NZ245084A - Shaped articles comprising pesticidal active compounds and an elastomeric styrene/butylene block copolymer as carrier - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £45084 24 0 0 9 4 Patents Form 5 Priority Dctc(s): .1"^-. > >; ,<f\\ Co.,^IU[U rc(.J;:c = !io:; Filed: Cl»*s: PubJicat-C£f 2 4 FEB 1995' J3£^.

M WMWN&S f' : H 11 NOV 1332 N.Z. No.

NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION SHAPED ARTICLES WHICH CONTAIN ACTIVE COMPOUNDS AND ARE BASED ON ELASTOMERIC STYRENE/BUTYLENE BLOCK COPOLYMERS WHICH CAN BE PROCESSED AS THERMOPLASTICS. PROCESSES FOR THEIR PRODUCTION AND THEIR USE FOR CONTROL OF PESTS We, BAYER AKTIENGESELLSCHAFT, a Company registered under the laws of the Federal Republic of Germany, of Leverkusen, Gefmany do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- - I - (Followed by I A) 245084 The present invention relates to new shaped articles which contain active compounds and are based on elasto-meric styrene/butylene block copolymers which can be processed as thermoplastics, their production and their 5 use for control of pests, in particular in stock and domestic animals.

Shaped articles which comprise active compounds for controlling pests are known. They are based on the slow release of active compounds from a carrier matrix of 10 plastics which contains active compounds (compare, for example, Aries et al US P 3 814 061, Greenberg US-P 3 918 407, Miller et al US-P 3 944 662, Millionis et al US-P 4 041 151, Pasarela US-P 4 145 409, Greenberg and Cloud US-P 4 158 051, v. Bittera et al 15 US-P 4 225 578. McDaniel et al EP-OS 0 052 411, Grubb et al US-P 3 852 416 and Pearce US-P 4 536 388).

The carrier employed practically almost exclusively for known shaped articles is PVC. Although other carriers are mentioned in the literature, as yet they have not found 20 acceptance in practice. Thus, US-P 4 195 075 mentions, inter alia, that thermoplastic elastomers are also possible as carrier polymers for ear marks. However, this citation also describes exclusively examples using plasticiser-containing PVC as the carrier polymer.

This is also not surprising. PVC is inexpensive and Til * B8 - i A- 9 /, K r' 0 /, C. H u - f readily accessible. It is also miscible with other substances, in particular plasticisers, within wide limits. These plasticisers in PVC bodies containing active compounds have the function of keeping the active 5 compound dissolved in the carrier and of transporting it slowly to the surface of the body. At the surface, the active compound evaporates or is rubbed off from the surface, together with the plasticiser. The interaction of the three components PVC carrier, plasticiser and 10 active compound determines whether and to what extent the shaped article can be employed in practice.

If one component of the overall system is changed, it can no longer be predicted whether the system still acts in practice. This applies in particular if the plasticiser, 15 which indeed has a key function in transportation of the active compound, is changed or omitted.

For various reasons, it is desirable to replace PVC as the carrier material. It is also advantageous to dispense partly or completely with the use of plasticisers. It was 20 therefore a matter of discovering an active compound/ shaped article system in which PVC, as the carrier material, and plasticiser can be dispensed with and which nevertheless has a good action in practice.

Thermoplastic elastomers are materials which comprise 25 elastomeric phases either mixed physically or bonded chemically in polymers which can be processed as thermoplastics. A distinction is made between polyblends, 245084 in which the elastomeric phases are present in physically mixed-in form, and block polymers, in which the elastomeric phases are a constituent of the polymeric matrix. Hard and soft regions are present side by side as a 5 result of the build-up of the thermoplastic elastomers. The hard regions form a crystalline network structure or a continuous phase, the interstices of which are filled by elastomeric segments. On the basis of this build-up, these materials have rubber-like properties.

A distinction may be made between 5 main groups of thermoplastic elastomers: 1. Copolyesters 2. Polyether block amides (PEBA) 3. Thermoplastic polyurethanes (TPU) 15 4. Thermoplastic polyolefins (TPO) . Styrene block copolymers These 5 main groups show similar macroscopic physical properties, coupled with a completely different chemical build-up. In spite of these macroscopically similar 20 properties, these main groups behave completely differently in respect of mixing in and release of active compounds.

The use of thermoplastic elastomers based on copolymers as carriers for active compounds is known. The use of 25 styrene/butadiene block copolymers as carriers is described in EP-OS (European Published Specification) 338 821. 2 •■'} 5 0 8 4 The use of polyurethane/polydisiloxane copolymers as carriers is described in EP-OS (European Published Specification) 338 732.

The present invention relates to 1. Shaped articles which contain active compounds, characterised in that they comprise, as carriers, thermoplastic elastomers based on styrene/butylene block copolymers, as well as customary additives if appropriate. 2. Processes for the production of shaped articles containing active compounds, characterised in that thermoplastic elastomers based on styrene/butylene block copolymers are mixed with active compounds and if appropriate customary additives, and the mixture is processed in the customary manner.

It was surprising that active compounds also arrive at the polymer surface from the polymer matrix from thermoplastic elastomers based on styrene and butylene without addition of plasticisers, since this capacity is limited to only a very few polymers. If only one component of the overall system is changed, the effects are unpredictable. Thermoplastic elastomers based on thermoplastic olefins (TPO) or thermoplastic polyurethanes, for example, are not capable of allowing active compounds to migrate to the surface. !■ » afl rjljgi The styrene/butylene block copolymers which can be used according to the invention consist of a polyethylene-butylene rubber central block with a polystyrene end block linked chemically to both ends. The polystyrene 5 content is less than 30%. The polystyrene end blocks are distributed uniformly in the ethylene rubber matrix as spherical polystyrene domains.

Processes for the synthesis of suitable styrene block copolymers are known, for example, from US-P 3 485 787, 10 4 006 116 and 4 039 629.

Suitable styrene/butylene block copolymers are obtainable, for example, under the commercial names ®Kraton G and ®Elexar from Shell Chemie GmbH and ®Thermolast-K-Compounds from Kraiburg.

Active compounds which may be mentioned for the shaped articles according to the invention are, preferably, insecticides, in particular parasiticides, for use on animals. The insecticides include phosphorus-containing compounds, such as phosphoric or phosphonic acid esters, 20 naturally occurring and synthetic pyrethroids, carbamates, amidines, juvenile hormones and juvenoid synthetic active compounds.

The phosphoric or phosphoric acid esters include: 0-ethyl 0-(8-quinolyl) phenyl-thiophosphate (quintiofos), 0,0-diethyl 0-(3-chloro-4-methyl-7-couinarinyl) thiophosphate (coumaphos), 0.0-diethyl O-phenylglyoxylonitrile oxime thiophosphate (phoxim), 0,0-diethyl O-cyanochlorobenzaldoxime thiophosphate (chlorphoxim), 0.0-diethyl 0-(4-bromo-2,5-dichlorophenyl) phosphoro-thionate (bromophos-ethyl), 0,0,0',0'-tetraethyl-S,S'-methylene di(phosphorodi-thionate) (ethion), 2, 3-p-dioxanedithiol-S,S-bis(0,0-diethyl phosphorodi-thionate, 2-Chloro-l-(2,4-dichlorophenyl)-vinyl diethyl phosphate (chlorfenvinphos), and 0,0-dimethyl 0-(3-methyl-4-methylthiophenyl) thionophos-phate (fenthion).

The carbamates include: 2-isopropoxyphenyl methylcarbamate (propoxur) and 1-naphthyl N-methylcarbaunate (carbaryl).

The synthetic pyrethroids include compounds of the formula I R R COO-CH- formula I R in which R1 and R2 represent halogen, optionally halogen-substi-tuted alkyl or optionally halogen-substituted phenyl, R3 represents hydrogen or CN, R* represents hydrogen or halogen and R5 represents hydrogen or halogen, Preferred synthetic pyrethroids are those of the formula I in which R1 represents halogen, in particular fluorine, chlorine or bromine, R2 represents halogen, in particular fluorine, chlorine, bromine, trihalogenomethyl, phenyl or chlorophenyl, 24 1j R3 represents hydrogen or CN, RA represents hydrogen or fluorine and R5 represents hydrogen.

Particularly preferred synthetic pyrethroids are those of the formula I in which R1 represents chlorine, R2 represents chlorine, trifluoromethyl or p- chlorophenyl, R3 represents CN, R* represents hydrogen or fluorine and R5 represents hydrogen.

Compounds of the formula I which may be mentioned in particular are those in which R1 represents chlorine, R2 represents chlorine or p-chlorophenyl, R3 represents CN, A O /. h ^ rw L j 'j.

R* represents fluorine in the 4-position and R5 represents hydrogen.

Compounds which may be mentioned specifically are: (a-cyano-4-fluoro-3-phenoxy)-benzyl 3-[2-(4-chloro-phenyl) -2-chlorovinyl]-2,2-dimethyl-cyclopropanecarboxyl-ate (flumethrin), a-cyano(4-fluoro-3-phenoxy)-benzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylate (cyfluthrin) and its enantiomers and stereomers, tt-cyano-3-phenoxybenzyl (±)-cis,trans-3-(2,2-dibromo-vinyl ) -2 , 2-dimethylcyclopropanecarboxylate (deltamethrin) , a-cyano-3-phenoxybenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylate (cypermethrin), 3-phenoxybenzyl (±)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (permethrin), o-cyano-3-phenoxy-benzyl a-(p-Cl-phenyl)-isovalerate (fenvalerate) and 2-cyano-3-phenoxybenzyl 2-(2-chloro-a,a,a-trifluoro-p-toluidino)-3-methylbutyrate (fluvalinate). 4 5 0 8 4 The amidines include: 3-methyl-2-[2,4-dimethyl-phenylimino]-thiazoline, 2-(4-chloro-2-methylphenylimino)-3-methylthiazolidine, 2-(4-chloro-2-methylphenylimino)-3-(isobutyl-l-enyl)-thiazolidine and 1,5-bis-(2,4-dimethylphenyl)-3-methyl-l,3, 5-triazapenta-1,4-diene (amitraz).

The juvenile hormones or substances like juvenile hormones include substituted diaryl ethers, benzoylureas and triazine derivatives. The juvenile hormones and substances like juvenile hormones include, in particular, compounds of the following formulae: i S0-H7C3 DCH- *■ ft BO liW 9 /, e n o / £ H u o 4 ch3 0 ch3 ch3 The substituted diaryl ethers include, in particular, 24 L; C substituted alkoxydiphenyl ethers or -diphenylmethanes of the general formula I wherein R1 represents hydrogen, halogen, alkyl, alkoxy, alkyl-thio, halogenoalkyl, halogenoalkoxy, halogenoalkyl-thio, dioxyalkylene, dioxyhalogenoalkylene, CN, N02, alkenyl, alkinyl, alkoxyalkyl, alkoxyalkoxy or hydroxyalkoxy, R2 represents the radicals mentioned for R1, R3 represents the radicals mentioned for R1, R* represents hydrogen, alkyl, halogenoalkyl or halogen, R5 represents the radicals mentioned for R*, Het represents optionally substituted heteroaryl, which is not bonded to the rest of the radical via the hetero atom, X and Y independently of one another represent -0- or -S- Z represents -0-, -S-, -CH2-, -CHCH3- or -C(CH2)2- and m and n independently of one another represent 0, 1, 2 or 3, but their sum is equal to or greater than 2.

Particularly preferred compounds of the formula I are those in which R1 represents hydrogen, methyl, trifluoromethyl, methoxy, trifluoromethoxy, chlorine or fluorine R2 represents hydrogen, R3 represents hydrogen, fluorine, chlorine or methyl, R* represents hydrogen or methyl, R5 represents methyl, ethyl, trifluoromethyl or hydrogen, Het represents pyridyl or pyridazinyl, which are optionally substituted by fluorine, chlorine, methyl, N02, methoxy or methylmercapto, X represents 0, 24 1 \J vj c Y represents 0, Z represents 0, CH2 or -C(CH3)2-, m represents 1 and n represents 1.

The following compounds may be mentioned specifically: r1 w-= V r5 1 ■o-ch2-ch- n j r3 f1 r3 r5 r 6 z h h ch3 h 0 h h ch3 2-c1 0 -f h ch3 h 0 h h cf3 h 0 h h c2h5 h 0 h h h h 0 h h ch3 h ch2 h h ch3 h c(ch3) h BO 24 C 24 5 0 8 4 The benzoylureas include compounds of the formula (V): R2 represents hydrogen or halogen, R3 represents hydrogen, halogen or C^-alkyl and R4 represents halogen, 1-5-halogeno-C^-alkyl, C^-alkoxy, l-S-halogeno-Cj^-alkoxy, C^-alkylthio, 1-5-halogeno-C^-alkylthio, phenoxy or pyridyloxy, which can optionally be substituted by halogen, C1.A-alkyl, 1-5-halogeno-C^-alkyl, C^-alkoxy, 1-5-halogeno-C^-alkoxy, C^-alkylthio or 1-5-halogeno-C^-C,,-alkylthio.

The following compounds may be mentioned in particular: (V) wherein R represents halogen 24 5 0 8 4 The triazines include compounds of the formula (VI) he. * BO 93ft 24 5 0 8 4 wherein Rx represents cyclopropyl or isopropyl; R2 denotes hydrogen, halogen, Ci-C^-alkylcarbonyl, cyclopropylcarbonyl, C^C^-alklcarbamoyl, Ci-C12-5 alkylthiocarbamoyl or C2-C6-alkenylcarbamoyl; and R3 represents hydrogen, C^C^-alkyl, cyclopropyl, C2-C6-alkenyl, C^C^-alkylcarbonyl, cyclopropylcarbonyl, Ci-C12-alky lcarbamoyl, Cj-C^-alkylthiocarbamoyl or C2-C6-alkenylcarbamoyl, and acid addition salts 10 thereof which are non-toxic to warm-blooded animals.

Compounds which may be mentioned in particular are: F?1 R2 R3 Cyclopropyl H H Cyclopropyl H CH3 Cyclopropyl H C2H5 Cyclopropyl H C3H7-n fru H BO fl» (Continuation) 24 5 0 8 4 R1 R2 r3 Cyclopropy1 H L4H9-n Cyclopropyl H C5H11 ~n Cyclopropyl H C6H13-n Cyclopropyl H C7H15 ~n Cyc1opropy1 H C8H17~n Cyc1opropyl h C12H25 ~n Cyclopropyl H CH2-C4H9-t Cyc1opropy1 H ch2ch(ch3 )c2h, Cyc1opropy1 H ch2ch=ch2 Cyclopropyl CI C2H5 Cyclopropyl CI C6H13"n Cyclopropyl CI c8hi7-n Cyclopropyl CI C12H25 ~n Cyclopropy 1 H Cyc1opropyl Cyclopropyl H coch3 Cyclopropyl h COCH3'HC1 Cyc1opropyl h COC2H5-HC1 Cyclopropyl H coc2h5 Cyc1opropyl H COC3H7—n Cyclopropyl H COC3^^ ~ i Cyclopropyl H COC4H9-t-HC1 Cyclopropyl h COC4H9-n Cyclopropyl H c°c6hi3-n Cyclopropyl H COC1j-H23-n Cyc1opropy1 COCH3 coc2h5 Cyclopropyl COC ~^ COC6H13~n Cyc1opropy1 coch3 COC ~ n 245084 (Continuation) Ri R2 R3 Cyclopropyl coc2h5 C0C3H7-n Cyclopropyl H COCyclopropyl Cyclopropyl COCylclopropyl COCyclopropyl Cyclopropyl coch3 coch3 I sopropyl H H I sopropyl H coch3 Isopropyl h COC3H7-n Cyclopropyl H conhch3 Cyc1opropyl H CONHC3H7-i Cyc1opropy1 conhch3 conhch3 Cyclopropy1 H csnhch3 Cyclopropyl H conhch2ch=ch2 Cyc1opropyl conhch2ch=ch2 conhch2ch=ch2 Cyclopropyl csnhch3 csnhch3 The active compounds having the comnon names propoxur, cyfluthrin, flumethrin, pyriproxyf en, methoprene, Diazinon, amitraz and fenthion may be singled out in 5 particular.

The active compounds can be present in the shaped articles by themselves or as a mixture with one another.

The active compounds are present in the shaped articles in concentrations of 0.1 - 20 % by weight, preferably of 10 between 1 and 10 % by weight.

The shaped articles according to the invention can furthermore comprise the additives customary for plastics. Customary additives are, for example, pigments, 4 5 0 8 4 stabilisers, flow agents, lubricants and mould release agents.

Examples of customary additives are: 1. Antioxidants 1.1 Alkylated monophenols. for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethyl-phenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-i-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (a-methyl-cyclohexyl)-4,6-dimethylphenol, 2,6-di- octadecyl-4-methylphenol and 2,4,6-tricyclohexyl-phenol, 2,6-di-tert-butyl-4-methoxymethylphenol. 1.2 Alkylated hvdroauinones. for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydro- quinone, 2,5-di-tert-amyl-hydroquinone and 2,6- diphenyl-4-octadecyloxyphenyl. 1.3 Hvdroxvlated thiodiphenvl ethers, for example 2,2'-thio-bis-(6-tert-butyl-4-methylphenol), 2,2'-thio-bis-{4-octylphenol), 4,4'-thio-bis-(6-tert-butyl-3- methylphenol) and 4,4'-thio-bis-(6-tert-butyl-2- methylphenol). 1.4 Alkvlidene-bisphenols. for exaunple 2,2 '-methylene-bis-(6-tert-butyl-4-methylphenol), 2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol), i* #x CO ' n n k ^ 0 8 4 2,2' -methylene-bis-(4-methyl-6(a-methylcyclohexyl)-phenol, 2,2'-methylene-bis-(4-methyl-6-cyclohexyl-phenol), 2,2'-methylene-bis-(6-nonyl-4-methyl-phenol) , 2,2'-methylene-bis-(4,6-di-tert-butyl-5 phenol), 2,2'-ethylidene-bis-(4,6-di-tert-butyl- phenol), 2,2'-ethylidene-bis-(6-tert~butyl-4-iso-butylphenol), 2,2'-methylene-bis-[6-(a-methyl-benzyl)-4-nonylphenol], 2,2'-methylene-bis-[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-methylene-bis-10 (2,6-di-tert-butylphenol), 4,4'-methylene-bis-(6- tert-butyl-2-methylphenol), 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane, 2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-15 butane, 1,1-bis-(5-tert-butyl-4-hydroxy-2-methyl- phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis-[3,3-bis-(3 '-tert-butyl-4'-hydroxyphenyl)-butyrate], di-(3-tert-butyl-4-hydroxy-5-methyl-phenyl)-dicyclopentadiene and di-[2-(3'-tert-butyl-20 2 '-hydroxy-5 '-methylbenzyl)-6-tert-butyl-4-methyl- phenyl] terephthalate. 1.5 Benzyl compounds. for example 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulphide, 25 isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto- acetate, bis-(4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl) dithiol-terephthalate, l,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) JIL A 10 WS I \ V/" O i i \ isocyanurate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate and 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid monoethyl ester calcium salt. 1.6 Acvlaminophenols. for example 4-hydroxy-1auric acid anilide, 4-hydroxystearic acid anilide, 2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanil-ino)-s-triazine and octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate. 1.7 Esters of fl-(3,5-di-tert-butvl-4-hvdroxvphenvl)-propionic acid with mono- or polyhydric alcohols, such as, for example, methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaeryth-ritol, tris-hydroxyethyl isocyanurate and di-hydroxyethyl-oxalic acid diamide. 1. 8 Esters of 8-(5-tert-butvl-4-hvdroxv-3-methvlphenvl) -propionic acid with mono- or polyhydric alcohols, such as, for example, with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate and di-hydroxyethyl-oxyalic acid diamide. 1.9 Amides of fl-(3.5-di-tert-butvl-4-hvdroxvphenvll-propionic acid, such as, for example, N,N'-di-(3,5-di-tert-butl-4-hydroxyphenylpropionyl)- *iu li BO t 2 4 n n / <J L" U 4 hexamethylenediamine, N,N'-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -trimethylenediamine and N,N' -di- (3, 5-di-tert-butyl-4-hydroxyphenylpropion-yl)- hydrazine. 2. UV absorbers and light stabilisers 2.1 2-(2'-Hvdroxyphenvl)-benzotriazoles, such as, for example, the 5'-methyl, 3' ,5'-di-tert-butyl, 5'-tert-butyl, 5' - (1,1,3,3-tetramethylbutyl), 5-chloro-3 ', 5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'- methyl, 3'-sec-butyl-5'-tert-butyl, 4'-octoxy, 3',5'-di-tert-amyl and 3',5'-bis-(a,a-dimethyl-benzyl) derivative. 2.2 2-Hvdroxvbenzophenones. such as, for example, the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyl- oxy, 4-benzyloxy, 4,2',4'-trihydoxy and 2'-hydroxy- 4,4'-dimethoxy derivative. 2.3 Esters of optionally substituted benzoic acids, such as, for example, 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenz- oylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate. 2.4 Acrvlates. such as, for example, ethyl or isooctyl a-cyano-/9,0-diphenylacrylate, methyla-carbomethoxy- iiu ft BO MS 2 a n r r S W V_-' cinnamate, methyl or butyl a-cyano-0-methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-p-methoxy-cinnamate and N-(/S-carbomethoxy-/9-cyanovinyl)-2-methyl-indoline. 2.5 Nickel compounds, such as, for example, nickel complexes of 2,2'-thio-bis-[4-(l,l,3,3-tetramethyl-butyl) -phenol ], such as the 1:1 or 1:2 complex, optionally with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyl-dieth-anolamine, nickel dibutyl-dithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzyl-phosphonic acid monoalkyl esters, such as of the methyl or ethyl ester, nickel complexes of ketoximes, such as 2-hydroxy-4-methyl-phenyl undecyl ketone oxime, and nickel complexes of l-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additional ligands. 2.6 Sterically hindered amines, such as, for example, bis-(2,2,6,6-tetramethylpiperidyl) sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl-malonate, the condensation product of l-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N,N'-(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-l,3,5-s-triazine, tris-(2,2,6,6-tetramethyl-4-piperidyl) nitrotriacetate, i\ z n i ^ ^ O f vj Ljt tetrakis- (2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylic acid and 1,1'-(1,2-ethanediyl) -bis- (3,3,5,5-tetramethylpiperazinone) . 2.7 Oxalic acid diamides. such as, for example, 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide, 2,2' -di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis- (3-dimethyl-aminopropyl) -oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2 ' -ethyl-5,4' -di-tert-butyl-oxanilide and mixtures of o- and p-methoxy- and of o- and p-ethoxy-disubstituted oxanilides. 3. Metal deactivators, such as, for example, N,N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyl-oylhydrazine, N,N'-bis-( salicyloylhydrazine, N,N'-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine, 3-salicyloylamino-l,2,4-triazole and bis-benzylidene-oxalic acid dihydrazide. 4. Phosphites and phosphonites. such as, for example, triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tri-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) -phosphite, diisodecylpentaeryth-ritol diphosphite, di-(2/4-di-tert-butylphenyl)-pentaerythritol diphosphite, tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylpheny1)- P / ^ 0 n f i U 0 l } 4,4'-biphenylene diphosphonite and 3,9-bis-(2,4-di-tert-butylphenoxy-2,4,8,10-tetraoxa-3,9-diphospha-spiro[5,5]undecane.

. Peroxide-destroying compounds, such as, for example, esters of £-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mer-captobenzimidazole, the zinc salt of 2-mercapto-benzimidazole, zinc dibutyl-dithiocarbamate, di-octadecyl disulphide and pentaerythritol tetrakis-(f) -dodecy lmercapto) -propionate. 6. Polvamide stabilisers, such as, for example, copper salts in combination with iodides and/or phosphorus compounds, and salts of divalent manganese. 7. Basic costabilisers. such as, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, amines, polyamides, polyurethanes and alkali metal and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg stearate, Na riconoleate, K palmitate, antimony pyrocatecholate or tin pyrocatecholate. 8. Nucleating agents, such as, for example, 4-tert-butylbenzoic acid, adipic acid and diphenylacetic acid. 9. Fillers and reinforcing agents. such as, for example, calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulphate, metal oxides and hydroxides, carbon black and graphite.

. Other additives, such as, for example, plasticisers, lubricants, emulsifiers, pigments, optical brighten-ers, flameproofing agents, antistatics and blowing agents.

The shaped articles according to the invention are obtained by mixing the individual components. Mixing can be carried out by known techniques in any manner, for example via kneaders or extruders. Further processing is carried out by the known techniques of thermoplastic processing, for example by extrusion or injection moulding.

Shaped articles according to the present invention are neck collars, neck collar pendants (medallions), ear, tail and foot tapes, ear marks, films, peel-off films, adhesive strips, strips, sheets and granules. Neck collars and medallions for dogs and cats may be mentioned as preferred.

The shaped articles are used for combating parasites on the host animal, which live on the host animal and in the environment of the host animals, such as domestic animals, pets and stock animals. 2 ^ C ^ / £ . ^ u o 4 The domestic animals, pets and stock animals include mammals, such as, for example, cattle, sheep, goats, horses, pigs, dogs and cats.

The pests include: From the order of the Anoplura, for example, Haematopinus spp., Linognathus spp., Solenopotes spp., Pediculus spp. and Pthirus spp.; from the order of the Mallophaga, for example, Trimenopon spp., Menopon spp., Eomenacanthus spp., Menacanthus spp., 10 Trichodectes spp., Felicola spp., Damalinea spp. and Bovicola spp.; from the order of the Diptera, for example, Aedes spp., Culex spp., Simulium spp., Phlebotomus spp., Chrysops spp., Tabanus spp., Musca spp., Hydrotaea spp., Muscina 15 spp., Haematobosca spp., Haematobia spp., Stomoxys spp., Fannia spp., Glossina spp., Lucilia spp., Calliphora spp., Auchmeromyia spp., Cordylobia spp., Cochliomyia spp., Chrysomyia spp., Sarcophaga spp., Wohlfartia spp., Gasterophilus spp., Oesteromyia spp., Oedemagena spp., 20 Hypoderma spp., Oestrus spp., Rhinoestrus spp., Melophagus spp. and Hippobosca spp..

From the order of the Siphonaptera, for example, Ctenocephalides spp., Echidnophaga spp., Ceratophyllus spp..

From the order of the Metastigmata, for example, Hyalomma spp., Rhipicephalus spp., Boophilus spp., Amblyomma spp., Eaemaphysalis spp., Dermacentor spp., Ixodes spp., Argas 2 4 5 f; O / spp./ Ornithodorus spp. and Otobius spp.; from the order of the Mesostigmata, for example, Dermanyssus spp., Ornithonyssus spp. and Pneuroonyssus spp..

From the order of the Prostigmata, for example, Cheyletiella spp., Psorergates spp., Myobia spp., Demodex spp. and Neotrombicula spp.; from the order of the Astigmata, for example, Acarus spp., Myocoptes spp., Psoroptes spp., Chorioptes spp., 10 Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Neoknemidocoptes spp. Cytodites spp. and Laminosioptes spp..

The following examples of insecticidal mouldings based on copolyether block amides are intended to illustrate the 15 invention without limiting it: Example A Composition: ^-Cyfluthrin 12.00 g Styrene block copolymer 20 (Thermolast K®) 92.50 g 100.00 g Production: The mixture is extruded to form neck collars for dogs in 25 a conventional manner. 24 5 0 C Example B 0-Cyfluthrin Pyriproxifen Triacetin .00 g 0.35 g 5.00 g Styrene block copolymer (Thermolast K*)84.65 g 100.00 g Production: The active compounds and triacetin are heated together until a clear solution results. Thermolast K is wetted with the warm solution of active compounds and triacetin in a mixer. The components are mixed until the mixture is homogeneous. Heating the mixture, for example as a result of increasing the speed of rotation of the mixer, promotes absorption of the solution into the styrene block copolymer. The mixture is extruded on an extruder to form sheets, from which medallions (= pendants for neck collars) of 2 x 4 cm are stamped. 24 5 on Example C Composition: Propoxur 7.50 g Styrene block copolymer (Thermolast K®) 92.50 g 100.00 g Production: The active compound is applied to the carrier in an intensive mixer and the mixture is shaped to form neck collars for dogs by injection moulding. 245

Claims (18)

WHAT WE CLAIM IS:

1. A shaped article which comprises an active compound selected from the group consisting of phosphoric or phosphonic acid esters, naturally occurring and synthetic pyrethroids, carbamates, amidines, juvenile hormones and analogous substances, and juvenoid synthetic active compounds; and a carrier comprising thermoplastic elastomers based on styrene/butylene block, copolymers; together with customary additives if appropriate.

2. A shaped article as claimed in claim 1, wherein the active compound is a phosphoric or phosphonic acid ester selected from the group consisting of 0-ethyl 0-(8-quinolyl) phenyl-thiophosphate (quintiofos), 0,0-diethyl 0-(3-chloro-4-methyl-7-coumarinyl) thiophosphate (coumaphos), 0,0 -diethyl O-phenylglyoxylonitrile oxime thiophosphate (phoxim), 0,0-diethyl O-cyanochlorobenzaldoxime thiophosphate (chlorphoxim), 0,0 -diethyl 0-(4-bromo-2,5-dichlorophenyl) phosphoro-thionate (bromophos-ethyl), 0,0,0',0'-tetraethyl-S,S'-methylene di(phosphorodi-thionate) (ethion), 2,3-p-dioxanedithiol-S,S-bis(0,0-diethyl) phosphorodi-thionate, 2-Chloro-l-(2,4-dichlorophenyl)-vinyl diethyl phosphate (chlorfenvinphos), and 0,0-dimethyl 0-(3-methyl-4-methylthiophenyl) thionophos-,-' phate (fenthion). 33

3. A shaped article as claimed in claim 1, wherein the active compound is a carbamate selected from the group consisting of 2-isopropoxyphenyl methylcarbamate (propoxur) and 1-naphthyl N-methylcarbamate (carbaryl).

4. A shaped article as claimed in claim 1, wherein the active compound is a synthetic pyrethroid.

5. A shaped article as claimed in claim 4, wherein the synthetic pyrethroid is a compound of the formula I Ri *1 /==\°7 \ R R4 R5 in which R1 and R2 represent halogen, optionally halogen-substi-tuted alkyl or optionally halogen-substituted phenyl, R3 represents hydrogen or CN, R4 represents hydrogen or halogen and R5 represents hydrogen or halogen. 34 Oh R n i! , •' ;

6. A shaped article as claimed in claim 5, wherein the synthetic pyrethroid is a compound of the formula I in which R1 represents fluorine, chlorine or bromine, represents fluorine, chlorine, bromine, trihalogenomethyl, phenyl or chlorophenyl, R3 represents hydrogen or CN, R* represents hydrogen or fluorine, and R5 represents hydrogen.

7. A shaped article as claimed in claim 6, wherein the synthetic pyrethroid is a compound of the formula I in which R1 represents chlorine, Rz represents chlorine or p-chlorophenyl, R3 represents CN, R* represents fluorine in the 4-position, and R5 represents hydrogen. 35 2450

8. A shaped article as claimed in claim 4, wherein the synthetic pyrethroid is a compound selected from the group consisting of: (a-cyano-4-fluoro-3-phenoxy)-benzyl 3-[2-(4-chloro-phenyl) -2-chlorovinyl] -2,2-dimethyl-cyclopropanecarboxyl-ate (flumethrin), a-cyano(4-fluoro-3-phenoxy)-benzyl 2 , 2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylate (cyfluthrin) and its enantiomers and stereomers, a-cyano-3-phenoxybenzyl (±)-cis,trans-3-(2,2-dibromo-vinyl)-2,2-dimethylcyclopropanecarboxylate (deltamethrin), a-cyano-3-phenoxybenzyl 2, 2-dimethy1- 3 - (2 , 2 -dichlorovinyl)-cyclopropanecarboxylate (cypermethrin), 3-phenoxybenzyl (±) -cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (permethrin) , a-cyano-3-phenoxy-benzyl a-(p-Cl-phenyl)-isovalerate (fenvalerate), and 2-cyano-3-phenoxybenzyl 2-(2-chloro-a,a,a-trifluoro-p-toluidino)-3-methylbutyrate (fluvalinate) .

9. A shaped article as claimed in claim 1, wherein the active compound is an amidine selected from the group consisting of: 3-methyl-2- [ 2,4-dimethyl-phenylimino ] -thiazoline, 2- (4-chloro-2-methylphenylimino) -3-methylthiazolidine, 2-(4-chloro-2-methylphenylimino) -3- ( isobutyl-l-enyl) -thiazolidine, and / 1,5-bis-(2,4-dimethylphenyl) -3-methyl-1,3, 5-triazapentia.-1,4-diene (amitraz). 36

10. A shaped article as claimed in claim 1, wherein the active compound is a juvenile hormone or an analogous substance selected from the group consisting of substituted diaryl ethers, benzoylureas, and triazine derivatives.

11. A shaped article as claimed in claim 10, wherein the substituted diaryl ether is a substituted alkoxydiphenyl ether, -diphenylmethane or thioether analogue of the general formula II wherein R1 represents hydrogen, halogen, alkyl, alkoxy, alkyl-thio, halogenoalkyl, halogenoalkoxy, halogenoalkyl-thio, dioxyalkylene, dioxyhalogenoalkylene, CN, N02, alkenyl, alkinyl, alkoxyalkyl, alkoxyalkoxy or hydroxyalkoxy, R2 represents the radicals mentioned for R1, R3 represents the radicals mentioned for R1, r4 and R5 are the same or different and represent hydrogen, alkyl, halogenoalkyl or halogen, Het represents optionally substituted heteroaryl, which is not bonded to the rest of the radical via the hetero atom, X and Y independently of one another represent -0- or -S- , Z represents -0-, -S-, -CH2- , -CHCH3- or -C (CH3) 2- , and m and n independently of one another represent 0, 1, 2 or 3, but their sum is equal to or greater than 2. 37 24503

12. A shaped article as claimed in claim 11, wherein the substituted alkoxydiphenvl ether or -diphenylmethane is of the general formula \ J - % . '/ 2 CH C ' ,/ n— where the variables R1. R3. R5. R\ and Z are denned as follows: r.'- 93 R5 z h u L n 2 jj 0 h h ch3 2-CI 0 5-f h ch3 h 0 h h cf3 h 0 •j h c2h5 h 0 h h h h 0 u u ch3 u ch h h ch3 h co

13. A shaped article as claimed in claim 10, wherein the active compound is a benzoylurea of the formula V R1 wherein R1 represents halogen, ^' R2 represents hydrogen or halogen, R3 represents hydrogen, halogen or C,_*-alkyl and R,, represents halogen, l-5-halogeno-C:_,-alkyl, C,.t-alkoxy, 1-5-halogeno-C^-aikoxy, C:_t-alkyithio, 1-5-halogeno-C^-alkylthio, phancxy or pyridyloxy, which phenoxy or pyridyloxy can optionally be substituted by halogen. CM-alkyl, l-5-halogeno-C,.»-alkyl, C^-alkoxy, 1-5-halogeno-C,_t-alkoxy, C,.4-alJcylthio or l-5-halogeno-C,-C;-alkylthio. 18

14. A shaped article as claimed in claim 10, wherein the active compound is a triazine of the formula VI NH-R R2~HN 1 nh-r- (vi) wherein R; represents cyclopropyl or isooroDvl; R2 denotes hydrogen, halogen, Ci-C^-alkylcarbonyl, cyclopropylcarbonyl, CrCu- alkylcarbamoyl, C,-CI2-aikvlthiocarbamoyl or C2-Cs-alkenylcarbamovl; and R3 represents hydrogen, C:-C12-alkyl, cyclopropyl, C,-Cs-alkenyl, C,-C12-alkylcarbonyl, cyclopropylcarbonyl, C;-C12-alkylcarbamoyl, C.-C,2-alkylthiocarbamoyl or C2~C5-alkenylcarbainoyl, and acid addition salts thereof which are non-toxic to warm-blooded animals.

15. A shaped article as claimed in claim 1, wherein the active compound is selected from the group consisting of propoxur, cyfluthrin, flumethrin, pyriproxyfen, methoprene, diazinon, amitraz and fenthion.

16. A process for the production of a shaped article as claimed in any one of claims 1-15, characterised in that thermoplastic elastomers based on styrene/butylene block copolymers are mixed with the active compound and if appropriate together with customary additives, and the mixture is processed in the customary manner. /?***("o 39

17. A shaped article according to claim 1 substantially as herein described or exemplified.

18. A process according to claim 16 substantially as herein described or exemplified. BAYER AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES LTD-Per: 40