of the mixture 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 vacuum pump can be removed during extrusion. 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 cross-section 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 shaped and discharged as a strand with a circular cross section.

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 quickly and finely distributed when the formulation is dissolved in water, and a stable dispersion also results.

The invention furthermore relates to the use of one or more binders from the group of the polyvinylpyrrolidones or the copolymers of N-vinylpyrrolidone or a mixture of one or more polyvinylpyrrolidones with one or more copolymers of N-vinylpyrrolidone for producing a solid preparation according to the invention Pesticide.

The invention furthermore relates to the use of the solid preparation according to the invention of a crop protection agent for combating 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 method according to the invention is suitable, for example, for processing crop protection agents having 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, diphenamide, etobenzanide (benzchlomet), flamprop-methyl, fosamine, isoxaben, monalide,

Naptalame, pronamide (propyzamide), propanil

Aminophosphoric acids, such as bilanafos, (bialaphos), buminafos, glucosinate-ammonium, glyphosates, sulfosates

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, butene chloride, diethyl ethyl, dimethachlor, metazachlor, metolachlor, pretilachlor, propachlor, prynachlor, terbuchlor, thenyl chlorine, xylachlor Cyclohexenones such as Alloxydim, Caloxydim, Clethodim, Cloproxydim, Cycloxydirr., Sethoxydim, Tralkoxydim, 2- {1- [2- (4-chlorophenoxy) propyloxyimino] 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

Dinitroaniiine such as Benefin, Butralin, Dinitra in, 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, fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen

Dipyridylenes such as cyperquat, difenzoquat methyl sulfate, diquat, paraquat dichloride

Urea, such as benzthiazuron, buturon, chlorbromuron, chloroxuron, chlorotoluron, cumyluron, dibenzyluron, cycluron, dimefuron, diuron, dymron, ethidimuron, fenuron, fluorometuron, isoproturon, isouron, carburonuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronururon , 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-ethyi, fenoxaprop-p-ethyi, fenthia-propethyl, fluazifop-butyl, fluazifop-p-butyl, haloxyfop-ethoxye- thyl, haloxyfop-methyl, haloxyfop-p-methyl, isoxapyrifop, propaquizafop, 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, ethoxysulfuron, flazasulfuron, halosulfuron-methyl, imazosulfuron-methyl, proz -ethyl, rimsulfone, sulfometuron-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl

Triazines such as Ametryn, Atrazin, Aziprotryn, Cyanazine, Cyprazine, Desmetryn, Dirnethamethryn, Dipropetryn, Eglinazin-ethyl, Hexazinone, Procyazine, Prometon, Prometryn, Propazin, Secbumeton, Simazin, Simetryn, Terbumeton, Terbutrin, Trietutyzine, Terbutyzine

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, Triazethan, 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 ethylenebisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese-zinc-ethylenediamine-bis-dithiocarbamate, tetramethylthiuron-bis-dithiocarbamate, ammonium-bis-dithiocarbamate, ammonium-bis-dithiocarbamate, ammonium-bis-dithiocarbamate, ammonium-bis-dithiocarbamate, ammonium-bis-dithiocarbamate, -dithi-bis-dithi-carbamate, , Ammonia complex of zinc (N, N '-propylene-bis-dithiocarbamate), zinc (N, N' -propylene-bis-dithiocarbamate), N, N '-polypropylene-bis- (thiocarbamoyl ) disulfide;

Nitroderivatives, such as dinitro- (1-methylheptyl) phenylcrotonate, 2-sec-butyl-4, 6-dinitrophenyl-3, 3-dimethylacrylate, 2-sec-butyl-, 6-dinitrophenyl-isopropyl carbonate, 5-nitro- di-isopropyl isophthalate;

heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2, -dichloro-6- (o-chloroanilino) -s-triazine, 0, O-diethyl-phthalim-dophosphonothioate, 5-amino-l- [bis- (dimethyla ino) - phosphinyl] -3-phenyl-l, 2, 4-triazole, 2, 3-dicyano-l, 4-dithioanthraquinone, 2-Thio-l, 3-dithiolo [4, 5-b] quinoxaline, 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimi-dazol, 2- (furyl- (2)) - benzimidazole, 2- (thiazolyl- (4)) -benzimidazole, N- (1, 1, 2, 2-tetrachloroethylthio) -tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthiophthalimide,

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-chloro-phenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2, 3-dihydro-5-carboxa- nilido-6-methyl-l, 4-oxathiin, 2, 3-dihydro-5-carboxanilido-6-methyl-1, 4-oxathiin-4, 4-dioxide, 2-methyl-5, 6-dihydro- 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-carboxylic acid amide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, N-formyl-N-morpholine-2,2,2-trichloroethyl acetal, piperazin-1,4-diyl bis-1- (2,2,2-trichloroethyl) formamide, 1- (3,4-dichloroanilino ) -1- formylamino-2, 2, 2-trichloroethane, 2, 6-dimethyl-N-tride ecyl-morpholine or its salts, 2, 6-dimethyl-N-cyclododecyl-morpholine or its salts, N- [3- (p-tert. -Butylphenyl) -2-methylpropyl] cis-2, 6-dimethyl-morpholine, N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine, 1- [2- ( 2, 4-dichlorophenyl) -4-ethyl-l, 3-dio-xolan-2-yl-ethyl] -1H-1, 2, 4-triazole, 1- [2- (2, 4-dichlorophenyl) -4 -n-propyl-1, 3-dioxolan-2-yl-ethyl] -1H-1, 2,4-triazole, N- (n-propyl) -N- (2,4, 6-trichlorophenoxyethyl) - N 'imidazol yi urea, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-l-yl) -2-butanone, 1- ( 4-chlorophenoxy) -3, 3-dimethyl-l- (1H-1,2,4-triazol-l-yl) -2-butanoi, (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-dimethyla-mino-4-hydroxy-6-methyl-pyrimidine, bis- (p-chlorophenyl) -3-pyridine-methanol, 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-Me- thyl-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-dimethylphenyl) -N -furoyl (2) -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- (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- (ethylaminocarbonyl) -2 -methoximino] -acetamide, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2,4-difluoro-a- (1H-1,2) triazolyl-1-methyl) -benzhydryl alcohol, N- (3-chloro-2, 6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine,

1- ((bis- (4-Fluorophenyl) methylsilyl) methyl) -1H-1,2,4-triazole.

Strobilurins, such as methyl-E-methoxyimino- [a- (o-tolyloxy) -o-tolyl] acetate, methyl-E-2- {2- [6- (2-cyanophenoxy) pyrimi - din-4- yloxy] -phenyl} -3-methoxyacrylate, methyl-E-methoxyimino- [a- (2-phenoxyphenyl)] acetamide, methyl-E-methoxyimino- [a- (2,5-dimethylphenoxy) -o-tolyl] - acetamide,

From the class of strobilurins, fungicidally active compounds of the formulas IA containing a nucleus Q or IB containing a nucleus T are also to be mentioned,

in which —— represents a single or double bond and the nucleus, the index and the 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;

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 (0CH 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 is bonded directly or via an oxy, mercapto, amino or alkylamino group; for example optionally substituted aryloxy, substituted hetaryloxy, substituted aryloxymethylene, substituted hetaryloxymethylene, substituted arylethenylene , 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 is attached to the via an oxygen atom (0) Scaffold is bound;

where hetaryloxy, e.g. is a 5- or 6-membered heterocycle (heterocyclyl) containing, 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, haloalkenyi, alkenyloxy, haloalkenyloxy, alkynyl, haloalkynyl, alkynyloxy, haloalkynyloxy, alkoxy, haloalkoxy, alkyl hio, haloalkylthio, alkylamino, alkylcarbonylamino , Alkoxycarbonyl, alkylcarbonyloxy,

Alkylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonylamino, alkoxycarbonylamino, alkylcarbonyl-N-alkylamino and alkylcarbonyl-N-alkylamino, the alkyl groups in these radicals preferably containing 1 to 6 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, contains one or more heteroa- may contain atoms from the group consisting of oxygen, sulfur and nitrogen;

R * -OC [CO ₂ CH ₃ ] = CHOCH ₃ , -0C [CO ₂ CH ₃ ] = CHCH ₃ , -OC [CO ₂ CH ₃ ] = CHCH CH ₃ , -SC [CO 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 ;

\

Ry -0- = 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;

Cyano, nitro, halo, C_-C ₄ -alkyl, C haloalkyl, Cι-C ₄ -alkoxy, C ₄ haloalkoxy, Cι ~ C ₄ alkylthio;

in the event that n> 1, a C ₃ -C ₅ alkylene, C ₃ -Cs alkenylene, oxy-C -C alkylene, oxy-Cι- bonded to two adjacent C atoms of the phenyl ring C ₃ -alkyleneoxy, oxy-C -C -alkenylene, oxy-C -C -alkenyleneoxy or butadienediyl group, these chains in turn can carry one to three of the following radicals: halogen, C ₁ -C ₄ alkyl , _Cι-C4 haloalkyl, Cι-C ₄ -alkoxy, C ₄ -haloalkoxy or Cι-C ₄ alkylthio,

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

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

They are of particular importance for combating a large number of fungi on various crops such as cotton, vegetable plants (eg cucumber, beans and pumpkin family), barley, grass, oats, coffee, corn, fruit plants, rice, rye, soybeans, wine, wheat , Ornamental plants, sugar cane and a variety of seeds. They are particularly suitable for combating the following plant diseases:

AI ternaria types of vegetables and fruits,

Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines,

Cercospora arachidicola on peanuts,

Eryεiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants,

Erysiphe graminis (powdery mildew) on cereals,

Fusarium and Verticillium species on different plants,

-ieI_nint_aosporiu.il species on cereals,

Mycosphaerella species on bananas,

P__ytop__ti_ora 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,

Rizoctonia species on cotton, rice and lawn,

Septoria nodorum on wheat,

Uncinula necator on vines,

L / 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 melts generally contain 1 to 80, preferably 20 to 80, particularly preferably 50 to 80% by weight of one of the compounds IA or IB or the mixture of the compounds IA or IB.

The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to ¹ H-NMR or HPLC spectrum).

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.

Another object of the invention is the subsequent processing of the melt. The still plastic melt is cooled (e.g. on a conveyor belt) after being discharged from the mixing device, broken and / or ground. The ground or broken material is either mixed directly with the tablet and tabletting auxiliaries described below or prepared beforehand by classification (e.g. by sieving). The secondary fractions obtained can be returned to the melting process or the grinding process.

The fractionated granules used for tableting, in particular for direct tabletting in the examples, are fractions of 200-400 μm obtained by sieving and <200 μm of the melt granulated and ground after cooling. The use of melt granules of other grain size ranges should not be ruled out, however, but can vary within wide limits depending on the desired release rate and processability. Just like the melt granulate, the tabletting mixture to be added, consisting of tablet auxiliaries and tableting auxiliaries, can be ground and, if necessary, classified. In addition, the comminuted material can be ground together with tablet auxiliaries and tableting auxiliaries.

According to the invention, the comminuted and optionally classified material (100 parts by weight) is mixed with 0-10 parts by weight of water-dispersible or water-insoluble tableting auxiliaries and 10-300 parts by weight of water-soluble tablet auxiliaries and compressed into tablets. Optionally, lubricants, flow regulators, wetting agents, preservatives, adsorbents, mold release agents and disintegrants can be added (see, for example, R. Voigt, Textbook of Pharmaceutical Technology, VCH-Verlag, Weinheim, pp. 178-185 , 1987) which, as tablet animal aids, enable or improve the tablettability of the overall mixture.

Flow regulators improve the sliding and free-flowing properties of the material to be tabletted. Talc, siliconized talc, calcium, magnesium and aluminum stearate, stearic acid, palmitic acid, starch, Aerosil® and stearyl, cetyl and myristyl alcohol may be mentioned as flow regulators.

Lubricants reduce metal friction and tablet / metal friction. Examples of lubricants which may be mentioned are talc, siliconized talc, calcium, magnesium and aluminum stearate, stearic acid, palmitic acid, starch, Aerosil®, stearyl and cetyl alcohol and paraffin.

Mold release agents reduce the sticking of the tabletting compound or the tablet to the punches and die wall. Examples of mold release agents include talc, siliconized talc, stearic acid, paraffin, calcium and magnesium stearate, hydrogenated fats (e.g. Cutina HR®) and silicone emulsions.

The amount of water-dispersible or water-insoluble tableting auxiliaries can vary within wide limits depending on the tablettability, release rate and dispersibility, but should not exceed 10 parts by weight, based on the mixture as a whole, in order to obtain sufficiently quickly and finely dispersed tablets. Thus, the amount of water-dispersible or water-insoluble tabletting aids can be in the range from 0-10 parts by weight, preferably 0-5 parts by weight, based on the total preparation to be tabletted. The only mandatory condition is that the preparation can still be tabletted.

In addition to the water-dispersible or water-insoluble tabletting auxiliaries to be optionally added, water-soluble tablet auxiliaries are added to the total mixture before tableting.

Tablet auxiliaries, in the sense of the invention, are water-soluble substances with a water solubility of more than 1 g / 1, preferably more than 5 g / 1, particularly preferably more than 10 g per liter at a temperature of 20 ° C. The tablet auxiliaries according to the invention are, on the one hand, Solubility suitable to release the active ingredient-containing melt particles from the tablet association quickly and successively into the main liquid stream. The melt particles in turn can release the active ingredient in water more or less separately from one another. The melt particles are more or less isolated in the tablet matrix due to the tablet excipients depending on the grain size and weight percentage. On the one hand, this increases the storage stability with regard to sticking of the melt particles in the dry state as well as the risk of sticking and clumping of the melt particles when the formulation is introduced into water. The pesticide tablets can be used solid or dispersed in water. When dispersing in spray tanks, it is also possible to use induction devices with coarse-meshed nets which prevent the tablets from entering the pumping circuit too quickly.

Water-soluble tablet auxiliaries for the purposes of the invention are, on the one hand, inorganic water-soluble ammonium, alkali and alkaline earth metal salts, in particular the sulfates, chlorides, carbonates and hydrogen carbonates, phosphates and nitrates, borates and boric acid such as e.g. Ammonium sulfate, sodium hydrogen carbonate and ammonium chloride.

In addition, low molecular weight, water-soluble organic substances such as citric acid, urea, neopentyl glycol, pentaerythritol, sodium acetate, sodium citrate and anionic or nonionic surfactants such as e.g. Sodium dodecyl sulfate, sodium diisobutylnaphthalene sulfonate or ethoxylated fatty alcohols.

Substances which are preferably used are those which do not damage the plant and its surroundings in the application amounts customary for crop protection agents and which, as such, can be used without problems in agriculture, such as, for example, urea, ammonium sulfate, ammonium nitrate and phosphates, which are used, inter alia, as fertilizers .

Because of their rapid water solubility and their good tableting properties, inorganic ammonium salts such as ammonium sulfate, ammonium chloride and ammonium nitrate are particularly preferred.

The amount of water-soluble tablet excipients in the overall preparation can vary within wide limits depending on the tablettability of the overall mixture and the dispersing properties of the tablets. For example, the amount of water-soluble tabletting auxiliaries can range from 10-300 parts by weight, preferably from 10-200

Parts by weight and particularly preferably 10-100 parts by weight, based on the total preparation to be tabletted. The only one an imperative condition is that the preparation can still be tabletted.

The shape and size of the tablets, which result from the compression of the overall mixtures, can be varied within wide limits, depending on the application and property profile. It is also possible to provide the tablets with water-soluble, water-swellable or water-vapor-permeable coatings.

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

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, if appropriate, additives (for example nonionic surfactants) given in the examples were mixed or introduced separately into a co-operating, closely intermeshing twin-screw extruder ZSK 30 (Werner & Pfleiderer GmbH, Stuttgart), extruded over 12 temperature zones and passed through a 5 X 2 mm nozzle bar discharged onto a cooled conveyor belt.

The following table shows the temperature profile (° C) in the extruder (zone 1 - 12 and head nozzle) and the cooled conveyor belt:

The speed of the screws can be varied in the range of 100-300 rpm, at temperatures between 20 and 100 ° C in the delivery zone (zone 1) and 100-180 ° C in the melting, kneading and mixing zones (zone 2 - 12). The throughput was 10-12 kg / h and the residence time r> egg 1-2 mm. The active ingredient, the polymer and the additives were fed in via metering scales at the extruder inlet and melted. Resin-like or liquid-like components at room temperature were optionally fed in with heating and incorporated with mixing and kneading elements. It was also possible to degas in several extruder zones. The melt emerging through a nozzle at the end of the extruder was discharged onto a cooled conveyor belt. From there, the product, cooled to room temperature, was introduced into a strand granulator 1.1 mm, type SGS 100 / E, CF Scheer & CIE and pre-assembled into cylindrical granules with an average cross section of 1-2 mm. The resulting granulate was ground with a Fritsch pulverisette 14 - Rotorschnellmühle, Fritsch GmbH, Idar-Oberstein and classified with sieve sets in two fractions (<200 μm and 200-400 μm). The sieve fractions obtained in this way were mixed with the corresponding commercially available tablet animal auxiliaries and tablet auxiliaries, as a powder or crystal fraction with particle sizes <1000 μm, and tabletted together. The entire preparations were made into a circular 1.00 with an automatic eccentric press of the brand Kilian KS 1, Kilian & Co. GmbH, Maschinenfabrik Köln-Niehl, at upper ram pressures of 2.8-3.1 bar, with a lifting capacity of 25 strokes / minute and with a lower ram stroke of 18 mm g Boli with a diameter of 16 mm and a height of 5 mm pressed.

example 1

Various solid melt preparations of pesticides of different compositions A - D were produced as described in the general procedure. The formulations also contained as an active ingredient kresoxim-methyl (IUPAC name: methyl methoxyimino-α- (o-tolyloxy) -o-tolylacetate), as a binder Luviskol ^® K 30, Luviskol ^® VA 64, or as an additive Lutensol ^® AT 25th

The amounts added are shown in the table below.

The melt formulation A was after melt extrusion and subsequent packaging to <200 μm and 200-400 μm broken granules in the manner described above with the following tableting aids. Mixed substances and tablet excipients and tabletted to 1.00 g boluses.

Example 2

The following table contains the total composition of the tablets produced from formulation A in parts by weight and the sieve residues explained in Example 3 in% by weight, based on the amount used.

1. The formulation without water-soluble tablet auxiliaries results in a strongly adhesive residue in water. 2. The blind formulation without melt preparation from active ingredient and polyvinylpyrrolidone cannot be tabletted, it remains in powder form Formulations B - D show similarly favorable application properties as formulation A.

Aerosil®; highly disperse silicon dioxide, Degussa AG, Germany Wettol NT1®; Diisobutylnaphthalenesulfonic acid sodium, BASF AG, Germany

Magnesium stearate, ammonium chloride, sodium hydrogen carbonate, citronic acid; Aldrich, Germany urea, BASF AG, Germany

Example 3

The dispersibility or the sieve residue was determined as follows:

In each case two 1.0 g tablets of the respective formulation are mixed with stirring (Ikamag RET-G magnetic stirrer, Janke & Kunkel GmbH & Co. KG., Staufen, Germany; Teflon stirrer 1 = 4 cm) in a 1 1 standing flask with a bottom diameter of 10 cm 1000 ml of tap water (T = 20 ° C) entered at a stirring speed of 300 rpm (0.05% dispersion based on the active ingredient). After 40 minutes, the filter is filtered through 50 μm sieves and the sieve residue is determined in% by weight based on the starting quantity (2.0 g). In each case, double determinations were carried out to determine the sieve residues. The sieves were dried to constant weight in a vacuum drying cabinet.

The active substance content of the respective formulations was checked by means of HPLC. The active ingredient is molecularly dispersed in the melt matrix and can be quickly and finely dispersed in water from the compressed melt and tablet mixture. The tabletting and dispersing properties are almost independent of the particle size of the melt granulate used. The speed of dissolution is consequently significantly faster when using boluses with weights of <500 mg than that of the 1.0 g tablets. The speed of dissolution can also be adjusted depending on the application by the type of tabletting matrix.

The pesticide tablets produced are suitable for both spraying and scattering applications.

Claims

claims

1. 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 water-soluble thermoplastic binder with a melting or glass temperature of more than 70 ° C and a water solubility of more than 1.0 g per liter at 20 ° C

0-20% by weight additives,

where the sum of all ingredients is 100% by weight,

subsequent cooling, breaking and / or grinding,

Subsequent addition to the comminuted and optionally classified material (100 parts by weight) of

0-10 parts by weight of water-dispersible or water-insoluble tableting aids and

10-300 parts by weight of water-soluble tablet excipients,

then mixing the entire preparation and pressing into tablets.

2. Solid preparation of a plant protection product according to claim 1 containing as thermoplastic binder one or more polyvinylpyrrolidones.

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

4. Solid preparation of a plant protection product according to claim 1 containing as the thermoplastic binder a mixture of one or more polyvinylpyrrolidones and one or more copolymers of N-vinylpyrrolidone.

5. Solid preparation of a plant protection product according to claim 1 to 4 containing at least one fungicidal, herbicidal, insecticidal, acaricidal or growth-regulating compound or an active ingredient mixture from the group of these compounds.

6. Solid preparation of a plant protection product according to claim 5 containing as 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;

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 [CO 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 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, contains one or more heteroatoms from the group consisting of oxygen, sulfur and nitrogen may contain;

R ^X -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 ;

\

Ry -0- = 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, C1-C ₄ -alkyl, -C-C ₄ -haloalkyl, Cι-C ₄ -alkoxy, Cχ-C ₄ -haloalkoxy, Cι ~ C ₄ -alkylthio;

in the event that n> 1, a C ₃ -C ₅ alkylene, C ₃ -Cs-alkenylene, oxy-CC ₄ -alkylene, oxy-Cι-C bonded to two adjacent C atoms of the phenyl ring ₃ -alkyleneoxy, oxy-CC ₄ -alkenylene, oxy-C -C ₄ -alkenyleneoxy or butadienediyl group, these chains in turn can carry one to three of the following radicals: halogen, -C ₄ -alkyl, Cχ -C-haloalkyl, -C-C ₄ -alkoxy, -C-C-haloalkoxy or Cι-C -alkylthio,

7. Solid preparation of a plant protection product according to claim 1 containing inorganic salts as water-soluble tablet excipients.

8. Solid preparation of a plant protection product according to claim 7 containing inorganic water-soluble tablet auxiliaries - see ammonium salts, such as ammonium sulfate, ammonium chloride or ammonium nitrate.

9. Solid preparation of a plant protection product according to claim 1 containing effervescent propellants made of sodium hydrogen carbonate and citric acid as water-soluble tablet auxiliaries.

10. Solid preparation of a plant protection product according to claim 1 containing urea or other solid fertilizers as water-soluble tablet excipients.

11. A process for the preparation of a solid preparation of a crop protection agent according to one or more of claims 1 to 10, characterized in that at least one active ingredient, at least one water-soluble thermoplastic binder with a melting or glass transition temperature of more than 70 ° C and optionally conventional additives melts into a plastic mixture that cools the melt, breaks and / or grinds, if necessary classified, mixed with tablet excipients and compressed into tablets.

12. A method for producing a solid preparation of a crop protection agent according to claim 11, characterized in that the melt is produced in an extruder.

13. A method for combating phytopathogenic fungi, undesired plant growth, undesirable insect or mite infestation and / or for regulating the growth of plants, characterized in that a solid preparation of a crop protection agent according to one or more of claims 1 to 10 in solid or loosened form and on plants, their habitat or on seeds.

14. A method for controlling insects or wood-destroying fungi, characterized in that a solid preparation of a crop protection agent according to one or more of claims 1 to 10 is used in dissolved form and is allowed to act on insects, their habitat or on wood.