IL103699A - Shaped articles which contain active compounds and are based on elastomeric copolyesters which can be processed as thermoplastics their production and their use for control of pests - Google Patents

Abstract

The present invention relates to mouldings containing active ingredients, which are characterised in that they contain, as support, thermoplastic elastomers based on copolyesters, optionally with conventional additives, to a process for their production, and to their use for the control of pests on animals.

Description

O > "ICON > !? ϊ 01p t?V D>DD13ni nit?> -) ninmn D>!?>DQn 0>3i<1VQ 0>0>~l-) vnn>v>rn ΟΊΊ.<> > ,D> ^oo^Diom o>-iniro -ni>yt? o>jn>jn , o > > ~in i ootw D>p> to mmni? oro Shaped articles which contain active compounds and are based on elastomeric copolyesters, which can be processed as thermoplastics, their products and their use for control of pests BAYER AKTIENGESELLSCHAFT, C: 87668 The present invention relates to new shaped articles which contain active compounds and are based on elasto-meric copolyesters which can be processed as thermoplastics, their production and their 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 plastics which contains active compounds (compare, for example, Aries et al US P 3 814 061, Greenberg US-P 3 918 407, Miller and Morales US-P 3 944 662, Millionis and Spicer US-P 4 041 151, Pasarela US-P 4 145 409, Greenberg and Cloud US-P 4 158 051, v. Bittera et al US-P 4 225 578. McDaniel and Pruitt EP-OS 0 052 411 Bl, 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 acceptance in practise. 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.

Le A 28 556 - 1 - This is also not surprising. PVC is inexpensive and 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 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 active compound determines whether and to what extent the shaped article can be employed in practise.

If one component of the overall system is changed, it can no longer be predicted whether the system still acts in practise. This applies in particular if the plasticiser, 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 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 practise.

'Thermoplastic elastomers are materials which comprise elastomeric phases either mixed physically or bonded chemically in polymers which can be processed as Le A 28 556 - 2 - thermoplastics. A distinction is made between polyblends; to 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 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) 4. Thermoplastic polyolefins (TPO) 5. 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 properties, these main groups behave completely differently in respect of mixing in and release of active compounds .

The use of certain thermoplastic elastomers as carriers for active compounds is known, for example, from EP-OS 338 821 and DE-OS (German Published Le A 28 556 - 3 - Specification) 3 611 137. The use of styrene/butadiene block copolymers as carriers is described in EP-OS (European Published Specification) 338,821. The use of polyether block amides as carriers for volatile active compounds is described in DE-OS (German Published Specification) 3,611,137.

The use of copolyesters as carriers for active compounds is not known.

The present invention relates to 1. Shaped articles which contain active compounds, characterised in that they comprise, as carriers, thermoplastic elastomers based on copolyesters, 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 copolyesters are mixed with active compounds and if appropriate customary additives and the mixture is processed in the customary manner.

In spite of having similar macroscopic properties, the main groups of the thermoplastic elastomers behave completely differently as regards mixing in and release of active compounds. Thus, for example, shaped articles based on thermoplastic polyurethane and thermoplastic olefins exhibit a completely inadequate release of active Le A 28 556 - 4 - compound. It is therefore not possible to draw conclusions from the behaviour of one representative of a main group of the thermoplastic elastomers on the other main groups.

It was surprising that shaped articles which contain active compounds and are based on elastomeric copolyesters which can be processed as thermoplastics having a good and long action under conditions in practice. It was particularly surprising that the shaped articles according to the invention lead to an adequate and long-lasting release of the active compound.

Suitable copolyesters (segmented polyester elastomers) are built up, for example, from a large number of recurring, short-chain ester units and long-chain ester units, which are combined by ester bonds, the short-chain ester units making up about 15-65% by weight of the copolyester and having the formula I.

•C-R-C-O-D-0- (I) in which R represents a divalent radical of a dicarboxylic acid, which has a molecular weight of less than about 350, and Le A 28 556 - 5 - D represents a divalent radical of an organic diol, which has a molecular weight of less than about 250, The long-chain ester units make up about 35-85% by weight of the copolyester and have the formula II II -c-R-c-0-σ-ο- II I! 0 0 in which R represents a divalent radical of a dicarboxylic acid, which has a molecular weight of less than about 350, and G represents a divalent radical of a long-chain glycol, which has an average molecular weight of about 350 to 6000.

The copolyesters which can be used according to the invention can be prepared by polymerizing with one another a) one or more dicarboxylic acids, b) one or more linear, long-chain glycols and c) one or more low molecular weight diols.

The dicarboxylic acids for the preparation of the copolyester can be aromatic, aliphatic or cycloaliphatic . The preferred dicarboxylic acids are the aromatic acids having 8-16 C atoms, in particular phenylene-dicarboxylic acids, such as phthalic, terephthalic and isophthalic Le A 28 556 acid.

The low molecular weight diols for the reaction to form the short-chain ester units of the copolyesters belong to the classes of acyclic, alicyclic and aromatic dihydroxy compounds. The preferred diols have 2-15 C atoms, such as ethylene glycol, propylene glycol, tetramethylene glycol, isobutylene glycol, pentamethylene glycol, 2,2-dimethyltrimethylene glycol, hexamethylene glycol and decamethy lene glycol, dihydroxycyclohexane , cyclohexanedimethanol, resorcinol, hydroquinone and the like. The bisphenols for the present purpose include bis-(p-hydroxy ) -diphenyl, bis- (p-hydroxyphenyl ) -methane, bis-(p-hydroxyphenyl ) -ethane and bis- (p-hydroxyphenyl) -propane .

The long-chain glycols for the preparation of the soft segments of the copolyesters preferably have molecular weights of about 600 to 3000. They include poly (alkylene ether ) glycols in which the alkylene groups have 2-9 carbon atoms.

Glycol esters of poly- (alkyleneoxide) -dicarboxylic acids can also be used as the long-chain glycol.

Polyester glycols can also be used as the long-chain glycol.

The long-chain glycols also include polyformals, which are obtained by reaction of formaldehyde with glycols.

Le A 28 556 - 7 - Polythioether glycols are also suitable. Polybutadiene glycols and polyisoprene glycols, copolymers thereof and saturated hydrogenation products of these materials are satisfactory long-chain polymeric glycols.

Processes for the synthesis of such copolyesters are known from DOS (German Published Specification) 2 239 271, DOS (German Published Specification) 2 213 128, DOS (German Published Specification) 2 449 343 and US-P 3 023 192.

Suitable copolyesters in the context of the invention are obtainable, for example, under the commercial names ®Hytrel from Du Pont, "Pelpren from Toyobo®, Arnitel from Akzo, ®Ectel from Eastman Kodak and ®Riteflex from Hoechst.

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, 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), Le A 28 556 - 8 - 0 O-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 ' -tetraethy1-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 ) 0,0-dimethyl 0- ( 3-methyl-4-methylthiophenyl ) thionophos-phate (fenthion) The carbamates include: 2-isopropoxyphenyl methylcarbamate (propoxur) 1-naphthyl N-methylcarbamate (carbaryl).

Le A 28 556 - 9 - The synthetic pyrethroids include compounds of the formula I formul in which R1 and R2 represent halogen, optionally halogen-substituted 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, Le A 28 556 - 10 - R3 represents hydrogen or CN, R* represents hydrogen or fluorine and R5 represents hydrogen.

Particularly preferred synthetic pyrethroids are those of the formula I in which R1 represents chlorine, Rz 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, Le A 28 556 - 11 - 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, Q-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) , Q-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) .

Le A 28 556 - 12 - 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: Le A 28 556 - 13 - Le A 28 556 - 14 - substituted alkoxydiphenyl ethers or -diphenylmethanes of the general formula I R4 R5 (CH)n-(CH)m-X-Het (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, Le A 28 556 - 15 - 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, Le A 28 556 - 16 - X represents 0, 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 R3 R5 R6 Z H H CH3 H 0 H H CH3 2-Cl 0 5-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)2 R1 R3 R5 R6 Z H H CH3 H 0 Le A 28 556 - 17 - Le A 28 556 - 18 - The benzoylureas include compounds of the formula (V) : wherein R1 represents halogen, R2 represents hydrogen or halogen, R3 represents hydrogen, halogen or C1.-alkyl and R4 represents halogen, l-5-halogeno-C1.A-alkyl, C^- alkoxy, l-S-halogeno-C^-alkoxy, C1.4-alkylthio, 1-5- halogeno-C^-alkylthio, phenoxy or pyridyloxy, which can optionally be substituted by halogen, C^-alkyl, l-S-halogeno-C^-alkyl, C^-alkoxy, 1-5-halogeno- C^-alkoxy, C^-alkylthio or 1-5-halogeno-Ci-C,,- alkylthio.

The following compounds may be mentioned in particular: Le A 28 556 - 19 - R1 R2 R4 H CI CF3 CI CI CF3 F F CF3 H F CF3 H CI SCF3 F F SCF3 H F SCF3 H CI OCF3 F F OCF3 The triazines include compounds of the formula (VI) R-,- wherein Le A 28 556 - 20 - represents cyclopropyl or isopropyl; R2 denotes hydrogen, halogen, C1-C^-alkylcarbonyl , cyclopropylcarbonyl, C^C^-alklcarbamoyl, ^-012- alkylthiocarbamoyl or C2-C6-alkenylcarbamoyl ; and R3 represents hydrogen, C^-C^-alkyl, cyclopropyl, C2-C6- alkenyl, C1-C^-alkylcarbonyl, cyclopropylcarbonyl, C^C^-alkylcarbamoyl, C^C^-alkylthiocarbamoyl or C2-C6-alkenylcarbamoyl, and acid addition salts thereof which are non-toxic to warm-blooded animals.

Compounds which may be mentioned in particular are: Rl R2 R3 r' Cyc 1 opropy1 H H Cyc lopropy 1 H CH3 Cyc 1 opropy 1 H C2H5 Cyc 1 opropy 1 H C3H7-n Cyc 1 opropy1 H C^H^-n Cyclopropyl H C5H11-n Cyc lopropy1 H C6H13"n Cyc 1 opropyl H C7H15"n Cyc 1 opropyl H CQH17-n Le A 28 556 - 21 - (Continuation) Rl R2 R3 Cyc lopropy1 H C12H25~n Cyc 1 opropy1 H - t.

Cyc 1 opropy1 H CH2CH ( H^ ) C^H Cyc 1 opropy1 H CH2CH=CH2 Cyc 1 opropy1 CI C2H5 Cyc 1 oprop 1 CI C6H13"n Cyc 1 opropy 1 CI C8H17-n Cyc 1 opropy 1 CI C12H25"n Cyc 1 opropy 1 H Cyc 1 opropy 1 Cyc 1 opropy 1 H COCH3 Cyc 1 opropy 1 H COCH3 'HCl Cyc 1 opropy1 H COC2H5 'HCl Cyc 1 opropyl H COC2H5 Cyc 1 opropyl H COC3H7-n Cyc 1 opropyl H COC3H7-i Cyc lopropy 1 H COC4H9- t * HC 1 Cyc 1 opropyl H C0C4H9-n Cyc 1 opropyl H COC6H13"n Cyc 1 opropyl H C0Cll"H23-n Cyc 1 opropyl COCH3 COC2H5 Cyc 1 opropyl COC3H7-n COC6H13"n Cyc opropyl COCH3 COC3H7-n Cyc lopropy 1 C0C2H5 COC3H7-n Cyc 1 opropyl H COCyc lopropyl Cyc lopropy 1 COCylclopropyl COCyc loprop 1 Cyc 1 opropyl COCH3 COCH3 I sopropyl H H Le A 28 556 - 22 - ( Continuation ) Rl R2 R3 I sopropy 1 H COCH3 I sopropyl H COC3H7-n Cyc 1 opropyl H CONHCH3 Cyc 1 opropyl H CONHC3H7-i Cyc lopropyl CONHCH3 CONHCH3 Cyc 1 opropyl H CSNHCH3 Cyc 1 opropyl H CONHCH2CH=CH2 Cyc 1 opropyl CONHCH2CH=CH2 CONHCH2CH=CH2 Cyc 1 opropyl CSNHCH3 CSNHCH3 The active compounds having the common names propoxur, cyfluthrin, flumethrin, pyriproxyfen, methoprene, Diazinon, amitraz and fenthion may be singled out in 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 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, Le A 28 556 - 23 - 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 hydroquinones . 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 Hydroxylated thiodiphenyl 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 Alkylidene-bisphenols . for example 2,2 '-methylene- bis-(6-tert-butyl-4-methylphenol) , 2,2 '-methylene- bis- ( 6-tert-butyl-4-ethylphenol ) , Le A 28 556 - 24 - 2,2' -methylene-bis- ( 4-methyl-6 ( α-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-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-( 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 ) -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-2 ' -hydroxy-5 ' -methylbenzyl ) -6-tert-butyl-4-methyl-phenyl] terephthalate .

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 , isooctyl 3 , 5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetate, bis- (4-tert-butyl-3-hydroxy-2 , 6-dimethylbenzyl) 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 ) 28 556 - 25 - 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 Acylaminophenols . for example 4-hydroxy-lauric acid anilide, -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 B- 13.5-di-tert-butyl-4-hvdroxyphenyl ) - 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 3- ( 5-tert-butYl-4-hydroxy-3-methylphenyl ) - 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 θ- ( 3.5-di-tert-butyl-4-hydroxyphenyl ) - propionic acid, such as, for example, N,N'-di-(3,5- di-tert-butl-4-hydroxyphenylpropionyl ) - Le A 28 556 - 26 - hexamethylenediamine, Ν, '- ( 3 , 5-di-tert-butyl-4-hydroxyphenylpropionyl ) -trimethylenediamine and N,N'-di- ( 3 , 5-di-tert-butyl-4-hydroxyphenylpropion-yl)- hydrazine.

UV absorbers and light stabilisers 2- 1 2 ' -Hydroxyphenyl ) -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 ^-dimethyl-benzyl) derivative. 2-Hydroxybenzophenones . 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 .

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 .

Acrylates . such as, for example, ethyl or isooctyl a-cyano-/9,0-diphenylacrylate, methyl a-carbomethoxy- cinnamate, methyl or butyl o-cyano-^-methyl-p-methoxy-cinnairtate, methyl a-carbomethoxy-p-methoxy-cinnamate and N-(j8-carbomethoxy- -cyanovinyl)-2-methyl-indoline .

Nickel compounda. such as, for example, nickel complexes of 2 , 2 '-thio-bis- [4- ( 1 , 1, 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.

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, '-( 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 , V 28 556 - 28 - 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 ) .

Oxalic acid diamides. such as, for example, 4,4 '-di-octyloxy-oxanilide , 2,2' -di-octyloxy-5 , 5 ' -di-tert-buty1-oxanilide , 2,2' -di-dodecyloxy-5 , 5 ' -di-tert-butyl-oxanilide, 2-ethoxy-2 '-ethyl-oxanilide, Ν,Ν'-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.

Metal deactivators, such as, for example, Ν,Ν'-diphenyloxalic acid diamide, N-salicylal-N'-salicyl-oylhydrazine, N, '-bis- ( salicyloylhydrazine, Ν,Ν'-bis- ( 3 , 5-di-tert-butyl-4-hydroxyphenylpropionyl ) -hydrazine, 3-salicyloylamino-l,2,4-triazole and bis-benzylidene-oxalic acid dihydrazide.

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-butylphenyl ) - 28 556 - 29 - 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-deBtroyinq compounds , such as, for example, esters of ,9-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-( 0-dodecylmercapto ) -propionate .

Polyamide stabilisers, such as, for example, copper salts in combination with iodides and/or phosphorus compounds, and salts of divalent manganese.

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 .

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. 10. 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.

Le A 28 556 - 31 - 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., 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 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., 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., Haemaphysalis spp., Dermacentor spp., Ixodes spp., Argas Le A 28 556 - 32 - spp., Ornithodorus spp. and Otobius spp.; from the order of the Mesostigmata, for example, Dermanyssus spp., Ornithonyssus spp. and Pneumonyssus 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., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Neoknemidocoptes spp. Cytodites spp. and Laminosioptes spp..

The following examples of insecticidal mouldings based on copolyesters are intended to illustrate the invention without limiting it: Example A Composition: ^-Cyfluthrin 12.00 g Copolyester (Hytrel®) 88.00 g 100.0 Production: The mixture is extruded to form neck collars for dogs a conventional manner.

Le A 28 556 - 33 - Example B Composition: 0-Cyfluthrin 10.00 g Pyriproxifen 0.35 g Triacetin 5.00 g Copolyester (Hytrele) 84.65 g 100.00 g Production r The active compounds and triacetin are heated together until a clear solution results. Hytrel 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, pro-motes absorption of the solution into the copolyester. The mixture is extruded on an extruder to form sheets, from which medallions ( = pendants for neck collars) of 2 x 4 cm are stamped.

Example C Composition: Propoxur Copolyester (Riteflex*) 100.00 g Production: The active compound is applied to the carrier Le A 28 556 - 34 - intensive mixer and the mixture is shaped to form neck collars for dogs by injection moulding.

Le A 28 556 - 35 -

Claims (4)

103699/2 - 36 - Claims I . ·

1. Neck collars and neck collar pendants for combating parasites on animals, comprising synthetic pyrethroids as parasitically active ingredients and, as carriers, thermoplastic elastomers based on copolyesters, optionally together with customary additives.

2. Neck collars and neck collar pendants according to Claim 1 which comprise, as active ingredients, synthetic pyrethroids of the formula I. formuJ in which 1 2 R and R represent halogen, optionally halogen-substituted alkyl or optionally halogen-substituted phenyl, represents hydrogen or CN, represents hydrogen or halogen and R 5 represents hydrogen or halogen, a-cyano-3-phenoxy-benzyl a- (p-Cl-phenyl) -isovalerate ( fenvalerate) . or 2-cyano-3-phenoxybenzyl 2- ( 2-chloro-c* , a , a-trifluoro-p-toluidino) -3-methylbutyrate ( fluvalinate ) . 103699/ 1 - 37 -

3. Neck collars and neck collar pendants according to Claim 1 which comprise, as active ingredients, cyfluthrin or flumethrin.

4. A process for the production of neck collars and neck pendants according to any one of Claims 1 to 3, characterised in that thermoplastic elastomers based on copolyesters are mixed with active compounds and, if appropriate, customary additives and the mixture is processed in a customary manner. Fo r tfcie Appl i cants , RE I NUOUXCOHN AND PARTNERS