Europaisches Patentamt ® 3 European Patent Office (31) Publication number: 0 327 467 Office europeen des brevets A2 EUROPEAN PATENT APPLICATION ® Application number: 89400317.7 @ Int. CI/': A 01 N 53/00 //(A01 N53/00,53:00,43:30) (g) Date of filing: 03.02.89 (gjj) Priority: 05.02.88 HU 54088 Hldasl, Gydrgy 7/aSarretu. @ pate of publication of application: H-1 142 Budapest (HU) 09.08.89 Bulletin 89/32 Zoltan,, „.. Sandor 7/aSarkdzyu. @ Designated Contracting States: H-1 140 Budapest (HU) BE CH DE FR GB IT LI LU NL SE Deak,Anlk6 2,3L?"Sf k- ® Applicant: CHINOIN Gyogyszeres Vegy6szeti bf' U\ ,„.„ TermekekGyaraRT. H-1 142 Budapest (HU) Toutca1-5 . H-1045 Budapest IV (HU) Hegedus, Agnes llj TOnKGS Ui H-1225 Budapest (HU) @ Inventor: Pap, Laszl6, Dr. 1 9, Vadon u. Bertbk, Bela, Dr. H-1112 Budapest (HU) 44,Jaku. H-1222 Budapest (HU) Sarkazl, Peter, Dr. 19, Varfok u. Botar, Sandor, Dr. H-1014 Budapest (HU) 49,AranyJ.U. H-1222 Budapest (HU) Somfal, Eva, Dr. 8, Tancslcs M. u. Gajary, Antal, Dr. H-1014 Budapest (HU) 15/a, Bolonl Gy. u. H-1021 Budapest (HU) Szego, Andras, Dr. 8, Krudy u. Nagy, Lajos H-1 088 Budapest (HU) 16, Vasarhelyi K. ter H-2000Szentendre (HU) Szekely, Istvan, Dr. H-2ir20CDunakeszl ® 1(HU) ' CABINET REGIMBEAU 26, avenue Kleber F-75116 Paris (FR) 3! @ Arthropodlcldal compositions. @ The present Invention relates to synergistic arthropodicidal composition of several pyrethroidal active ingredients causing CI- CM no damage to warm-blooded organisms comprising pyre- CO throides and piperonyl butoxide as active ingredient which comprises as pyrethroidal active ingredient 0.1-20 o/o by weight CI' of 1 StransR-alpha-oyano-3-phenoxy-benzyl-3-/2,2-dichlorvinyl/ -2,2-dimethylcyclopropane-cyrboxylate of the Formula I Q. LU Bundesdruckerei Berlin u.uo-iu u/o Dy weigni ot cis-irans-teirametnnn /3,4,t>,e-tetrahy- drophtalimido-methyl/1RS/-cis-trans-chrysantemate/ or trans- tetramethrin of the Formula II CH3^ N/ x0-CH2-N^JJ) u. UH3 UH3 and optionally a further pyrethroide, 0.1-40 0/0 by weight of piperonyl butoxide of the Formula III 0 { YyCH2OCH2CH20CH2CH20C4H9 0 ^AcH2CH2CH3 UL EP 0 327 467 A2 Description ARTHROPODIC1DAL COMPOSITIONS The present invention relates to arthropodicidal compositions containing several pyrethroidal active ingredients. The invention particularly relates to synergistic arthropodicidal compositions containing several pyrethroidal active ingredients which are not toxic to warm-blooded organisms. The compositions contain as a pyrethroidal active ingredient 1StransR-alpha-cyano-3-phenoxy-benzyl~ 3-/2,2-dichlorvinyl/-2,2-dimethyl-cyclopropane carboxylate of the Formula I CI :c=ch CI and tetramethrin or trans-tet/amethrin of the Formula II CH3x. OCH CH3 II. and optionally a further pyrethroidal substance as well as piperonyl butoxide of the Formula III and optionally additives. CH2OCH2CH20CH2CH2OCZf H9 III. CH2CH2CH3 The compound of the Formula I amounts to 0.1-20 % by weight and the compound of the Formula II to 0.05-100/0 by weight and the piperonyl butoxide of the Formula III amounts to 0.1-40% by weight. The remaining amount up to 100% consists of additives. The following abbreviations are used throughout the specification: Alphaniethrin = /S/-alpha-cyano-3-phenoxybenzyi-/1R,3R/-3/2,2-dichlorvinyl/-2,2-dimethylcyclopropane- carboxylate and /R/-a|pha-cyano-3-phenoxy-benzyl-/1S,3S/-3/2,2-dichlorvinyl/-2,2-dimethyl-cyclopropane carboxylate TET =*= tetramethrin = 3,4,5,6-tetrahydro-phtalimido-methyl/1RS/-cis-trans-chrysanthemate deltamethrin = /S/-alpha-cyano-3-phenoxy-benzyl/1R,3R/-3-/2,2-dibrombinyl/-2,2-dimethyl-cyclopropane EP 0 327 467 A2 carboxylate trans TET = trans tetramethrin = 3,4,5,6-tetrahydro-phtalimidomethyl/1RS/-trans chrysanthemate TRX = transmix = a mixture of 1StransR-alpha-cyano-3-phenoxy-benzyl-3-/2,2-dichlorvinyl/-2,2-dimethyl cyclopropane carboxylate and 1 RtransS-alpha-cyano-3-phenoxy-benzyl-3-/2,2-dichlorvinyl/-2,2-dimethyl-cy- clopropane carboxylate 5 SF = synergistic factor PBO - piperonyl butoxide The composition according to the invention may be used in all those locations wherein only such substances may be applied which are substantially not toxic to warm-blooded organisms, such as agricultural and horticultural pests, i.e. pests occurring in preserved food industry and refrigerating industry. Various 10 parasitic arthropodal pests cause significant harm in stock breeding. By disquieting the animals the pests cause a reduction of their yield capacity, their gain in weight, they disturb their behaviour and their technology tolerance increasing thereby the number of compulsory slaughtering. Significant yield losses are caused by the store arthropoda as well, and this is worsened by the fact that these crops are already produced /i.e. costs are already involved/ and the protection is needed for the whole provision storing period during the utilization 15 of the crops to avoid the presence of substances being harmful for men and animals in provision. During the protection against diseases propagated by various arthropoda such as malaria, yellow disease, sleeping disease, dysentery, plague, it is important that only such agents may be applied which are not toxic to warm-blooded organisms, are intoxic dermally, do not cause dermal irritation and allergy. As the most widely used insecticides are neuroactive substances /nerve poison/ the function of such 20 nerves is damaged which can be found in both inferior and superior animals /F. Matsumura: Differential toxicities of insecticides and halogenated aromatics, Pergamon Press 1984/. Consequently, the selectivity of most of the compositions is not sufficient. The compositions according to the invention show an outstanding activity against the following pests: flies such as Hydrotaea irritans, Morellia simplex, M. Hortorum, Haematobla spp., Stomoxys calcitrans, Musca 25 domestica, M. autumnalis, Glossina app., Simulium spp., Culicoides, Phlebotomus spp., Tabanidae/; fleas such as Xenopsylla spp., Pulex spp., Ctenocephalides app./; bugs such as Cimex spp., Triatoma spp., Rhodnius spp., Triatoma spp./; louses such as Pediculus spp., Phthirius pubis, Damalinia, Haematophinus; ticks resp. mites such as Ixodes, Sporoptes spp., scabiei; mosquitoes such as Anopheles spp., Aedes spp., Culex spp., Mansonia spp.; cockroaches such as Blattella germanica, Blatta orientalis, Periplaneta americana, 30 Periplaneta australasie, Supella longipalpa; various store pests such as Tribolium spp., Trogoderma spp., Stegobium spp., Sitophilus spp., Tenebrio spplk, Stagobium paniceum, Sitotroga cerealella, Zaorotes subfasciatus, Rhyzopertha dominica, Ptinus spp., Cryzaephilus surinamensis, O. mercator, Lasioderma serricorne, Necrobia spp., dermestes spp., Carpopohilus spp., Dryptolestes spp., Mezium spp., Alphitobius diapersinus, A.laevigatus, Callosobruchus spp., Bruchus spp., Anthrenus verbasci, Ephestia spp., Plodia 35 interpunctella, Acaris siro, Tyrophagus putres, T.centiale, T.longinor, Tyrolichus casei; agricultural pests belonging to genera Lepidoptera, Coleoptera, Heteroptera, Homoptera, Hymenoptera, Diptera and Acariformes. A preferred form of the composition according to the present invention contains as a further active ingredient 1RtransS-alpha-cyano-3-phenoxy-benzyl-3-/2,2-dichlorvinyl/-2,2-dimethylcyclopropane-carboxy- 40 late in an amount of 0.1-20% by weight. The ratio of IStransR to IRtransS amounts to 0.7-1.3:1.3-0.7, preferably 1:1. We have now found that IStransR isomer being the least active out of the 4 trans isomers of cypermethrin can be transformed to a synergistic active and stable composition when combined with tetramethrin and piperonyl butoxide. Thus the advantages of the very low toxicity against warm-blooded animals can be utilized 45 and outstanding selective arthropodicidal composition may be prepared. The data relating to synergistic compositions are shown in Table 1. 3 EP 0327 467 A2 Table 1 Interaction of transmix isomers and piperonyT butoxide on house fly /Musca domestica/ tested by topical method isomers activity activity with PBO/1:2/x and active without ingredient PBO 10 mixtures LDsom resp. ng/fly ng/fly SF IRtransS 5.78 4.58 1.26 IStransR 571.50 278.62 2.05 TRX 6.70 3.76 1.78 TRX+TET 8.02 2.97 2.70 (10|1) TRX+TET 8.41 2.87 2.93 (10;5) x =1 calculated to trans cypermethrins As excipients anionic tensides, such as calcium alkyl aryl sulfonate, calcium dodecyl benzene sulfonate or 25 non-jonic surfactants such as nonyl or dinonyl phenol ethoxylates /EO = 16-20/ are used. The composition may contain further non-ionic components such as tristyryl phenol ethoxylates /ED = 20/ etc. As filling agent the composition may contain solvents such as xylene, aromatic solvent mixture, aliphatic hydrocarbon mixtures, alkyl benzene, mineral or vegetable oile and solid carriers etc. The formulation of the composition depends on the method of application. In order to prepare emulsifiable 30 qompositions anionic tensides, non-ionic surfactants and other non-jonic components and solvents are preferable admixed to the mixture. As anionic tensides 2 to 5 % by weight of calcium alkyl aryl sulfonate, and as non-ionic surfactant 1 to 2 % by weight of nonyl-, dinonyl phenol ethoxylates /EO = 16-20/ and as further non-jonic components 0.5-2 o/o by weight of tristyryl phenol ethoxylates (EO = 20/ and as solvent xylene may preferably be used. 35 A transparent emulsifiable composition may be prepared by using as anionic tenside 2.5-9 % by weight of a calcium salt of alkyl aryl sulfonate,, and as non-ionic surfactant 1 .25-3.5 % by weight of nonyl-, dinonyl phenol ethoxylates /EO = 16-20/ and as further non-ionic component 0.7-3.5 % by weight of tri-styryl phenol ethoxylates /EO = 20/ and as solvent preferably 5-10 % by weight of xylene, 1-3 % by weight of ethylene glycol and water up to 100% by weight. 40 Wettable powders can also be prepared by adding dispersing agents and carriers. According to a preferred feature as dispersing agent 1-2 % by weight of dioctyl sulfosuccinate and 6-8 % by weight of polymerized sodium naphtaline sulfonate and as carrier silicic acid and talc may be used.