US006063393A United States Patent (19) 11 Patent Number: 6,063,393 Tsuboi et al. (45) Date of Patent: *May 16, 2000

54 PLANT TREATMENTAGENTS 56) References Cited 75 Inventors: Shin-ichi Tsuboi, Tochigi, Atsumi U.S. PATENT DOCUMENTS Kamochi, Kochi, Nobuhiro Yamashita, 1661,577 3/1928 Renner et al.. Kochi, Ikuya Saito, Kochi, Yuzuru 3,068,087 12/1962 Davis. Wada, Hachioji, Kunihiro Isono, 4.291,497 9/1981 Manankov . Tochigi, Shigeharu Koyama, Oyama, 4,401,454 8/1983 Fritz et al...... 504/165 all of Japan 4,666,706 5/1987 Farquharoon et al...... 424/408

4,743,448 5/1988 Bahadir et al...... 424/405 73 Assignee: Nihon Bayer Agrochem K.K., Tokyo, 5,034,524 7/1991 Shrokawa et al...... 544/124 Japan 5,157,207 10/1992 Carlson et al...... 800/200 5,201.925 4/1993 Itzel et al.. * Notice: This patent issued on a continued pros FOREIGN PATENT DOCUMENTS ecution application filed under 37 CFR 1.53(d), and is subject to the twenty year O179588 4/1986 European Pat. Off.. patent term provisions of 35 U.S.C. O 254 196 1/1988 European Pat. Off.. 154(a)(2). 2 449 664 9/1980 France. Primary Examiner Neil S. Levy 21 Appl. No.: 08/041,077 Attorney, Agent, or Firm Norris, McLaughlin & Marcus, P.A. 22 Filed: Apr. 1, 1993 30 Foreign Application Priority Data 57 ABSTRACT The present invention relates to a process for the treatment Apr. 9, 1992 JP Japan ...... 4-115.283 of individual plants with Solid shaped plant treatment agents (51) Int. Cl...... A01N 25/08 which are introduced into the Sap conduction paths of the 52 U.S. Cl...... 424/409; 424/405; 424/406; plants, new Solid shaped plant treatment agents and their 424/407; 424/408 production. 58 Field of Search ...... 424/407, 408, 424/409, 405, 406 6 Claims, No Drawings 6,063,393 1 2 PLANT TREATMENTAGENTS the Sap conduction paths of individual plants, character ised in that active compounds are mixed and physically or The present invention relates to a process for the treat chemically shaped with Substances forming the matrix of ment of individual plants with Solid shaped plant treatment a Solid carrier. agents which are introduced into the Sap conduction paths of The proceSS according to the invention is Suitable for the the plants, new Solid shaped plant treatment agents and their treatment of valuable individual plants. These include stock production. and ornamental plants. Stock and ornamental plants which It has already become known to inject Solutions of may be mentioned are: herbaceous plants, annual and peren certain insecticides or to implant pulverulent formulations nial shrubs and Woody plants, Such as bushes and trees. into the trunks of deciduous and coniferous trees (Chemical The herbaceous plants include vegetables, Such as Abstracts CA 108: 181 188w; CA 99: 83 692v, CA 99: 181 tomatoes, paprika, aubergines, cucumbers, melons, cabbage 184; and CA 87: 146 712). Species, potatoes and tobacco. The perennial shrubs include The method is limited to readily water-soluble active tea and coffee. The woody plants include the known berry compounds having a Systemic action. Handling of the and fruit-bearing Woody plants, pomaceous/stone fruit, method under conditions in practise, that is to Say admin 15 berries, bananas, citrous, grapevines, palms (for example oil istering an adequate amount of active compound into the Sap trees), cacao, olives, hops, roses and rhododendron, and also Stream and thereby damaging the plant only minimally not the Woody plants used in forestry, Such as beech, oak, Spruce only under experimental purposes on a very few plants, is and fir. unsatisfactory. Cuttings, Slips, tubers, bulbs and parts of leaf used for It has already become known to embed active com propagation may furthermore be mentioned. pounds in a polymer matrix, from which they are released Pests which may be mentioned are phytopathogenic again only slowly. Such Slow-release shaped articles are insects, arachnids and nematodes, and also fungi and bac used to release active compounds in the Soil over a relatively teria. long time (Chemical Abstract CA 100: 47 099 n; and U.S. The insects include: Pat. No. 3,269,900). Other polymer/active compound for 25 From the order of the Isopoda, for example, Oniscus aSellus, mulations are employed to release readily vapourisable Armadillidium vulgare and Porcellio Scaber. active compounds uniformly into the atmosphere over a From the order of the Diplopoda, for example, Blaniulus relatively long period of time (U.S. Pat. No. 3,318,764). Yet guttulatus. other polymer/active compound formulations are employed From the order of the Chilopoda, for example, Geophilus to protect animals from parasites. For this, the active carpophagus and Scutigera Spec. compound, which migrates to the polymer Surface, is rubbed From the order of the Symphyla, for example, Scutigerella off mechanically by the coat of the animal and distributed immaculata. over the animal (U.S. Pat. No. 3,852,416). From the order of the Thysanura, for example, Lepisma In the customary treatment of plants by atomising, Saccharina. Spraying, dusting and the like, the active compound is 35 From the order of the Collembola, for example, Onychiurus distributed in a suitable formulation as far as possible over (iringiitis. the entire Surface of the plants. It then either encounters From the order of the Orthoptera, for example, Blatta directly the plant pests to be combated, or it has to penetrate Orientalis, Periplaneta americana, Leucophaea maderae, the protective layers of the plants in order to arrive at the Blattella germanica, Acheta domeSticus, Gryllotalpa spp., Sites of action via the Sap Stream of the plant. These 40 LOCusta migratoria migratorioides, Melanoplus differen treatment methods are associated with a high loSS of active tialis and Schistocerca gregaria. compound. The same applies to methods where active From the order of the Dermaptera, for example, Forficula compound formulations are used in the root region, in which auricularia. the active compound is taken up via the roots and arrives at From the order of the Isoptera, for example, Reticulitermes the Site of action via the Sap Stream. Here also, the active 45 Spp. compound must be present in the Soil in a Sufficiently high From the order of the Anoplura, for example, Phylloxera concentration for the plants to be able to absorb enough vaStatrix, Pemphigus spp., Pediculus humanus CorpOris, active compound. Haematopinus spp. and Linognathus spp. To match the amount of active compound to be applied From the order of the Mallophaga, for example, Tri as precisely as possible to the actual requirement of the 50 chodectes spp. and Damalinea spp. plant, it would be desirable for the required amount of active From the order of the Thysanoptera, for example, Hercino compound to be introduced directly into the Sap Stream of thrips femoralis and Thrips tabaci. the plant. A prerequisite here is, however, that the plant (for From the order of the Heteroptera, for example, Eurygaster example valuable productive fruit trees) is not damaged spp., Dysdercus intermedius, PieSma quadrata, Cimex even after Several applications. 55 lectularius, Rhodnius prolixus and Triatoma spp. The present invention relates to: From the order of the Homoptera, for example, Aleurodes 1. a process for the treatment of individual plants with Solid brassicae, Bemisia tabaci, Trialeurodes vaporariorum, shaped plant treatment agents in which the active com Aphis gossypii, Brevicoryne brassicae, Cryptomyzus pounds are contained in a matrix of a Solid carrier material ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, and which are introduced into the region of the Sap 60 Hyalopterus arundinis, Macrosiphum avenae, Myzus conduction paths of the plants. spp., Phorodon humuli, RhopaloSiphum padi, Empoasca 2. Solid shaped plant treatment agents in which the active spp., EuScelis bilobatus, NephOtettix cincticeps, Lecanium compounds are contained in a matrix of a Solid carrier corni, Saissetia Oleae, Laodelphax Striatellus, Nilapar material and which are introduced into the region of the vata lugenS, A.Onidiella aurantii, Aspidiotus hederae, Sap conduction paths of individual plants. 65 Pseudococcus spp. and Psylla spp. 3. A process for the production of Solid shaped plant From the order of the Lepidoptera, for example, Pectino treatment agents which are introduced into the region of phora gossypiella, Bupalus piniarius, Cheimatobia 6,063,393 3 4 brumata, Lithocolletis blancardella, Hyponomeuta Peronospora Species, Such as, for example, Peronospora pisi padella, Plutella maculipennis, MalacoSoma neuStria, or P. brassicae, Euproctis chrySOrrhoea, Lymantria spp. Bucculatrix Erysiphe Species, Such as, for example, Erysiphe graminis, thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa Sphaerotheca Species, Such as, for example, Sphaerotheca spp., Feltia spp., Earias insulana, Heliothis spp., fuliginea, Spodoptera exigua, MameStra brassicae, Panolis Podosphaera Species, Such as, for example, Podosphaera flammea, PrOdenia litura, Spodoptera spp., Trichoplusia leucotricha, ni, Caprocapsa pomonella, Pieris spp., Chilo spp., Venturia Species, Such as, for example, Venturia inaequalis, Pyrausta nubilalis, Ephestia kuehniella, Galleria Pyrenophora Species, Such as, for example, Pyrenophora mellonella, Tineola bisselliella, Tinea pellionella, Hofm teres or P graminea (conidia form: Drechslera, Syn: annophila pseudospretella, CaCOecia podiana, Capua Helminthosporium); reticulana, Choristoneura fumiferana, Clysia ambiguella, Cochliobolus species, Such as, for example, Cochliobolus Homona magnanima and Tortrix viridana. Sati vu S (conidia form: Drechslera, Syn: From the order of the Coleoptera, for example, Anobium Helminthosporium); punctatum, Rhizopertha dominica, Bruchidius Obtectus, Uromyces Species, Such as, for example, Uromyces appen Acanthoscelides Obtectus, Hylotrupes bajulus, Agelastica 15 diculatus, alni, Leptinotarsa decemlineata, Phaedon cochleariae, Puccinia Species, Such as, for example, Puccinia recondita, Diabrotica spp., Psylliodes chrysocephala, Epilachna Tilletia Species, Such as, for example, Tilletia caries, varivestis, Atomaria spp., Oryzaephilus Surinamensis, Ustilago Species, Such as, for example, Ustilago nuda or Anthonomus spp., Sitophilus spp., Otiorrhynchus Ustilago avenae, Sulcatus, CosmopoliteS SOrdidus, CeuthOrrhynchus Pellicularia Species, Such as, for example, Pellicularia aSSimilis, Hypera postica, Dermestes spp., Trogoderma Sasakii, spp., Anthrenus spp., Attagenus spp., Lyctus spp., Pyricularia Species, Such as, for example, Pyricularia Melligethes aeneus, Ptinus spp., Niptus hololeucus, Gib Oryzae, bium psylloides, Tribolium spp., Tenebrio molitor; Agri Fusarium species, Such as, for example, Fusarium cul otes spp., Conoderus spp., Melolontha melolontha, 25 mortin, Amphimallon Solstitialis and Costelytra zealandica. Botrytis Species, Such as, for example, Botrytis cinerea, From the order of the Hymenoptera, for example, Diprion Septoria Species, Such as, for example, Septoria nodorum, spp., Hoplocampa spp., Lasius spp., Monomorium phara Leptosphaeria Species, Such as, for example, Leptosphaeria Onis and Vespa spp. nodorum, From the order of the Diptera, for example, Aedes spp., CercoSpora Species, Such as, for example, Cercospora cane Anopheles spp., Culex spp., Drosophila melanogaster, ScenS, Musca spp., Fannia spp., Caliphora erythrocephala, Alternaria Species, Such as, for example, Alternaria brassi Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophi Cae and lus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Pseudocercosporella Species, Such as, for example, Hypoderma spp., Tabanus spp., Tannia spp., Bibio 35 Pseudocercosporella herpOtrichoides. hortulanus, Oscinella frit, Phorbia spp., Pegomyia The good toleration, by plants, of the active compounds, hyOScyami, Ceratitis capitata, Dacus Oleae and Tipula at the concentrations required for combating plant diseases, paludosa. permits treatment of above-ground parts of plants, of Veg From the order of the Siphonaptera, for example, Xenopsylla etative propagation Stock and Seeds. cheopis and Ceratophyllus spp. 40 The agents according to the invention are employed in the From the order of the Arachnida, for example, Scorpio form of nails, pegs, Spikes, plugs, needles, hollow nails, maurus and LatrodectuS mactans. Strips, sheets, films, clamps, tapes, wires, threads, fibres, From the order of the Acarina, for example, Acarus Siro, woven fabrics or knitted fabrics. Argas spp., Ornithodoros spp., DermanySSuS gallinae, These are either forced, pressed or knocked into Soft Eriophyes ribis, Phylocoptruta oleivora, Boophilus spp., 45 tissue or pushed under carefully detached and raised bark or Rhipicephalus spp., Amblyomma spp., Hyalomma spp., plant rubbers and covered with the detached bark or plant Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes foliage again. spp., TarSonemus spp., Bryobia praetiosa, Panonychus Application of the Shaped articles using one of the com spp. and Tetranychus spp. mercially available nailing or tacking apparatuses, for The phytoparasitic nematodes include Pratylenchus spp., 50 example based on compressed air, may be mentioned in Radopholus Similis, Dity lenchus dipsaci, Tylenchulus particular. Semipenetrans, Heterodera spp., Meloidogyne spp., Aph The active compounds include, in particular, insecticides elenchoides spp., Longidorus spp., Xiphinema spp. and and fungicides. Trichodorus spp. Insecticides which may be mentioned as preferred are The agents causing fungal and bacterial diseases include: 55 organic phosphorus compounds, Such as phosphoric acid Xanthomonas Species, Such as, for example, Xanthomonas esters, carbamates, pyrethroids, urea derivatives, Such as campestris pv. Oryzae, be n Zoylu reas, tria Zine S, nitro methylene S and Pseudomonas Species, Such as, for example, Pseudomonas nitroguanidines. Juvenile hormones and juvenoid Synthetic Syringae pv. lachrymans, compounds, Such as, for example, pyriproxyfen, methoprene Erwinia Species, Such as, for example, Erwinia amylovOra, 60 and hydroprene, may also be mentioned. Pythium species, Such as, for example, Pythium ultimum, The pyrethoids include: Phytophthora Species, Such as, for example, Phytophthora Alethrin=2-methyl-4-oxo-3-(2-propenyl)-2-cyclopenten-1- infeStans, yl 2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropane Pseudoperonospora Species, Such as, for example, Pseudop carboxylate. eronospora humuli or PseudoperOnospora cubense, 65 Barthrin=(6-chloro-1,3-benzodioxol-5-yl)-methyl 2,2- Plasmopara Species, Such as, for example, Plasmopara dimethyl-3-(2-methyl-1-prope nyl)-cyclopropane viticola, carboxylate.

6,063,393 9 10 Omethoate=O,O-dimethyl S-2-(methylamino)-2-oxo Vamid oth ion = O, O-dimethyl S-2-(1- ethyl phosphorothioate. methylcarbamoylethyleneethyl phosphorothioate. Oxydemeton-methyl=S-2-(ethylsulphinyl)ethyl O,O- dimethyl phosphorothioate. The benzoylureas include compounds of the formula: Oxydisulphoton=O,O-diethyl S-2-(ethyl-Sulphinyl)-ethyl phosphorodithioate. R1 Parathion=O,O-diethyl O-4-nitrophenyl phosphorothioate. Parathion-methyl=O,O-dimethyl O-4-nitrophenyl phospho CO-NH-CONH / y R' rothioate. S R4 Phenkap to n = O,O - diethyl S-(2,5-dichloro 1O phenylthiomethyl) phosphorodithioate. R2 Phenthoate=ethyl C.-(dimethoxyphosphinothioyl)thio benzene-acetate. Phorate=O,O-diethyl S-ethylthiomethyl phosphorodithioate. Phosalone=S-(6-chloro-2-oxo(2H)-benzoxazolyl)methyl 15 O-diethyl phosphorodithioate. wherein Phospholan=diethyl 1,3-dithiolan-2-ylidene phosphorami date. R" represents halogen, Phosmet=S-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)- methyl O,O-dimethyl phosphorodithioate. R represents hydrogen or halogen, PhoSnichlor=O,O-dimethyl O-4-chloro-3-nitrophenyl phos R represents hydrogen, halogen or C-alkyl and phorothioate. Phosphamidon=2-chloro-3-(diethylamino)-1-methyl-3-oxo R represents halogen, 1-5-halogen-C-alkyl, C 1-propenyl dimethyl phosphate. alkoxy, 1-5-halogeno-C-alkoxy, C-alkylthio, 1-5- Phoxim=C.-diethoxyphosphinothioyl)oxy)imino)- 25 halogeno-C-alkylthio phenoxy or pyridyloxy which benzeneacetonitrile. can optionally be Substituted by halogen, C-alkyl, Pirimiphos-ethyl=O-2-(diethylamino)-6-methyl-4- 1-5-halogeno-C-alkyl, C-alkoxy, 1-5-halogeno pyrimidinyl O,O-diethyl phosphorothioate. C-alkoxy, C-alkylthio, 1-5-halogeno-C-C- Pirimiphos-methyl=O-2-(diethylamino)-6-methyl-4- alkylthio. pyrimidinyl O,O-dimethyl phosphorothioate. Benzoylureas which may be mentioned in particular are Profenofos=O-(4-bromo-2-chlorophenyl) O-ethyl S-propyl those of the formula: phosphorothioate. Propetamphos=(E)-1-methylethyl 3-(ethylamino)- methoxyphosphinothioyloxy-2-butenoate. Prothidathion=O,O-diethyl S-(2,3-dihydro-5-isopropyl-2- 35 R1 OXO-1,3,4-thiadiazol-3-yl-methyl) phosphorodithioate. Prothoate=O,O-diethyl S-2-(1-methylethyl)amino-2-oxo ethyl phosphorodithioate. Quinallphos=O,O-diethyl O-2-quinoxalinyl phosphorothio CONHCO -(-)- ate. 40 Quinothion=O,O-diethyl 2-methylcquinolin-4-yl phospho R2 rothioate. Quintiofos=O-ethyl O-8-quinolinoyl phenylphosphonothio R R2 R4 ate. H C CF, Sophamide =O,O-dimethyl S-(N-methoxy-methyl)- 45 Cl C CF, F F CF, carbamoylmethyl phosphorodithioate. H F CF, Sulfotepp=tetraethyl thiodiphosphate. H C SCF, Sulprofos=O-ethyl O-(4-methylthiophenyl) S-propyl phos F F SCF, phorodithioate. H F SCF, H C OCF, Temephos=O,O'-(thiodi-4, 1-phenylene) O, O,O", O'- 50 tetramethyl di(phosphorodithioate). F F OCF, Tepp=tetraethyl diphosphate. H F OCF, Terbufos=S-(1,1-dimethylethyl)thiomethyl O,O-diethyl F F phosphorodithioate. Tetrachlorvinphos=dimethyl trans-2-chloro-1-(2,4,5- 55 trichlorophenyl) vinyl phosphate. O,O,O',O'-tetrapropyl dithiopyrophosphate=tetrapropyl F F thiodiphosphate. Thiometon=O,O-dimethyl S-2-(ethylthio)ethyl phospho rodithioate. 60 O -( )- CF Thionazin=O,O-diethyl O-pyrazinyl phosphorothioate. Triazophos=O,O-diethyl O-(phenyl-1H-1,2,4-triazol-3-yl) F F phosphorothioate. Trichloronat=O-ethyl O-2,4,5-trichlorophenyl eth O -( )- CF ylphosphonothioate. 65 Trichlorphon=dimethyl 1-hydroxy-2,2,2-trichloroethyl phosphonate. 6,063,393 11 12 The triazines include compounds of the formula (I) 1.NH-R R-NC-(z)(A)

in which wherein R represents hydrogen or optionally Substituted acyl, R represents cyclopropyl or isopropyl; alkyl, aryl, aralkyl, heteroaryl or heteroarylalkyl radi R. denotes hydrogen, halogen, C-C2-alkylcarbonyl, cals, cyclopropylcarbonyl, C-C2-alkylcarbamoyl, A represents a monofunctional group from the Series C - C - alkylthio carbamoyl or C-C- comprising hydrogen, acyl, alkyl and aryl, or represents alkenylcarbamoyl; and 15 a bifunctional group, which is linked to the radical Z, R represents hydrogen, C-C2-alkyl, cyclopropyl, E represents an electron-withdrawing group, Such as, for C - C - alkenyl, C - C - alkyl carbonyl, example, NO or CN; cyclopropylcarbonyl, C-C2-alkylcarbamoyl, X represents the radicals -CH= or=N-, wherein the C - C - alkylthiocarbamoyl or C - Co radical -CH= can be linked to the radical Z instead alkenylcarbamoyl, and acid addition Salts thereof of an H atom; and which are non-toxic to warm-blooded animals. Z represents a monofunctional group from the Series Compounds which may be mentioned in particular are: comprising alkyl, -O-R, -S-R or

25 R R R Cyclopropy H H Cyclopropy H CH Cyclopropy H CHs Cyclopropy H CH-n or represents a bifunctional group, which is linked to Cyclopropy H CH-n the radical A or the radical X. Cyclopropy H C5H1-n Cyclopropy H CH-n Particularly preferred compounds of the formula are those Cyclopropy H C7Hs-n in which the radicals having the following meaning: Cyclopropy H CH17-n R represents hydrogen, or represents optionally Substi Cyclopropy H C12H2s-n Cyclopropy H CH-CH-t 35 tuted radicals from the Series comprising acyl, alkyl, Cyclopropy H CHCH(CH)C.Hs aryl, aralkyl, heteroaryl and heteroarylalkyl. Cyclopropy H CH-CH=CH, Acyl radicals which may be mentioned are formyl, Cyclopropy C CHs alkylcarbonyl, arylcarbonyl, alkylsulphonyl, arylsul Cyclopropy C CH-n Cyclopropy C CH17-n phonyl and (alkyl)- or (aryl)-phosphoryl, which can in Cyclopropy C C12Hs-n 40 turn be substituted. Cyclopropy H Cyclopropyl Alkyl which may be mentioned is Co-alkyl, in particu Cyclopropy H COCH, Cyclopropy H COCHHCI lar C-alkyl, specifically methyl, ethyl, i-propyl or Cyclopropy H COCHs HCl Sec- or t-butyl, which can in turn be Substituted. Cyclopropy H COCHs Aryl which may be mentioned is phenyl or naphthyl, in Cyclopropy H COCH-n 45 Cyclopropy H COCH-i particular phenyl. Cyclopropy H COCH-t HCl Aralkyl which may be mentioned is phenylmethyl or Cyclopropy H COCH-n phenethyl. Cyclopropy H COCH-n Cyclopropy H COC-H2-n Heteroaryl which may be mentioned is heteroaryl having Cyclopropy COCH, COCHs 50 up to 10 ring atoms and N, O or S, in particular N, as Cyclopropy COCH-n COCH-n hetero atoms. Radicals which may be mentioned spe Cyclopropy COCH, COCH-n cifically are thiophenyl, furyl, thiazolyl, imidazolyl, Cyclopropy COCHs COCH-n Cyclopropy H COCyclopropyl pyridyl and benzothiazolyl. Cyclopropy COCy: cyclopropyl COCyclopropyl Hetero arylalkyl which may be mentioned is Cyclopropy COCH, COCH, heteroarylmethyl, or heteroarylethyl having up to 6 ring Isopropyl H H 55 Isopropyl H COCH, atoms and N, O and S, in particular N, as hetero atoms. Isopropyl H COCH-n Substituents which may be mentioned as examples and as Cyclopropy H CONHCH, preferred are: Cyclopropy H CONHCH-i Cyclopropy CONHCH, CONHCH, alkyl having preferably 1 to 4, in particular 1 or 2, carbon Cyclopropy H CSNHCH, 60 atoms, Such as methyl, ethyl, n- and i-propyl and n-, i Cyclopropy H CONHCH-CH=CH, and t-butyl, alkoxy having preferably 1 to 4, in par Cyclopropy CONHCH-CH=CH, CONHCH-CH=CH, ticular 1 or 2, carbon atoms, Such as methoxy, ethoxy, Cyclopropy CSNHCH, CSNHCH, n- and i-propyloxy and n-, i- and t-butyloxy; alkylthio having preferably 1 to 4, in particular 1 or 2, carbon The nitromethylenes and nitroguanidines and cyanimides 65 atoms, Such as methylthio, ethylthio, n- and include compounds which can preferably be Summarised i-propylthio and n-, i- and t-butylthio; halogenoalkyl under the general formula I having preferably 1 to 4, in particular 1 or 2, carbon 6,063,393 13 14 atoms and preferably 1 to 5, in particular 1 to 3, halogen he Xy methylene imine, morpholine and atoms, the halogen atoms being identical or different N-methylpiperazine. and preferred halogen atoms being fluorine, chlorine or Compounds which may be mentioned as compounds bromine, in particular fluorine, Such as trifluoromethyl, which can especially preferably be used according to the hydroxyl; halogen, preferably fluorine, chlorine, bro 5 mine and iodine, in particular fluorine, chlorine and invention are those of the general formulae II and III: bromine; cyano, nitro, amino; monoalkyl- and dialky lamino having preferably 1 to 4, in particular 1 or 2, (II) carbon atoms per alkyl group, Such as methylamino, Substing CH 1 Z. methylethyl-amino, n- and i-propylamino and methyl n-butylamino; carboxyl, carbalkoxy having preferably QN (CH) N-12 2 to 4, in particular 2 or 3, carbon atoms, Such as carbomethoxy and carboethoxy; sulpho(-SOH); X-E alkylsulphonyl having preferably 1 to 4, in particular 1 or 2, carbon atoms, Such as methylsulphonyl and eth 15 ylsulphonyl; arylsulphonyl having preferably 6 or 10 in which aryl carbon atoms, Such as phenylsulphonyl; and het eroarylamino and heteroarylalkylamino, Such as chlo in represents 1 or 2, ropyridylamino and chloropyridylmethylamino. SubSt. represents one of the abovementioned Substituents, A represents hydrogen or optionally Substituted radicals in particular halogen, especially chlorine, and from the Series comprising acyl, alkyl and aryl, which preferably have the abovementioned meanings. A fur A, Z, X and E have the abovementioned meanings, thermore represents a bifunctional group. Optionally Substituted alkylene having 1 to 4, in particular 1-2, C (III) atoms, Substituents which may be mentioned being the 25 Subst. Nt Substituents listed above, may be mentioned. (A) A and Z, together with the atoms to which they are S (CH) NC-(Z) bonded, can form a Saturated or unsaturated heterocy | clic ring. The heterocyclic ring can contain a further 1 X-E or 2 identical or different hetero atoms and/or hetero groupS. Preferred hetero atoms are oxygen, Sulphur or nitrogen, and hetero groups are N-alkyl, the alkyl of the N-alkyl group preferably containing 1 to 4, in particular in which 1 or 2, carbon atoms. Methyl, ethyl, n- and i-propyl and n-, i- and t-butyl may be mentioned as alkyl. The 35 the radicals have the abovementioned meaning. heterocyclic ring contains 5 to 7, preferably 5 or 6, ring The following compounds may be mentioned specifically: members. Examples of the heterocyclic ring which may be men tioned are imidazolidine, tetrahydropyrimidine, thiazolidine, 2H-thiazine, hexahydro-1,3,5-triazine, 40 - Y - i. pyrrollidine, pipe ridine, piper a Zine, -(-)- r he Xy methylene imine, morpholine and N-methylpiperazine. represents an electron-withdrawing radical, No CN, halogenoalkylcarbonyl, Such as 1-5-halogeno-Ca 45 carbonyl, especially COCF, being mentioned in par ticular. p1 X represents -CH= or -N=. N Z represents optionally substituted alkyl, -OR, -SR or 2 -NRR radicals, wherein R and the substituents pref 50 erably have the abovementioned meaning. Z, together with the atom to which it is bonded and the radical in the position of X, can form a Saturated or unsaturated heterocyclic ring. The heterocyclic ring can contain a further 1 or 2 identical or different hetero 55 atoms and/or hetero groups. Preferred hetero atoms are oxygen, Sulphur or nitrogen, - Y - and hetero groups are N-alkyl, the alkyl of the N-alkyl group preferably containing 1 to 4, in particular 1 or 2, -(-)- carbon atoms. Methyl, ethyl, n- and i-propyl and n-, i 60 and t-butyl may be mentioned as alkyl. The heterocy clic ring contains 5 to 7, preferably 5 or 6, ring members. Examples of the heterocyclic ring which may be men tioned are imidazolidine, tetrahydropyrimidine, 65 thiazolidine, 2H-thiazine, hexahydro-1,3,5-triazine, pyrrollidine, pipe ridine, piper a Zine, 6,063,393 15 16 -continued German Offenlegungsschriften No. 3 639877 and 3712 307; Japanese Published Specifications No. 03 220 176, 02207 c-( )—cil- NH 083, 63.307 857, 63.287 764,03246 283,049371, 03 r 279 359 and 03 255 072; CH U.S. Pat. Nos. 5,034,524, 4,948,798, 4,918,086, 5,039, SNO, 686 and 5,034.404; PCT Applications No. WO 91/17 659 and 91/4965; t French Application No. 2 611 114; and c-()– CH-N N(CH3)2 1O r Brazilian Application No. 88 03 621. N-NO Reference is expressly made here to the generic formulae and definitions described in these publications and to the individual compounds described therein. / \, , , 15 Preferred fungicides which may be mentioned are: NF r Sulfenamides, Such as dichlorfluanid (Euparen), tolylflu CH anid (Methyleuparen), folpet and fluorfolpet; YNO, benzimidazoles, such as carbendazim (MBC), benomyl, fuberidazole, thiabendazole or salts thereof; fl. thiocyanates, Such as thiocyanatomethylthiobe n c-( )—cil- N(CH3)2 Zothiazole (TCMTB) and methylene bisthiocyanate r (MBT); N quaternary ammonium compounds, Such as benzyldim YoN ethyltetradecylammonium chloride, benzyl-dimethyl 25 dodecyl-ammonium chloride and dodecyl-dimethyl t ammonium chloride; morpholine derivatives, Such as C-C-4-alkyl-2,6-dimethyl-morpholine homo c-( =/)—cil----, logues (tridemorph), (-)-cis-4-(3-tert.-butylphenyl)-2- YoN methylpropyl)-2, 6 - dimethyl morpholine (fempropimorph) and fallimorph; th phenols, Such as o-phenylphenol, tribromophenol, tetrachlorophenol, pentachlorophenol, 3-methyl-4- rs chlorophenol, di-chlorophen, chlorophen or salts thereof; c-( )—cil- N-CH 35 r aZoles, Such a triadimefon, triadimenol, bitertanol, N-NO. te buconazole, prop iconazole, a Zacona Zole, hexaconazole, prochloraz, cyproconazole, 1-(2- ill chlorophenyl)-2-(1-chlorocyclopropyl)-3-(1,2,4- 40 triazol-1-yl)-propan-2-ol and 1-(2-chlorophenyl)-2-(1, c-(N )—cil---such,CH 2,4-triazol-1-yl-methyl)-3,3-dimethyl-butan-2-ol. SNO, Iodopropargyl derivatives, Such as iodopropargylbutyl carb amate (IPBC), chlorophenylformal, N fl. phenylcarbamate, hexylcarbamate and cyclohexylcar N 45 bamate and iodopropargyloxyethyl phenylcarbamate; iodine derivatives, Such as diiodomethyl-p-aryl c-( | r ) Sulphones, for example diiodomethyl-p-tolyl-Sulphone; S or bromine derivatives, Such as bromopol, N-NO isothiazolines, Such as N-methylisothiazolin-3-one, 50 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N- octyl-isothiazolin-3-one, N-octylisothiazolin-3-one Sr -( HCin 1\- N r NH (octilinone); H benzisothiazolinones and cyclopentene-isothiazolines, CH pyridines, Such as 1-hydroxy-2-pyridinethione and CH 55 tetrachloro-4-methylsulphonylpyridine, NO NO nitrites, Such as 2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil) and the like, and microbicides having an activated halogen group, Such as Cl-Ac, MCA, These compounds are agonists or antagonists of the 60 tectamer, bromopol and bromidox; nicotinergic acetylcholine receptors of insects, and are benzothiazoles, Such as 2-mercaptobenzothiazoles; . . . known as Such from the following publications: dazomet, and European Published Specifications No. 464 830, 428 941, quinolines, Such as 8-hydroxyquinoline. 425978,386,565,383 091,375 907,364,844, 315826, Insecticides which may be mentioned as particularly 259 738,254.859, 235 725, 212 600, 192060, 163855, 65 preferred are: 154178,136 636,303 570, 302833,306 696, 189972, phosphoric acid esters, Such as azinphoS-ethyl, azinphos 455 000, 135956, 471 372 and 302389; methyl, 1-(4-chlorophenyl)-4-(O-ethyl-S-propyl) 6,063,393 17 18 phosphoryloxypyrazole (TIA-230), chlorpyrifos, Polymeric carrier materials which may furthermore be coumaphos, demeton, demeton-S-methyl, diazinon, mentioned are thermoplastic elastomers. These are materials dichlorvos, dimethoate, ethoprophos, etrimfos, which contain elastomeric phases either physically mixed fe nitrothion, fention, heptenophos, parathion, into or chemically bonded in polymers which can be pro parathion-methyl, phosalone, phoXion, pirimiphos cessed as thermoplastics. A distinction is made between ethyl, pirimiphos-methyl, profenofoS, prothiofoS, polyblends, in which the elastomeric phases are present in SulprofoS, triaZophoS and trichlorphon. physically mixed-in form, and block copolymers, in which Carbamates, such as aldicarb, bendiocarb, BPMC (2-(1- the elastomeric phases are a constituent of the polymeric methylpropyl)phenyl methyl carb amate), matrix. As a result of the build-up of the thermoplastic butocarbo Xime, butoxycarboxime, carbary 1, elastomers, hard and Soft regions are present Side by Side. carbofuran, carboSulphan, cloethocarb, isoprocarb, The hard regions here form a crystalline network Structure or methomyl, oxamyl, pirimicarb, promecarb, propoXur a continuous phase, the intermediate Spaces of which are and thiodicarb. filled by elastomeric Segments. Because of this build-up, Pyrethroids, Such as alle thrin, alphame thrin, these materials have rubber-like properties. biores methrin, by fenthrin, (FMC 54 800), 15 A distinction is made between 5 main groups of the cycloprothrin, cyfluthrin, decamethrion, cyhalothrin, thermoplastic elastomers which may be mentioned as pre cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2- ferred at this point: methylbenzyl 2,2-dimethyl-3-(2-chloro-2- 1. Copolyesters trifluoromethylvinyl)cyclopropane carboxylate, 2. Polyether block amides (PEBA) fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, 3. Thermoplastic polyurethanes (TPU) flumethrin, fluvalinate, permethrin and reSmethrin; and nitroimino and nitroimides, Such as 1-(6-chloro-3- 4. Thermoplastic polyolefins (TPO) pyridinyl)-methyl-4,5-dihydro-N-nitro-1H-imidazol 5. Styrene block copolymers. 2-amine (imidacloprid). Mixtures of the polymerS mentioned can of course also be 25 used as the polymeric carrier materials. Substances forming the matrix of a Solid carrier are Solid Preferred polymeric carrier materials are polymers which degradable organic Substances Such as Solid fatty acids can be processed as thermoplastics and have processing and their Salts, Solid fats, waxes, Solid paraffins, Solid temperatures of 50-260 C., particularly preferably 50-200 Surface active agents and bentonite and furthermore C. polymeric carrier materials. Preferred are polymeric Polymers which can be degraded via photochemical carrier materials. processes, Such as ethylene/CO copolymers, Vinyl ketone Polymeric carrier materials which may be mentioned are: copolymers and polymers containing additives which ini all the polymers which can be used for the preparation of plastics moulding compositions, Such as, for example, tiate photodegradation, are furthermore preferred. polyolefins, Such as polyethylene, polyisobutylene and Particularly preferred polymers are those from the group polypropylene, Vinyl polymers, Such as polyvinyl chlo 35 of biodegradable polymers, Such as Starch polymers and ride (PVC), polyvinyl acetate, polyvinyl alcohol, poly Starch polymer/thermoplastic mixtures, Sugar polymers, cel Styrene and polyacrylonitrile, polyacrylates and poly luloses and cellulose derivatives, polyoxyalkylated cellulo methacrylates, polyacetals, polycondensates and SeS and Starches, hydrogels, Such as alginates, naturally polyadducts, Such as polyamides, polyesters, occurring resins, Such as colophony, gum Arabic and agar 40 agar, homo- and copolymers of lactic acid, Such as poly polyurethanes, polycarbonates and polyalkylene lactides and polylactide glycolides, as well as polygly terephthalates, polyaryl ethers and polyimides, as well collides. Poly-e-caprolactone and polymers from the group as high molecular weight polyalkylene oxides, Such as comprising polyhydroxyalkanoates, Such as poly-3- homo- and copolymers of ethylene oxide and propylene oxide, polyalkylenoxidalkylethers or polyalkylenox hydroxybutyric acid (PHB) and copolymers of 45 3-hydroxybutyric with 3-hydroxyvaleric acid (PHBV), are idealkylarylethers. especially preferred. Polymers which may furthermore be mentioned are Polymers from the group of polycondensates which are copolymers of olefin/vinyl esters, Such as ethylene/ particularly Suitable are polyamides and/or polyesters hav Vinyl acetate copolymers, ethylene/vinyl alcohol ing a melting or softening point of 50–160° C. From the copolymers, olefin/acrylate and methacrylate 50 Substance class of polyamides, those which are preferred are copolymers, Such as ethylene/acrylic acid copolymers, homopolyamides and/or copolyamides of (D-aminocaproic ethylene/ethyl acrylate copolymers and ethylene/ acid, ()-aminooenanthic acid, (D-aminocaprylic acid, methyl acrylate copolymers, and ABS copolymers, () -aminope largo nic acid, () -amino capric acid, Styrene/acrylonitrile copolymers, Styrene/butadiene ()-aminoundecylic acid, (D-aminolauric acid and/or copolymers and olefin/maleic anhydride copolymers, 55 caprolactam, lactam-7, lactam-8, lactam-9, lactam-10, Such as ethylene/maleic anhydride copolymers. lactam-11 or lauryllactam, and/or of dimethylenediamine, Polymeric carrier materials which can furthermore be trimethylene diamine, tetramethylene diamine, used are: pentamethylenediamine, hexamethylenediamine, polyether Starch polymers, Such as natural Starch, amylose and diamine and Oxalic acid, malonic acid, Succinic acid, glu Starch polymer/thermoplastic mixtures, Sugar 60 taric acid, adipic acid, pimelic acid, Suberic acid, azelaic polymers, Such as polymaltoses, and celluloses and acid, Sebacic acid, nonanedicarboxylic acid, decanedicar cellulose derivatives, Such as cellulose esters, cellulose boxylic acid, undecanedicarboxylic acid, dodecanedicar ethers and cellulose nitrate. boxylic acid and dimerised fatty acid. Polyoxyalkylated celluloses, Starches and lignin Sul Those of caprolactam, lauryllactam, ()-aminolauric acid, fonates. Hydrogels, Such as alginates. 65 ()-aminocaproic acid, hexamethylenediamine, polyether-di Naturally occurring resins, Such as colophony, gum Ara amine, adipic acid, dimerised fatty acid or mixtures thereof bic and agar-agar. are particularly preferred. 6,063,393 19 20 From the Substance class of polyesters, homopolyesters Such as polyethylene, polybut-1-ene and Vinyl resins, Such and/or copolyesters of () -hydroxyacetic acid, as polystyrene and PVC. Photoreactive additives are pref ()-hydroxypropionic acid, ()-hydroxybutyric acid, erably organic carbonyl compounds, Such as, for example, ()-hydroxy Valeric acid, () -hydroxy caproic acid, aromatic aldehydes, ketones, diketones and quinones. Ben ()-hydroxy oenanthic acid, ()-hydroxy caprylic acid, Zophenone and derivatives thereof are particularly preferred. ()-hydroxype largonic acid, ()-hydroxy capric acid, Another group of preferred photoreactive additives are inor ()-hydroxyundecylic acid, co-hydroxylauric acid and/or ganic and organic Salts, Such as, for example, chlorides, caprolactone, lactone-7, lactone-8, lactone-9, lactone-10, Stearates and Octoates, of transition metals, Such as, for lactone-11, lauryllactone and/or ethylene glycol, example, iron, nickel, cobalt, copper and manganese. propanediol, butanediol, pentanediol, hexanediol, an ali Organic complexes of transition metals, Such as, for phatic diol mixture having 2 to 18 C atoms and Oxalic acid, example, ferrocenes and, preferably, dithiocarbamates of malonic acid, Succinic acid, glutaric acid, adipic acid, iron and magnesium are likewise employed. pimelic acid, Suberic acid, azelaic acid, Sebacic acid, Of the Starch polymers, the Starches which can be pro nonanedicarboxylic acid, decanedicarboxylic acid, unde cessed as thermoplastics and the Starch polymer/ canedicarboxylic acid, dodecanedicarboxylic acid, tereph thermoplastic mixtures are preferably Suitable as the poly thalic acid, isophthalic acid and/or anhydrides thereof and/or 15 meric carrier materials. They can be employed by chlorides thereof and/or esters thereof are preferred. themselves and/or as a masterbatch, mixed with the ther Preferred polymeric carrier materials are formed from moplastics. The thermoplastics preferably comprise polyurethanes. Polyurethanes are prepared in a manner amounts of photodegradable polymers. which is known per se by reaction of polyisocyanates with Starch which can be processed as a thermoplastic is, for higher molecular weight compounds which contain at least example, natural Starch containing water as a Softener, as two groups which are reactive towards isocyanates, and if described, for example, in EPO 118 240; destructured starch, appropriate low molecular weight chain-lengthening agents as described, for example, in EP 0304 401 and 0.391853, and/or monofunctional chain stoppers (see, for example, S. and hydroxyalkoxylated Starch, Such as, for example, H. Saunders, K. C. Frisch; Polyurethanes, Part I, High hydroxyethyl- and hydroxypropyl-Substituted Starch. Polymer Science XVI, Interscience Publishers, New York 25 Softener-containing Starches having a high amylose content 1962). furthermore can be processed as thermoplastics, as Preferred polyisocyanates are in general the toluylene mentioned, for example, in DE 4013 344. Softeners which diisocyanates and the diphenylmethane diisocyanates. are preferably employed are polyhydric alcohols, Such as, It is of course possible to use mixtures of the above for example, glycerol, diethylene glycol, triethylene glycol, mentioned compounds having at least two hydrogen atoms Sorbitol, polyvinyl alcohol and citric acid oxide adduct. which are reactive towards isocyanates and a molecular The Starch polymer/thermoplastic mixtures include the weight of 400 to 10 000, for example mixtures of polyethers mixtures, comprising 6-15 parts by weight of Starch, with, and polyesters. for example, PVC, ethylene/vinyl acetate copolymers, poly PoSSible starting components for polyurethane polymeri urethane S and, preferably, polyolefins, Such as sation which are optionally to be enjoyed are also com 35 polypropylene, and particularly preferably polyethylene, pounds having at least two hydrogen atoms which are Such as are obtainable, for example, by the names EcoStar, reactive towards isocyanates and a molecular weight of 32 Polyclean, Amy plast and Poly-Grade. The starch used for to 400. In this case also, this is understood as meaning Such mixtures with thermoplastics can be Surface-modified, compounds containing hydroxyl groups and/or amino for example with Silanes, or can be employed as non groupS and/or thiol groups and/or carboxyl groups, prefer 40 modified starch in the dried State. The mixtures can addi ably compounds containing hydroxyl groups and/or amino tionally comprise additives. These are, for example, unsat groups, which Serve as chain-lengthening agents or urated compounds, Such as unsaturated fatty acid esters, for crosslinking agents. These compounds as a rule have 2 to 8 example Soya oil; Styrene/butadiene block copolymers, hydrogen atoms which are reactive towards isocyanates, naturally occurring rubber, and organic Salts of transition preferably 2 or 3 reactive hydrogen atoms. 45 metals, Such as, for example, cobalt naphthenate and anti Photodegradable polymers are polymers which contain oxidants of the known type. groups which are Sensitive to UV light and/or additives Starch polymer/thermoplastic mixtures having a Starch which initiate photochemical reactions. content of up to 95 parts by weight, Such as are obtained, for Polymers containing groups which are Sensitive to UV example, by mixing Starch with polymers containing car light which may be mentioned are the copolymers of eth 50 boxyl groups, Such as, for example, ethylene/acrylic acid ylene and carbon monoxide prepared by free radical copolymers, furthermore can be used according to the inven polymerisation, Such as are described, for example, in U.S. tion. Pat. No. 2,495,286 and DE 2,316,697 and U.S. Pat. No. The preparation of Such mixtures from the destructured 3,921,144. The copolymers, described, for example, in U.S. starch is described, for example, in EP 0404727. EP 0519 Pat. Nos. 3,759,952, 3,811,931, 385,814, 3,860,538 and 55 367 uses a starch which has been modified chemically by 3,878,169, of vinyl monomers containing keto groups, Such reaction of the OH groups with alkylene oxides and other as methyl Vinylketone, methyl isopropenylketone and ethyl Substances which form ethers, esters, urethanes, carbamates Vinyl ketone, with, for example, polyolefins, Such as and/or isocyanates for mixing with thermoplastics. ethylene, propylene and Vinyl compounds, Such as Styrene Copolyamides, copolyesters and/or polyolefins are pre and methyl methacrylate, may furthermore be mentioned. 60 ferred. Polyols, Such as, for example, glycerol, Sorbitol and Such products are obtainable, for example, under the name polyethylene glycol, as Softeners, urea and/or urea deriva “Ecolyte, and can be employed as the polymeric carrier tives and emulsifiers, Such as metal Stearates, glycerol materials either by themselves or, preferably, as a mixture monoStearates and polyoxyethylene fatty acid esters, Such with the corresponding base polymers in amounts of 5-10 as, for example, polyoxyethylene-20 Sorbitan monolaurate, parts by weight. 65 can additionally be added to these mixtures. Polymers containing additives as initiators for photodeg Starch polymer/thermoplastic mixtures which can be radation are preferably prepared on the basis of polyolefins, employed according to the invention can also comprise graft 6,063,393 21 22 copolymers of Starch with, for example, maleic anhydride esters, polyalkylene oxide alkyl esters, polyalkylene oxide and vinyl monomers, Such as, for example, Styrene, acry alkyl amines, poly fatty acid esters, polyalkylene oxide lonitrile and acrylic and methacrylic monomers, for example polyol ester ethers, alkylsulfonates, alkyl arylsulfonates, butyl and methyl methacrylate, as compatibilising agents. alkyl naphthalene Sulfonates, dialkyl SulfoSuccinates, poly CopolymerS Such as are obtained in accordance with DE 5 alkylene alkyl ether Sulfates, polyalkylene alkylaryl ether 3,007,433 by polymerisation of ethylene in the presence of Sulfates, poly Sulfates, polyalkylene oxide alkyl ether starch modified by Ziegler-Natta catalysts furthermore are phosphates, polyalkylene oxide alkyl aryl ether phosphates and polyol phosphates. The polymeric material can contain Suitable. appropriate additives Such as plasticizers. Celluloses and cellulose derivatives, Such as, for example, The plasticisers which are usually used for plasticising cellulose esters, for example cellulose acetate, cellulose Solid Vinyl resins are Suitable for production of the shaped propionate, cellulose butyrate and mixed esters, Such as, for articles based on polymers which can be processed as example, cellulose acetobutyrate; cellulose ethers, for thermoplastics, Such as, for example, polyvinyl resins. The example methyl-, ethyl- and hydroxyethylcellulose and plasticiser used depends on the resin and its compatibility Sodium carboxymethylcellulose, and cellulose nitrate are with the plasticiser. Examples of Suitable plasticiser are known and are Suitable as polymeric carrier materials. 15 esters of phosphoric acid, Such as tricresyl phosphate, esters Preferred substances are derivatives which can be pro of phthalic acid, Such as dimethyl phthalate and dioctyl cessed as thermoplastics and/or are degradable, Such as, for phthalate, and esters of adipic acid, Such as diisobutyl example, the mixtures, described in EP O 394 803, of adipate. It is also possible to use other esters, Such as the cellulose esters, Such as cellulose acetate and/or cellulose esters of azelaic acid, maleic acid, ricinoleic acid, myristic acetobutyrate, with biodegradable additives, Such as car acid, palmitic acid, oleic acid, Sebacic acid, Stearic acid and boxylic acid esters having Several ester and/or hydroxyl trimelitic acid, as well as complex linear polyesters, poly groups, for example esters of citric acid, tartaric acid or meric plasticisers and epoxidised Soya bean oils. The Succinic acid, as Softeners, linear polyesters and, if amount of plasticiser is about 10 to 50% by weight, pref appropriate, organic acids and/or acid esters which differ erably about 20 to 45% by weight of the total composition. from the Softener. Organic metal compounds, Such as, for 25 The Shaped articles can also comprise further example, iron(II) acetylacetonate or bis(cyclopentadienyl)- constituents, Such as Stabilising agents, lubricants, fillers, iron or derivatives thereof, can additionally be contained in Surface active agents and colouring agents, without the the mixture to increase the degradability. fundamental properties of the composition thereby being Particularly preferred polymeric carrier materials are changed. Suitable Stabilising agents are antioxidants and cellulose/lactone graft copolymers, Such as, for example, agents which protect the shaped article from ultraViolet cellulose polyhydroxyhexanoate. radiation and undesirable degradation during working, Such Polyhydroxyalkanoates are polymers of aliphatic and as extrusion. Some Stabilising agents, Such as epoxidised aromatic hydroxycarboxylic acids which are formed by Soya bean oils, also act as Secondary plasticisers. Lubricants prokaryotic microorganisms and can be prepared by means which can be used are, for example, Stearates, Stearic acid of fermentative processes, Such as are described, for 35 and polyethylene of low molecular weight. These constitu example, in EP 0015669, 0046 344 and 0 052 459. ents can be used in a concentration of up to 20% by weight Suitable polyhydroxyalkanoates are, for example, poly of the total composition. mers of 4-hydroxybutyric acid, 4-hydroxyvaleric acid and Fillers and additives which the polymeric carrier materials 5-hydroxyvaleric acid; of the 3-hydroxy derivatives of Satu contain, if appropriate, are to be understood as meaning rated carboxylic acids, Such as, for example, propionic acid, 40 Substances which are known per Se, Such as, for example, butyric acid, Valeric acid, hexanoic acid, heptanoic acid, fillers and short fibres on an inorganic or organic basis, octanoic acid, nonanoic acid, decanoic acid, undecanoic colouring agents, Such as dyestuffs and coloured pigments, acid, dodecanoic acid, 4-methylhexanoic acid, water-binding agents, Surface-active Solid Substances or 5-methylhexanoic acid, 5-methyloctanoic acid, pH-stabilising agents. 6-methyloctanoic acid and 7-methyloctanoic acid, of the 45 Examples which may be mentioned of inorganic fillers are 3-hydroxy derivatives of unsaturated carboxylic acids, Such baryte, titanium dioxide, quartz Sand, kaolin, carbon black as, for example, crotonic acid, 4-pentenoic acid, 4-hexenoic and glass microbeads. Of the organic fillers, for example, acid, 5-hexenoic acid, 6-octenoic acid, 7-octenoic acid, powders based on polystyrene or polyvinyl chloride can be 8-nonenoic acid, 9-decenoic acid, 6-dodecenoic acid, employed. 5-tetradecenoic acid and 5,8-tetradecadienoic acid; and of 50 Possible short fibres are, for example, glass fibres of 0.1 the 3-hydroxy derivatives of halogenocarboxylic acids, Such to 1 mm length or fibres of an organic origin, Such as, for as 6-bromohexanoic acid, 6-chlorohexanoic acid, example, polyester fibres or polyamide fibres. In order to 7-fluoroheptanoic acid, 8-bromo octanoic acid, impart the desired coloration to the polymeric carrier 8-chlorooctanoic acid, 9-fluorononanoic acid and materials, the dyestuffs or coloured pigments on an organic 11-bromoundecanoic acid. 55 or inorganic basis which are known per Se for colouring Preferred polymeric carrier materials are homo- and polymers can be used, Such as, for example, iron oxide copolymers of 3-hydroxybutyric acid, and copolymers pigments or chromium oxide pigments orphthalocyanine- or thereof with 3-hydroxyvaleric acid are particularly pre monoaZo-based pigments. The preferred water-binding ferred. Such products are obtainable, for example, under the agents are Zeolites. Solid Surface-active Substances which name “Biopol. 60 may be mentioned are, for example, cellulose powder, active AS a further preferred group of carrier materials may be charcoal, Silicic acid preparations and chrysotile asbestos. mentioned Solid fatty acids Such as capric acid, lauric acid, For production of the shaped articles according to the myristic acid, palmitic acid, Stearic acid; Solid fats, waxes invention, the various constituents can be mixed in the dry Such as Spermacetic and carnauba wax, paraffine waxes. State by known mixing processes, and moulded by known AS a further preferred group of carrier materials may be 65 extrusion or injection moulding processes. mentioned Solid Surface active agents Such as polyalkylene It is furthermore possible to mix the individual compo oxide alkyl or alkyl aryl ether, polyalkylene oxide fatty acid nents by dissolving them in a common Solvent, and then 6,063,393 23 24 precipitating the mixture in a Suitable non-Solvent. In this hydroxyvaleric acid) (Biopol) were extruded at 160° C. and procedure, the Solution is preferably forced through a die injection moulded to shaped articles. into a precipitating bath and the coagulating material formed is drawn off as filaments (wet spinning process). The pre EXAMPLE 5 cipitation is preferably carried out by means of the known dry and wet spinning processes. A mixture of 105 parts by weight of carbofuran, 0.2 part The choice of processing process for production of the by weight of triadimenol and 2 parts by weight of precipi shaped articles according to the invention in principle tated silicic acid were extruded with 150 parts by weight of depends in industry on the Theological properties of the the polymeric carrier material poly(e-caprolactone) at 145 shaped article material and the shape of the desired Structure. C. in the manner described in Example 1. The processing processes can be adjusted according to the The melt strand was drawn off at a rate of 35 m/minute, processing technology or according to the type of Shaping. So that a cable having a diameter of about 1 mm was formed, In the case of processing technology, the processes can be and, after cooling in a water bath, was wound onto a bobbin. classified according to the Theological States passed through Pins 2 cm long were produced by Subsequent cutting of during them. Pouring, pressing, Spraying and Spreading 15 the cable. accordingly are Suitable for Viscous shaped article materials, and injection moulding, extrusion, calendering, milling and EXAMPLE 6 if appropriate kneading are Suitable for elastoViscous poly By the procedure described in Example 5, a mixture of CS. 105 parts by weight of fenamiphos, 2 parts by weight of Classified according to the type of Shaping, the shaped articles according to the invention can be produced by triadimenol and 2 parts by weight of precipitated Silicic acid casting, dipping, compression moulding, injection was processed with 295 parts by weight of poly(e- moulding, extrusion calendering, embossing, bending, deep caprolactone) at 145 C. to give a shaped Strand. drawing, Spinning and the like. EXAMPLE 7 These processing processes are known and do not require 25 more detailed explanation. By the procedure described in Example 5, a mixture of 10.8 parts by weight of mefenacet, 0.2 part by weight of EXAMPLE 1. triadimenol and 2 parts by weight of precipitated Silicic acid To produce shaped articles according to the invention was processed with 87 parts by weight of a polyamide 6, 36 containing active compound, a) a mixture of 30.6 parts by (Priadit 2022) at 155° C. to give a shaped strand. weight of imidacloprid, 0.2 part by weight of triadimenol and 0.2 part by weight of precipitated silicic acid and b) 69 EXAMPLE 8 parts by weight of the polymeric carrier material copoly A mixture of 30 parts by weight of triadimenol and 0.2 (hydroxybutyric acid/hydroxyvaleric acid) (Biopol) were part by weight of precipitated Silicic acid was extruded with metered Separately into a twin Screw extruder Via differential 35 69.8 parts by weight of a thermoplastic polyurethane having balances. a Shore A hardness of 88, prepared from a poly(1,4- The components were homogenised in the extruder at butanediol adipate)-diol of average molecular weight 2250 160 C. in the course of 4 minutes, and the melt was and an OH number of 50, 4,4'-diisocyanatodiphenylmethane extruded into a water bath at a throughput of 1 kg/h. 40 and 1,4-butanediol (Desmopan 385), at 200° C. in the After granulation and drying, the moulding composition manner described in Example 1 and granulated. containing active compound was shaped to rods, pins, Strips The dried granules containing active compound were and Sheets with the aid of an injection moulding machine at melted in an extrusion Spinning apparatus and spun to a 150° C. 5-filament thread, while cooling with water. 45 EXAMPLE 2 Mixture a) from Example 1 was extruded at 190° C., in Spinning conditions: Extruder temperature: 193° C. Die temperature: 192 C. the manner described in that example, with b) 69 parts by Die (hole number/ 5/1.0 mm weight of the polymeric carrier material poly(11 diameter: 50 aminoundecanoic acid), and the mixture was then injection Screen filter: 1OOOO moulded to shaped articles. mesh/cm’ Take-off: 60 m/min EXAMPLE 3 Throughput: 13.8 g/min In the manner described in Example 1, a) a mixture of 20 parts by weight of cyfluthrin, 0.1 part by weight of 55 A multifilament containing active compound and having triadimenol, 80 parts by weight of B-cyclodextrin and 50 an overall titre of 300 dtex (180 um diameter) was obtained. parts by weight of Carbowax 20 M and b) 150 parts by weight of the polymeric carrier material copoly EXAMPLE 9 (hydroxybutyric acid/hydroxyvaleric acid) (Biopol) were 60 A mixture of 20 parts by weight of cyfluthrin, 0.1 part by extruded at 160° C. and injection moulded to shaped articles. weight of triadimenol, 80 parts by weight of B-cyclodextrin and 50 parts by weight of Carbowax 20 M was melted and EXAMPLE 4 mixed in an extruder with 150 parts by weight of a poly In the manner described in Example 1, a) a mixture of 200 (ether-ester) elastomer (Hytrel G-3548) at 185° C. in the parts by weight of triadimenol and 2 parts by weight of 65 manner described in Example 1. precipitated silicic acid and b) 198 parts by weight of the The melt was forced at 190° C. through a 75 mm wide slit polymeric carrier material copoly(hydroxybutyric acid/ die with a gap height of 0.5 mm, cooled by blowing on air 6,063,393 25 26 and taken off at a rate of 5 m/minute by means of a Teflon EXAMPLE 1.5 conveyor belt. Films having a thickness of about 50 um were obtained in this manner. Test on Cotton Aphid (Aphis goSyppi) EXAMPLE 10 29.7 g (49.5 parts by weight) of poly(e-caprolactone) Preparation of the shaped compositions were melted in a kneader of the Haake Rhoemix type at 150 imidacloprid 2.0 parts by weight C. and 50 revolutions per minute, and a mixture of 20 g (33.3 Bentonite 38.0 parts by weight parts by weight) of tolylfluanid, 5 g (8.3 parts by weight) of Clay 60.0 parts by weight tebuconazole, 0.3 g (0.5 part by weight) of precipitated Silicic acid and 5 g (8.3 parts by weight) of dextrin was added. For homogenisation, the mixture was kneaded for a The above-mentioned components are intimately mixed further 5 minutes after the active compound formulation had 15 and then formulated into granulated shaped compositions been added. according to the conventional granulation process. The resulting composition containing active compound Method was shaped in a press under a pressure of 200 bar and at 150 Cucumber plants (cv, Sharp) each grown to a height of C. to give sheets of 100 cm surface area and 2 mm about 180 cm were allowed to naturally inhabit cotton thickness. aphids having resistances to organic phosphorus composi tions and carbamate compositions. EXAMPLE 11 To each of the test plants was embedded a predetermined A mixture of 70 parts by weight of imidacloprid, 29 parts 25 dosage of the shaped composition prepared above under by weight of polyethyleneglycol(MW 7800 to 9000) and 1 Such conditions that the adult insects inhabited the plant at part of hydrophobic synthetic silica(Sipernat D 17 from a rate of 70 pieces a leaf, they were allowed to stand at 28 Degussa) was pulverized. The components were mixed in a C. in a hothouse, and then the number of the living insects blender until they became homogeneous. 1.44 g of the were determined on Seven, fourteen, twenty-one and twenty homogeneous powder was transferred into a cylinder of 6 eight days respectively after the treatment, thus calculating mm in diameter of a tabletting machine and the contents the control effect in % according to the following equation: were compressed with a piston up to 600 kg in total. The The results of the test is shown in Table 1. height of the obtained pellet was 40 mm. 35 EXAMPLE 12 the numberof living insects counted in a test X A mixture of 70 parts by weight of imidacloprid, 27 parts section after treatment by weight of carnauba wax and 3 parts by weight of hydrous Synthetic Silica was treated in the way in Example 11 to have the initial number homogeneous powder. 1.44 g of the homogeneous powder 40 of livinginsects in a untreated section was transferred into a cylinder of 9 mm in diameter of a Control effect (%) = 1 - x 100 tabletting machine and the contents were compressed with a the numberof living piston up to 600 kg in total, The height of the obtained pellet insects counted in the test X section before treatment was 18 mm. 45 the number of livinginsects in EXAMPLE 13 the untreated section when the counting has been carried out A mixture of 25 parts by weight of imidacloprid, 31 parts in the treated test section by weight of ethyleneglycol(MW 3000 to 7000) and 3 parts 50 by weight of hydrous Synthetic Silica was placed in a Stainless Steel container and the contents were melted by heating. The molten mixture was agitated to be homoge TABLE 1. neous. 1.44 g of the homogeneous molten mixture was 55 Concentration transferred into a metal mould of 9 mm in diameter. After of the active cooling, a pellet of 9 mm in diameter and of 18 mm in height component Control Effect (% was obtained. mg/plant body 7 days 14 days 21 days 28 days 3.0 1OO 1OO 1OO 95 EXAMPLE 1.4 60 2.5 1OO 1OO 98 93 2.O 98 1OO 95 90 A mixture of 2 parts by weight of imidacloprid, 38 parts 1.5 93 96 90 85 by weight of bentonite and 60 parts by weight of clay was mixed in a blender to have a homogeneous mixture. The mixture was kneaded by adding 18 parts of water. The 65 The number of living insects per leaf in the non-treated kneaded material was dried with a fluidized bed dryer. The Section counted in correspondence to the above-mentioned length of the dried pellet were cut into 1 mm in length. respective count days in the test Section. 6,063,393 28 The death of the trees was investigated 3 months after infestation.

Before treatment 7 days 14 days 21 days 28 days Number of 65 173 566 845 840 % of the death insects of the trees Test sample plot O Control plot 1OO EXAMPLE 16 1O For the Simultaneous control against aphids, thrips and It will be appreciated that the instant Specification and whiteflies on vegetables. claims are Set forth by way of illustration and not limitation, A cucumber plant being 2 months after transplanting on and that various modifications and changes may be made the ground in the greenhouse was treated on its stem by 15 without departing from the Spirit and Scope of the present insert with a small solid bar (1 mm in diameter, 5 mm in invention. length, 70% of imidacloprid, 30% PEG). 5 plants per plot We claim: were used the test. 1. A proceSS for making rods and pins to be pressed or 7 and 21 days after the treatment, living insects on the knocked into Sap conduction paths of individual plants plants were investigated, and then the mortality was calcu comprising organic insecticides and/or fungicides contained lated comparing with control plots. in a polymeric carrier material as a matrix, wherein Said carrier material is Selected from the group consisting of poly-e-caprolactone and polyhydroxyalkanoates, Said pro Mortality (% 25 ceSS comprising homogenizing 30.6 parts by weight of imidacloprid, 0.2 parts by weight of triadimenol, 0.2 parts by A. B C weight of precipitated Silicic acid and 69 parts by weight of 7 21 7 21 7 21 days copoly(hydroxybutyric acid/hydroxyvaleric acid) at 160 in Test sample plots 1OO 1OO 1OO 1OO 1OO 1OO the course of 4 minutes, extruding the result into a water Control plots O O O O O O bath, and granulating, drying and shaping at 150 C. 2. The agent according to claim 1 wherein Said insecticide A: Cotton aphid (Aphis gossypii) is Selected from the group consisting of carbamates, B: Greenhouse whitefly (Trialeurodes vaporariorum) pyrethroids, benzoylu reas, triazines, nitromethylenes, C: Thrips palmi (Southern yellow thrips) nitroguanidines, cyanamides, juvenile hormones and 35 juvenoid Synthetic compounds. EXAMPLE 1.7 3. The agent according to claim 1 wherein Said fungicides are Selected from the group consisting of Sulfenamides, For the control of Japanese pine Sawyer (Monochamus benzimidazoles, thiocyanates, quaternary ammonium alternatus) on Japanese pine tree. compounds, phenols, azoles, iodopropargyl derivatives, Solid shaped plant treatment material (6 mm in diameter, 40 isothiazolines, benzisothiazolinones, cyclopentene 40 mm in length, 70% imidacloprid, 30% PEG) was inserted isothiazolines, nitrites, benzothiazoles and quinolines. into a hole of the trunk of J. pine tree at 3 bars per 1 tree (Ca. 4. The agent according to claim 2 wherein Said insecticide 10-15 cm of trunk in diameter) in early Spring. 5 trees per is Selected from the group consisting of azinphoSethyl, plot were used the test. azinphoS-methyl, I-(4-chlorophenyl)-4-(O-ethyl-S-propyl)- 10 heads of newly emerged adults of. J. pine Sawyer were 45 phosphoryloxypyrazole (TIA-230), chlorpyrifos, infested artificially on a top wig of the tree at the end of July. coumaphos, demeton, demeton-S-methyl, diaZinon, Mortality was investigated 3 days after infestation. dichlorVOS, dimethoate, ethoprophos, etrimfos, fenitrothion, fention, heptenophos, parathion, parathion-methyl, phosalone, phoXion, pirimiphoSethyl, pirimiphoS-methyl, 50 profenofoS, prothiofoS, SulprofoS, triaZophos, trichlorphon, Mortality (%) aldicarb, bendiocarb, BPMC (2-(1-methylpropyl)-phenyl Test sample plot 1OO methylcarb amate), butocarboxime, butoxycarboxime, Control plot O carbaryl, carbofuran, carboSulphan, cloethocarb, isoprocarb, NIT 280 methomyl, oxamyl, pirimicarb, promecarb, propoxur, 55 thiodicarb, allethrin, alphame thrin, biore Smethrin, by fenthrin (FMC 54800), cycloprothrin, cyfluthrin, EXAMPLE 1.8 decame thrion, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl 2.2,-dimethyl-3-(2)- For the control of Pine wood nematode (Bursaphelenchus chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate, xylophilus) on Japanese pine tree. 60 fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, Solid shaped plant treatment material (6 mm in diameter, flumethrin, fluvalinate, permethrin resmethrin, and 1-(6- 40 mm in length, 60% mesulfenfos, 40% PEG) was inserted chloro-3-pyridinyl)-methyl-4,5-dihydro-N-nitro-1H into a hole of the trunk of J. pine tree at 5 bars per 1 tree (Ca. imidazol-2-amine. 10-15 cm of the trunk in diameter) in early spring. 5 trees 5. The agent according to claim 1 wherein Said insecti per plot were used the test. 65 cide S is Selected from the group consisting of 3000 heads of the P.W. nematoda were infested artificially nitromethylenes, nitroguanidines and cyanimides of the for on a top wig of the tree at the and of July. mula I 6,063,393 29 30 -continued (I) (III) (A) Subst. Nt R-NC 1(Z) - (A) S (CH2) NN - (Z) C | X-E in which R represents hydrogen or optionally Substituted acyl, alkyl, aryl, aralkyl, heteroaryl or heteroarylalkyl radi in which cals, A represents a monofunctional group from the Series SubSt. represents halogen, comprising hydrogen, acyl, alkyl and aryl, or represents 15 in represents 1 or 2, a bifunctional group, which is linked to the radical Z, E represents NO or CN; A represents a monofunctional group from the Series X represents the radicals -CH= or=N-, wherein the comprising hydrogen, acyl, alkyl and aryl, or represents radical -CH= can be linked to the radical Z instead a bifunctional group, which is linked to the radical Z, of an H atom; and E represents NO or CN; Z represents a monofunctional group from the Series X represents the radicals -CH= or=N-, wherein the comprising alkyl, -O-R or radical -CH= can be linked to the radical Z instead

R of an H atom; and 25 Z represents a monofunctional group from the Series comprising alkyl, -O-R, -S-R or

R or represents a bifunctional group, which is linked to N the radical A or the radical X. R, 6. The agent according to claim 1 in which the insecticide is selected from the group consisting of formulae II and III: or represents a bifunctional group, which is linked to (II) 35 the radical A or the radical X, Substine CH N1 Z. R represents hydrogen or optionally Substituted acyl, alkyl, aryl, aralkyl, heteroaryl or heteroarylalkyl radi V y -CH-)-N-0| cals. X-E