NO301682B1 - Active ingredient moldings based on thermoplastic workable elastomeric copolyester - 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

The present invention relates to shaped bodies containing active substances, more specifically collars and collar pendants, based on thermoplastically processable elastomeric copolyesters, for the control of pests, especially for utility and farm animals.

Molds containing active substances for the control of pests are known. They are based on the slow release of active substances from an active substance-containing carrier matrix of synthetic material (see for example Aries et al US-PS 3,814,061, Greenberg US-PS 3,918,407, Miller and Morales US-PS 3,944,662, Millionis and Spicer US-PS 4,041,151, Pasarela US-PS 4,145,409, Greenberg and Cloud US-PS 4,158,051, V. Bittera et al US-PS 4,225,578, McDaniel and Pruitt EP-OS 0,052,411 Bl, Grubb et al US-PS 3,852,416 and Pearce US-PS 4,536,388.

With the known molded bodies, the carrier used is almost exclusively PVC. Other carriers are admittedly mentioned in the literature, but have not yet found application in practice. Thus, for example, in US-PS 4,195,075 it is mentioned, among other things, that thermoplastic elastomers are also relevant as carrier materials for ear tags. Admittedly, examples with plasticizer-containing PVC as carrier polymer are also described in this quotation.

This is not surprising. PVC is inexpensive and readily available. It is also miscible in large areas with other substances, especially plasticizers. In the case of PVC bodies containing the active substance, these plasticizers have the function of keeping the active substance dissolved in the carrier, transporting this slowly to the surface of the body. The active substance evaporates or is torn from the surface together with the plasticizer. The interaction of the three components - PVC carrier, plasticizer and active ingredient - determines whether and whether the mold is practical.

If a component in the total system is changed, it is no longer possible to predict whether the system still works in practice. This applies in particular if the mucin, which has a key role in the transport of the active substance, is changed or removed.

For various reasons, it is desirable to replace PVC as a carrier material. It is also beneficial to completely or partially avoid the use of plasticizers. The aim is therefore to find an active substance-mould system that can be avoided using PVC as carrier material as well as plasticizer and which is nevertheless very effective in practice.

Thermoplastic elastomers are raw materials where the elastomeric phases in thermoplastically processable polymers are contained either physically mixed in or chemically bound. A distinction is made between polyblends where the elastomeric phases are physically mixed in and block copolymers where the elastomeric phases are components of the polymeric skeleton. Due to the construction of the thermoplastic elastomer, hard and soft areas exist next to each other. The hard areas here form a crystalline network structure or a continuous phase where the spaces are filled by elastomeric segments. Due to this structure, these raw materials have rubber-like properties.

One can distinguish between 5 main groups of thermoplastic elastomers:

1. Copolyester

2. Polyether block amide (PEBA)

3. Thermoplastic polyurethane

4. Thermoplastic polyolefins (TPO)

5. Styrene block copolymers

These 5 main groups show similar macroscopic physical properties due to their chemically completely different structure. Despite these macroscopically similar properties, these main groups behave completely differently when mixing and releasing active substances.

The use of certain thermoplastic elastomers as carriers for active substances is known, for example, from EP-OS 338,821, DE-OS 3,611,137. In EP-OS 338,821, the use of styrene butadiene block copolymer as carrier is described. DE-OS 3,611,137 described the use of polyether block amides as carriers for volatile active substances.

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

The subject of the present invention is collars and collar pendants (medallions) for combating parasites on animals, characterized by the fact that they contain thermoplastic elastomers based on copolyesters as carriers and as active ingredients contain parasiticidal active ingredients from the group of synthetic pyrethroids, possibly alongside common additives.

Despite similar macroscopic properties, the main groups of thermoplastic elastomers behave completely differently in relation to the incorporation and release of active substances. Thus, for example, molded bodies based on thermoplastic polyurethanes and thermoplastic olefins show a completely insufficient active ingredient release. It is also not possible to draw conclusions from the behavior of a representative of a main group of thermoplastic elastomers from the other main groups.

It was surprising that molded bodies containing active ingredients based on thermoplastically processable elastomeric copolyesters work well and for a long time under practical conditions. It was particularly surprising that the moldings of the invention achieved a sufficient and long-lasting active substance release.

Suitable copolyesters (segmented polyester elastomers) are, for example, made up of a plurality of repeating, short-chain ester units and long-chain ester units which are connected through ester linkages, where the short-chain ester units make up about 15 to 65% by weight of the copolyester and have formula I

where

R stands for a divalent residue of a dicarboxylic acid, which has a molecular weight of about 350,

D stands for a divalent residue of an organic diol that has a molecular weight below about 250.

The long-chain ester unit makes up about 35 to 85% by weight of the copolyester and has formula II

where

R stands for a divalent residue of a dicarboxylic acid having a molecular weight of less than about 350,

G stands for a divalent residue of a long-chain glycol having an average molecular weight of about 350 to 6000.

The applicable copolyesters of the invention are produced by polymerizing with each other 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 producing the copolyesters can be aromatic, aliphatic or cycloaliphatic. The preferred dicarboxylic acids are the aromatic acids with 8 to 16 carbon atoms, especially phenylenedicarboxylic acids, such as phthalic, terephthalic and isophthalic acids.

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

The long-chain glycols for producing the soft segments of the copolyester preferably have a molecular weight of around 600 to 3000. These include poly-(alkylene ether) glycols, where the alkylene groups contain 2-9 carbon atoms.

Glycol esters of poly(alkylene oxide) dicarboxylic acids can also find use as long-chain glycols.

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

The long-chain glycols also include polyformals, which are formed by reacting formaldehyde with glycols. Polythioether glycols are also suitable. Polybutadiene and polyisoprene glycol, blend polymers of the same, and saturated hydrogenation products of these materials make satisfactory long-chain polymeric glycols.

Procedures for a synthesis of these copolyesters are known from DOS 2,239,271, DOS 2,213,128, DOS 2,449,343 and US-PS 3,023,192.

Suitable copolyesters in the spirit of the invention are, for example, available under the trademarks ®Hytrel from Du Pont, ®Pelpren from Toyobo, Arnitel from Akzo, ®Ectel from Eastman Kodak and ®Riteflex from Hoechst.

Insecticides, especially parasiticides for use on animals, can preferably be mentioned as active substances for the shaped bodies of the invention. The insecticides include synthetic pyrethroids.

The synthetic pyrethroids include compounds with formula I

where

R<1> and R<**> stand for halogen, possibly halogen-substituted

alkyl, optionally halogen-substituted phenyl,

R<3> stands for hydrogen or CN,

R<4> stands for hydrogen or halogen,

r<5> stands for hydrogen or halogen.

In particular, mention may be made of: 3-[2-(4-chlorophenyl)-2-chlorovinyl]-2,2-dimethyl-cyclopropane-carboxylic acid [(a-cyano-4-fluoro-3-phenoxy)-benzyl]ester (Flurnethrin) , 2 , 2-dimethyl-3-( 2 , 2-dichlorovinyl )-cyclopropanecarboxylic acid-α-cyano(4-fluoro-3-phenoxy)-benzyl ester (Cyfluthrin) and its enantiomers and stereoisomers, α-cyano-3-phenoxybenzyl(±)-cis, trans-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate (Deltamethrin), 2, 2-dimethyl-3-(2,2-dichlorovinyl)- cyclopropanecarboxylic acid α-cyano-3-phenoxybenzyl ester (Cypermethrin),

3-phenoxybenzyl(± )-cis, trans-3-(2,2-dichlorovinyl)-2,2dimethyl-cyclopropanecarboxylate (Permethrin),

α -(p-Cl-phenyl )-isovaleric acid α-cyano-3-phenoxy-benzyl ester (Fenvalerate),

2-cyano-3-phenoxybenzyl-2-(2-chloro-α,α,α,-trifluoro-p-toluidino)-3-methylbutyrate (fluvalinate).

The active substances can be present in the molded bodies alone or in a mixture with each other.

The active substances are present in the shaped bodies in concentrations from 0.1 to 20 wt.*, preferably between 1 and 10 wt.*.

The moldings of the invention can also contain the usual additives for plastics. Common additives, for example pigments, or stabilisers, plasticisers, lubricants, release agents.

Examples of common additives are:

1. Antioxidants

1.1 Alkylated monophenol, for example 2,6-di-tert.butyl-4-methylphenol, 2-tert.butyl-4,6-dimethylphenol, 2,6-di-tert.butyl-4-ethylphenol, 2,6- di-tert.butyl-4-n-butyl-phenol, 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,

2,4,6-tricyclohexylphenol, 2,6-di-tert.butyl-4-methoxymethylphenol.

1.2 Alkylated hydroquinone, for example 2,6-di-tert.butyl-4-methoxyphenol, 2,5-di-tert.butyl-hydroquinone, 2,5-di-tert.amyl-hydroquinone, 2,6-diphenyl- 4-octadecyl-oxyphenyl.

1.3 Hydroxylated thiodiphenyl ether, 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), 4,4'-thio-bis-(6-tert.butyl-2-methyl-phenol).

1.4 Alkylated bisphenol, for example 2,2'-methylene-bis-(6-tert.butyl-4-methylphenol), 2,2'-methylene-bis-(6-tert.butyl-4-ethylphenol), 2, 2-methylene-bis-(4-methyl-6(α-methylcyclohexyl)-phenol), 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis-( 6-nonyl-4-methylphenol), 2,2'-methylene-bis-(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis-(4,6-di-tert-butyl -phenol), 2,2'-ethylidene-bis-(6-tert.butyl-4-isobutyl-phenol), 2,2'-methylene-bis-[6-(c-methylbenzyl )-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-methylphenyl)-3-n-dodecyl-mercaptobutane, ethylene glycol-bis-[3,3-bis-(3'-tert. butyl-4'-hydroxyphenyl)-butyrate], di-(3-tert.butyl-4-hydroxy-5-methyl-phenyl)-dicyclo-penta diene, di-[2-(3*-tert.butyl-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)-sulfide, 3,5-di-tert.butyl-4-hydroxybenzyl -mercaptoacetic acid isooctyl ester, bls-(4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl )-dithiol-terephthalate, 1 ,3,5-tris-(3,5-di-tert.butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris-(4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl) -i socyanurate, 3,5-di-tert. buty 1-4-hydroxybenzylphosphonic acid dioctadecyl ester, 3,5-di-tert.butyl-4-hydroxybenzylphosphonic acid monoethyl ester, calcium salt.

1.6 Acylaminophenol, for example 4-hydroxylauric anilide, 4-hydroxystearic anilide, 2,4-bis-octylmercapto-6-(3,5-di-tert.butyl-4-hydroxyanilino)-s-(triazine, N-(3,5-di-tert.butyl-4-hydroxy-phenyl)-carbamic acid octyl ester.

1.7 Ester of P-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionic acid with mono or polyhydric alcohols, such as methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, Pancreas erythritol, tris-hydroxyethyl isocyanurate, di-hydroxyethyl oxalic acid diamide.

1.8 Ester of p-(5-tert.butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols, such as with emtanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate, dihydroxyethyl oxalic acid diamide.

1.9 Amides of P-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionic acid, such as N,N'-di-tert.butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine, N,N' -

(3,5-di-tert.butyl-4-hydroxyphenylpropionyl)-

trimethylenediamine, N,N'-di-(3,5-di-tert.butyl-4-hydroxyphenylpropionyl)-hydrazine.

2. UV absorbers and light protection agent

2.1 2-(2'-Hydroxyphenyl)-benzotriazole, such as 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 The '-tert.butyl, 4'-octoxy-, 3', 5'-di-tert.amyl-, 3',5'-bis-(α,α-dimethylbenzyl) derivs.

2.2 2-hydroxybenzophenone, such as 4-hydroxy-,

The 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4'-trihydroxy-, 2*-hydroxy-4,4'-dimethoxy derivs.

2.3 Esters of optionally substituted benzoic acids, such as 4-tert.butyl-phenylsalicylate, phenylsalicylate, octylphenylsalicylate, dibenzoylresorcinol, bis-(4-tert.butylbenzoyl)-resorcinol, benzoylresorcinol, 3,5-di-tert.butyl-4- hydroxybenzoic acid 2,4-di-tert-butyl phenyl ester, 3,5-di-tert-butyl 4-hydroxybenzoic acid hexadecyl ester.

2.4 Acrylates, such as a-cyan-<p>,e-diphenylacrylic acid ethyl ester, respectively -isooctyl ester, a-carbomethoxy-panic acid, a-cyano-p<->methyl-p-methoxy-panic acid methyl ester, respectively -butyl ester, α-Carbomethoxy-β-methoxy-panel acid methyl ester, N-(ε-carbomethoxy-ε-cyanovinyl)-2-methyl-indoline.

2.5 Nickel compounds, such as nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl )-phenols], as 1:1- or 1:2 complex, optionally with additional ligands , such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyl-

dithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert.butylbenzylphosphonic acid monoalkyl esters, such as from the methyl or ethyl ester, nickel complexes of ketoximes, such as from 2-hydroxy-4-methyl-phenyl-undecylketonoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazoles, optionally with further ligands.

2.6 Sterically hindered amines, such as bis-(2,2,6,6-tetramethylpiperidyl)-sebacate, bis-(1,2,2,6,-6-pentamethylpiperidyl)-sebacate, n-butyl-3,5 -di-tert.butyl -4-hydroxybenzyl -malonic acid-bis-(1,2,2,6,6-pentamethylpiperidyl)-ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N'-(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-tert.octylamino-2,6-dichloro-1,3,5-s-triazine, tris-(2,2,6,6-tetramethyl-4-piperidyl)-nitrotriacetate, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylic acid, 1, 1'-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone).

2.7 Oxalic acid diamide, such as 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, mixtures of o- and p-methoxy- as well as of o- and p-ethoxydi- substituted oxanilides.

3. Metal deactivators, such as N,N'-di-phenyloxaic acid diamide, N-salicylal-f<P->salicyloyl-hydrazine, N,N'-bis-salicyloylhydrazine, N,N'-bis-(3,5- di-tert.butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis-benzylideneoxal acid dihydrazide.

4. Phosphite and phosphonite, such as triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tri-(nonyl-phenyl)-phosphite, trilaurylphosphite, trioctadecylphosphite, distearyl-pentaerythritol diphosphite, tris-(2,4-di-tert.butyl phenyl)-phosphite, diisodecyl pentaerythritol diphosphite, di-(2,4-di-tert.butylphenyl)-pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis-(2,4-di-tert.butylphenyl)-4,4'-biphenylene diphosphonite, 3 ,9-bis-(2,4-di-tert.butylphenoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane. 5. Peroxide interfering compounds, such as esters of ->thiodipropionic acid, for example lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazoles, zinc dibutyl dithiocarbamate, dioctadecyl disulphide, pentaerythritol tetrakis-(p-dodecylmercapto)-propionate. 6. Polyamide stabilizers, such as, for example, copper salt in combination with iodides and/or phosphorus compounds and salts of divalent manganese 7. Basic co-stabilizers, such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, horn substance derivatives, amine, polyamide, polyurethane, alkali and alkaline earth salts of higher fatty acids, for example Ca-stearate, Zn-stearate, Mg-stearate, Na-ricinoleate, K-palmitate, antimonbrenzcatechinate or tinbrezcatechinate. 8. Nucleating agent, such as 4-tert.butyl-benzoic acid, adipic acid, diphenylacetic acid. 9. Filler and reinforcing agent, such as calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulphate, metal oxides and hydroxides, rust, graphite. 10. Additional additives, such as plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, propellants.

The moldings of the invention are produced by mixing the individual components. The mixing can be done according to known techniques in different ways, for example a kneader or screw machine. The further processing is done by known techniques in thermoplastic processing, for example by extrusion or injection molding.

Forms according to the present invention are collars, collar pendants (medallions), ear, tail, foot bands, ear tags, foils, transfer foils, adhesive strips, strips, plates, granules. Preferably collars and medallions for dogs and cats can be mentioned.

The molded bodies serve to combat parasites from the host animals, and the host animal and in the environment of the host animals as domestic, hobby or utility animals.

Domestic, hobby and utility animals include mammals such as cattle, sheep, goats, horses, pigs, dogs and cats.

The pests include:

from the order anoplura for example Haematopinus spp., linognath-hus spp., solenopotes spp., pediculus spp., pthirus spp.;

for order mallophaga for example trimenopon spp., menopon spp., eomencanthus spp., menacanthus spp., trichodectes spp., felicola spp., damalinea spp., bovicola spp;

for the order diptera, for example æedes spp., culex spp., simulium spp., sclepotomus spp., chrysops spp., tabanus spp.,

musea spp., hydrotaea spp., museina spp., haematobosca spp., haematobia spp., stomoxys spp., fannia spp., glossina spp., lucilia spp., calliphora spp., auchmeromyia spp., cordyldbia spp., sochlimyia spp. ., chrysomyia spp., sarcophaga spp., wohlfartia spp., gasterophilus spp., oesteromyia spp., oedemagena spp., hypoderma spp., oestrus spp., rhinoestrus spp., melophagus spp., hippobosca spp..

From the order siphonaptera, for example ctenocephalidr spp., echidnophaga spp., ceratophyllus spp..

From the order metastigmata for example hyalomma spp., rhipi-cephalus spp., boophilus spp., amblyomma spp., haemaphysalis spp., dermacentor spp., ixodes spp., argas spp., ornithodorud spp., otobius spp.;

from the order mesostigmata for example dermanyssus spp., ornithonyssus spp., pneumonyssus spp..

From the order prostigmata for example cheyletiella spp., psorergates spp., myobia spp., demodex spp., neotrombicula spp.;

from the order astigmata for example acarus spp., myocoptes spp., psoroptes spp., chorioptes spp., otodectes spp., sarcoptes spp., notoedres spp., knemidocoptes spp., neoknemidocoptes spp. cytodites spp., laminosioptes spp..

The following examples of insecticidal moldings based on the copolyesters are intended only to illustrate the invention without inscribing it:

Example A

Manufacturing:

The mixture was extruded into dog collars in the usual way. Example B

Manufacturing:

The active substance and triacetin were heated together until a clear solution was formed. Hytrel was moistened in the warm solution of the active ingredient and triacetin in a mixer. One mixed until the mixture was homogeneous. This requires heating of the mixture, for example as a result of an increase in the speed of the mixer, the dissolution in the copolyester. The mixture is extruded in an extruder into sheets, from which medallions are punched (= pendants for necklaces) to 2 x 4 cm.

Example C

Manufacturing:

The active ingredient is brought into the carrier with an intensive mixture and the mixture is injection molded to form dog collars.

Claims (4)

1. Collars and collar pendants (medallions) for combating parasites on animals, characterized in that they contain thermoplastic elastomers based on copolyesters as carriers and as active ingredients contain parasiticidal active ingredients from the group of synthetic pyrethroids, possibly alongside common additives. 2. Collars and collar pendants (medallions) according to claim 1, characterized in that they contain synthetic pyrethroids of formula I as active ingredients where R<1> and R<2> stand for halogen, optionally halogen-substituted alkyl, optionally halogen-substituted phenyl, R<3> stands for hydrogen or CN, R<4> stands for hydrogen or halogen, R<5>stands for hydrogen or halogen, α - (p-Cl - phenyl )-isovaleric acid-α-cyano-3-phenoxy-benzyl ester (fenvalerate) or 2-cyano-3-phenoxybenzyl -2- (2 -chloro-α,α,α-trifluoro-p-toluidi-no)-3-methylbutyrate (fluvinate). 3. Necklaces or necklace pendants (medallions) according to claim 1, characterized in that they contain synthetic pyrethroids of formula I as active substances where R<1> stands for chlorine, R<2> stands for chlorine or p-chlorophenyl, R<3> stands for CN, R<4> stands for fluorine in the 4-position, R<5> stands for hydrogen, α-(p-Cl - phenyl)-isovaleric acid-α-cyano-3-phenoxy-benzyl ester (fenvalerate) or 2-cyano-3-phenoxybenzyl -2-(2-chloro-a , a ,a-tr i fluoro-p-t olui di - no)-3-methylbutyrate (fluvalinate). 4. Collars or collar pendants (medallions) according to claim 1, characterized in that they contain as active ingredient the active ingredient with the name cyfluthrin, flumethrin.