CA2095770A1 - Shaped articles for combating ectoparasites on animals - Google Patents

Abstract

Shaped articles for combating ectoparasites on animals A b s t r a c t The present invention relates to shaped articles, which contain the active compounds flumethrin and propoxur, for combating ectoparasites.

Le A 29 044

Description

2~95~7~

The present invention relates to shaped articles for combating ectoparasites on animals, comprising the active compounds flumethrin and propoxur.

~ -Cyano-3-phenoxy-4-fluorobenzyl 2,2-dimethyl-3-~2"-p-chlorophenyl-2~-chlorovinyl)-cyclopropane-l-carboxylate (common name flumethrin) and o-(2-isopropoxyphenyl) N-methylcarbamate (propoxur) are known.

Mixtures of flumethrin and propoxur which are used in the forms of sprays, dips or pour-on solutions for combating ectoparasites are known (DE-OS (German Published Specification) 2,932,920). In uses where they are applied together in defined concentration~, the active compounds influence each other synergistically.

Animal collars, to combat fleas, made of polymers, such as, for example, PVC and comprising propoxur as the active compound are known (U.S. Patent 3,852,416).
However, these collars have an only inadequate action against ticks. Furthermore, the duration of their action leaves something to be desired.

Although animal collars which comprise flumethrin as the active compound are not described in detail in the literature, they have demonstrated only inadequate actions against fleas and ticks in practical studies.
This action also cannot be increased by increasing the Le A 29 044 - 1 -active compound co~centrations in the polymer, since this leads to skin intolerances.

The present invention relates to 1. Shaped articles for combating ectoparasites in animals, which comprise flumethrin and propoxur as the active compounds.

2. Use of flumethrin and propoxur as ac~tive compounds in shaped articles for combating ectopara~ites on animals.

3. Use of flumethrin and propoxur as active compounds for the production of shaped articles for combating ectoparasites on animals.

The mutual synergistic influencing of flumethrin and propoxur was known from DE-OS (German Published Specification) 2,932,920. A prerequisite of this syner-gistic influencing is, however, that the two active compounds arrive at the place of use in a certain concen-tration ratio relative to one another~ In the case of direct u~e via sprays, dips and the like, this can be controlled by the user.

However, if the active compounds are incorporated into a polymeric carrier system, prediction of possible syner-gism i8 not possible. From the release of the active compounds from polymers which compri~e only one of the Le A 29 044 - 2 -209~770 active compounds, no conclusions can be drawn as to what extent and in what ratio relative to one another acti~e compound mixtures are released from polymers.

Analytical studies of the release of the active compound~
flumethrin and propoxur from PVC ~how that flumethrin is released lO times more slowly than propoxur.

Since flumethrin moreover indeed has an excellent action against ticks, but does not have an action against fleac which can be used in practice, it was not to be expected that a mixture of propoxur and flumethrin in polymeric carriers causes a significant prolonging in the action against fleas of an animal collar produced therefrom.
Precisely this increase in the duration of action against fleas was to be found in the shaped articles according to the invention.

Shaped articles according to the present invention are, inter alia, collars, pendants for collars (medallions), ear tags, tapes for attaching to lLmbs or parts of the body, adhesive strips and films and peel-off films.

Collars and medallions may be singled out in particular.

The shaped articles comprise propoxur in concentrations of 1 - 20 % by weight, preferably 5 - 20 % by weight, particularly preferably 10 % by weight. Flumethrin is present in concentrations of 0.001 - lO % by weight, preferably 0.01 - 5 ~ by weight, particularly preferably Le A 29 044 - 3 -2~77~
0.1 - 5 ~ by weight.

In the case of collars, the concentration of the active compounds is preferably 1 - 15 ~; in the case of medal-lions, pendants and ear tags, it is preferably 5 - 20 %, and in the case of films and adhesive strips it is preferably 0.1 - 5 %.

The shaped articles according to the invention can additionally comprise fragrances, spreading agents and skin and coat care substances.

Possible spreading agents or spreading oils are the following substances:

Silicone oils of varying viscosity; fatty acid esters, such as ethyl stearate, hexyl laurate and dipropylene glycol pelargonate; esters of branched fatty acids of medium chain length with saturated C16-C18-fatty alcohols, such as isopropyl myristate and isopropyl palmitate;
caprylic/capric acid esters of saturated fatty alcohols of chain length C12-C18, isopropyl stearate, decyl oleate and oleyl oleate; waxy fatty acid esters, diisopropyl adipate and est.er mixtures related to the latter, inter alia triglycerides, such as caprylic/capric acid trigly-ceride, triglyceride mixtures with plant fatty acids of chain length C8-C12 or other specifically selected natur-ally occurring fatty acids; and glyceride mixtures of saturated or unsatur~ted fatty acids, which may al~o contain hydroxyl groups, monoglyceride~ of C~-C10-fatty Le A 29 044 - 4 -2~9~77~
acids and others.

Substances which are furthermore possible are dibutyl stearate, dibutyl sebacate, paraffin oil, ethylhexyl palmitate/stearate or isotridecyl stearate and an isopro-S pyl myristate/isopropyl palmitate/isopropyl stearatemixture.

Thermoplastics and fle~ible thermosetting plastics, as well as elastomers and thermoplastic elastomers, are possible for production of the shaped articles according to the invention. Such substances which may be mention~d are polyvinyl resins, polyurethanes, polyacrylateæ, epoxy resinst cellulose, cellulose derivatives, polyamides and polyesters which are sufficiently compatible with the abovementioned active compound. The polymers must have an adequate strength and flexibility so that they do not tear or become fragile during shaping. They must have an adequate storage life, in order to be resistant to normal wear. Furthermore, the polymers must allow adequate migration of the active compound to the surface of the shaped article.

The polyvinyl resins include poly~inyl halides, such as polyvinyl chloride, polyvinyl chloride/vinyl acetate and polyvinyl fluoride; polyacrylate and polymethacrylate esters, such as polymethyl acrylate and polymethyl methacrylate; and polyvinylbenzenes, 8uch as polystyrene and polyvinyltoluene. Polyvinyl chloride may be singled out in particular.

Le A 29 044 - 5 -2~9;~7~
The pla~ticisers which are usually used for plasticising solid vinyl resins are suitable for production of the collars according to the invention based on polyvinyl resin. The plasticiser to be used depends on the resin and its compatibility with the plasticiser. Suitable plasticisers are, for example, esters of phosphoric acid, such as esters of phthalic acid, such as dimethyl phthal-ate and dioctyl phthalate, and eqters of adipic acid, such a~ diisobutyl adipate. It is also possible to use other esters, such as the esters of azelaic acid, maleic acid, ricinoleic acid, myristic acid, palmitic acid, oleic acid, sebacic acid, stearic acid and trimellitic acid, and complex linear polyesters, polymeric plasti-cisers and epoxidised soya bean oils. The amount of plasticiser is about 10 to 50 % by weight, preferably about 20 to 45 % by weight of the total composition.

The collars can also comprise other constituents, such as stabilising agents, lubricants, fillers and colouring materials, without thereby changing the fundamental properties of the composition. Suitable stabilising agents are antioxidants and agents which protect the collars from ultraviolet radiation and undesirable degradation during working, such as extrusion. Some stabilising agents, such as epoxidised soya bean oils, moreover serve as secondary plasticisers. Lubricants which can be used are, for example, stearates, stearic acid and polyethylenes of low molecular weight. These constituents can be used in a concentration o~ up to about 5 % by weight of the total composition.

Le A 29 044 - 6 -2~9S770 For production of the vinyl-based collars according to the invention, the various constituents are mixed by known processes and moulded by known extrusion or in~ec-tion moulding processes.

The choice of processing process for the production of the collars according to the invention in principle depends industrially on the rheological properties of the collar material and the shape of the desired collar. The processing processes can be adjusted according to the processing ~echnology or according to the nature of the shaping. In the case of the process technology, the processes can be classified according to the rheological states passed through during them. Accordingly, casting, compression moulding, injection moulding and application are suitable for viscous collar materials, and injection moulding, extrusion, calendering, rolling and, if appro-priate, edging are possible for elastoviscous polymers.
Classified according to the nature of the shaping, the shaped articles according to the invention can be pro-duced by casting, dipping, compression moulding, in~ec-tion moulding, extrusion, calendering, embossing, bend-ing, deep-drawing and the like.

These processing processes are known and require no more detailed explanation. The explanations given above by way of example for polyvinyl resins apply in principle to other polymers.

The polyurethanes which serve as the carrier material are Le A 29 044 - 7 -2 ~ 9 ~ 7 ~ (~
prepared in a manner which is known per se by reaction o~
polyisocyanates with higher molecular weight compounds containing at least two groups which are reactive towards isocyanates and if appropriate low molecular weight chain-lengthening agents and/or monofunctional chain stoppers.

Possible starting components for the preparation of the polyurethanes are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, such as are described, for example, by W. Siefken in Liebig's Annalen der Chemie, 562, pages 75 to 136. Examples which may be mentioned are: ethylene diisocyanate, tetramethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate, dodecane 1,12-diisocyanate, cyclobutane 1,3-diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate and any desired mixtures of these compounds, l-isocyanato-3,3,5.-trimethyl-5-isocyanatomethyl-cyclohexane (see DE-AS
(German Published Specification) 202,785 and U.S. Patent Specification 3,401,190), hexahydrotoluylene 2,4- and 2,6-diisocyanate and any desired mixture~ of these compounds; hexahydrophenylene 1,3- and/or 1,4-diisocyanate, perhydrodiphenylmethane 2,4'- and/or 4,4~-diisocyanate, phenylene 1,3- and 1,4-diisocyanate, toluylene 2,4- and 2,6-diisocyanate and any desired mixtures of these compounds; diphenylmethane 2,4'- and~or 4,4'-diisocyanate, naphthylene 1,5-diisocyanate, triphenylmethane 4,4', 4"-trii~ocyanate and polyphenyl-polymethylene polyisocyanate~, such as are obtained by aniline/formaldehyde condensation and subsequent Le A 29 044 - 8 -2 0 9 ~ 7 7 ~) pho~genation and are described, for example, in British Patent Specifications 874,430 and 848,671; m- and p-isocyanatophenyl-sulphonyl isocyanates according to U.S. Patent Specification 3,454,606; perchlorinated aryl polyisocyanates, such as are described, for example, in DE-AS (German Published Specification) 1,157,601 and in U.S. Patent Specification 3,277,138; polyisocyanates containing carbodiimide groups, such as are described in German Patent Specification 1,092,007 and in U.S. Patent Specification 3,152,162; diisocyanates, such as are described in U.S. Patent Specification 3,492,330; poly-isocyanates containing allophanate groups, such as are described, for example, in British Patent Specification 994,890, German Patent 5pecification 761,626 and published Dutch Patent Application 7,102,524;
polyisocyanates containing isocyanurate groups, such as are described, for example, in U.S. Patent Specification 3,001,973, in German Patent Specifications 1,022,789, 1,222,067 and 1,027,394 and in DE-OS (German Published Specification~) 1,929,034 and 2,004,048; polyisocyanates containing urethane groups, such as are described, for example, in German Patent Specification 752,261 or in U.S. Patent Specification 3,394,164~ polyisocyanates containing acyla~ed urea groups in accordance with German Patent Specification 1,230,778; polyisocyanates contain-ing biuret groups, such as are described, for example, in German Patent Specification 1,101,394, in U.S. Patent Specifications 3,124,605 and 3,201,372 and in British Patent SpecLfication 889,050; polyi80cyanate~ prepared by telomerisation reactions, such as are de~cribed, for Le A 29 044 - 9 -example, in U.S. Patent Specification 3,654,106;
polyisocyanates containing ester groups, such as are mentioned, for example, in British Patent Specifications 965,474 and 1,072,956, in ~.S. Patent Specification 3,567,763 and in German Patent Specification 1,231,688;
reaction products of the abovementioned isocyanates with acetals in accordance with German Patent Specification 1,072,385, and polyisocyanates containing polymeric fatty acid radicals, in accordance with U.S. Patent Specification 3,455,883.

-It is also possible to employ the distillation residues which are obtained during industrial isocyanate produc-tion and contain isocyanate groups, if appropriate di~solved in one or more of the abovementioned polyiso-cyanates. Furthermore, it is possible to use any desiredmixtures of the abovementioned polyisocyanates.

Preferred polyisocyanates are in general the toluylene diisocyanates and the diphenylmethane diisocyanates.

Starting co~ponents for the preparation of the polyureth-anes are furthermore compounds having at least two hydrogen atoms which are reactive towards isocyanates and a molecular weight aY a rule of 400 - 10 000. They are understood here, in addition to compounds containing amino groups, thiol groups or carboxyl groups, preferably polyhydroxy compounds, in particular compounds ha~ing 2 to 8 hydroxyl groups, specifically those of molecular weight 800 to 10 000, preferably 1 000 to 6 000, for Le A 29 044 - 10 -2 0 9 ~ 7 7 0 example polyesters, polyethers, polythioethers, polyacetals, polycarbonates and polyester-amides contain-ing at least two, as a rule 2 - ~, but preferably 2 - 4, hydroxyl groups, such as are known per se for the preparation of homogeneous and cellular polyurethanes.

The polyesters containing hydroxyl groups which are possible are, for example, reaction products of poly-basic, preferably dibasic, and if appropria~e additionally tribasic, carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof for the preparation of the polyesters. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and/or heterocyclic in nature, and if appropriate substituted, for example by halogen atoms, and/or unsaturated.

Examples of these which may be mentioned are: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexa-hydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimeric and trimeric fatty acids, such as oleic acid, if appropriate as a mixture with monomeric fatty acids, dimethyl terephthalate and terephthalic acid bi8-glycol ester.

Le A 29 044 - 11 -209~770 Possible polyhydric alcohols are, for example, ethylene glycol, propylene 1,2- and 1, 3-glycol, butylene 1,4- and 2, 3-glycol, hexane-1,6-diol., octane-1,8-diol, neopentyglycol, cyclohexanedimethanol (1,4-bis-hydroxy-methylcyclohexane)~ 2-methyl-1,3-.propanediol, glycerol, trimethylolpropane, hexane-1,2,6-triol, butane-1,2,4-triol, trimethylethane, pentaerythritol, quinitol, mannitol and sorbitol, methylglycositol, and furthermore diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, poly-propylene glycols, dibutylene glycol and polybutylene glycols. The polyesters can contain a proportion of terminal carboxyl groups. Polye~ters from lactones, for example 6 -caprolactone, or hydroxycarboxylic acids, for example ~-hydroxycaproic acid, can al80 be employed.

Possible polyhydric alcohols are polyethers which contain at least two, as a rule two to eight, preferably two to three, hydroxyl groups. These are known per se and are prepared, for example, by polymerisation of epoxides, such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, with themselves, for example in the presence of BF3, or by addition of these epoxides, if appropriate as a mixture or in succession, onto starting components having react-ive hydrogen atoms, such as water, alcohols, ammonia oramines, for example ethylene glycol, propylene 1,3- or 1,2-glycol, trimethylolpropane, 4,4'-dihydroxydiphenyl-propane, aniline, ethanolamine or ethylenediamine.
Sucrose polyethers such as are de~cribed, for example, in Le A 29 044 - 12 -2 ~ g S 7 rJ o DE-AS (German Published Specifications) 1,176,358 and 1,064,938 are also possible. Those polyethers which contain mainly (up to 90 % by weight, based on all the OH
groups present in the polyether) primary OH groups are often preferred. Polyethers modified by vinyl polymers, such as are formed, for ex2mple, by polymerisation of styrene and acrylonitrile in the presence of polyethers (U.S. Patent Specifications 3,383,351, 3,304,273, 3,523,093 and 3,110,695 and German Patent Specification 1,152,536) are also suitable, as are polybutadienes containing OH groups.

Amongst the polythioethers/ those which may be mentioned in particular are the condensation product~ of thiodiglycol with itself and/or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or aminoalcohols. The products are polythio-mixed ethers, polythioether-esters or polythioether-ester-amides, depending on the co-components.

Possible polyacetals are, for example, the compounds which can be prepared from glycols, such a~ diethylene glycol, triethylene glycol, 4,4'-dioxyethoxydiphenyl-dimethylmethane, hexanediol and formaldehyde. Polyacetals which are suitable according to the invention can also be prepared by polymerisation of cyclic acetals.

Po~sible polycarbonates containing hydroxyl groups are those of the type which is known per se, which can be prepared, for example, by reaction of diols, such a~

Le A 29 044 - 13 -propane-1,3-diol, butane-1,4-diol and/or hexane-1,6-diol, diethylene glycol, triethylene glycol or tetraethylene glycol, with diaryl carbonates, for example diphenyl carbonate, or phosgene.

The polyester-amides and polyamides include, for example, the mainly linear condensates obtained from polybasic saturated and unsaturated carboxylic acids or anhydrides thereof and polyhydric saturated and unsaturated aminoalcohols, diamines, polyamines and their mixtures.

Polyhydroxy compounds which already contain urethane or urea groups and optionally modified naturally occurring polyols, such as castor oil, carbohydrates or starch, can also be used. Addition products of alkylene oxides on phenol/formaldehyde resins or also on urea/formaldehyde resins can also be employed according to the invention.

Representatives of these compounds are described, for example, in High Polymers, Vol. XVI, I'Polyurethans, Chemistry and ~echnology", published by Saunders-Frisch, Interscience Publishers, New-York, London, Volume I, 1962, pages 32 - 42 and pages 44 - 54 and Volume II, 1964, pages 5 - 6 and 198 - 199, and in Xunststoff-Handbuch (Plastics Handbook), Volume VII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Munich, 1966, for example on pages 45 - 71.

Mixtures of the abovementioned compounds having at lea~t two hydrogen atoms which are reactive towards isocyanates Le A 29 044 - 14 -and a molecular weight of 400 - lO 000, for example mixtures of polyethers, can of course also be employed.

Compounds having at least two hydrogen atoms which are reactive towards isocyanates and a molecular weight of 32 - 400 are also possible starting components to be em-ployed, if appropriate. In this case also, these are understood as being compounds which contain hydroxyl groups and/or amino groups and/or thiol groups and/or carboxyl groups, preferably compounds which serve as chain-lengthening agents or crosslinking agentY. These compounds as a rule have 2 to 8 hydrogen atoms which are reactive towards isocyanates, preferably 2 or 3 reacti~e hydrogen atoms.

Examples of such compounds which may be mentioned are:

Ethylene glycol, propylene 1,2- and 1,3-glycol, butylene 1,4- and 2,3-glycol, pentane-1,5-diol, hexane-1,6-diol, octane-1,8-diol, neopentylglycol, 1,4-bis-hydroxymethyl-cyclohexane, 2-methyl-1,3-propanediol, glycerol, trimeth-ylolpropane, hexane-1,2,6-triol, trimethylolethane, pentaerythritol, quinitol, mannitol and sorbitol, di-eth~lene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols having a molecular weight of up to 400, dipropylene glycol, polypropylene glycols having a molecular weight of up to 400, dibutylene glycol, polybutylene glycols having a molecular weight o~
up to 400, 4,4'-dihydroxydiphenylpropane, di-hydroxy-methyl-hydroquinone, ethanolamine, diethanolamine, Le A 29 044 - 15 -209~77~

triethanolamine, 3-aminopropanol, ethylenediamine, 1,3-diaminopropane,1-mercapto-3-aminopropane,4-hydroxy-or -amino-phthalic acid, succinic acid, adipic acid, hydrazine, N,N~-dimethylhydrazine, 4,4'-diaminodiphenylmethane, toluylenediamine, methylene-bis-chloroaniline, methylene-bis-anthranilic acid esters, diaminobenzoic acid esters and the i~omeric chlorophenylenediamines.

In this case also, mixtures of various compounds having at least two hydrogen atoms which are reactive towards isocyanates and a molecular weight of 32 - 400 can be used.

It is also possible, however, to employ polyhydroxy compounds in which high molecular weight polyadducts or polycondensates are contained in finely dispersed or dissolved form. Such modified polyhydroxy compounds are obtained when polyaddition reactions (for example reac-tions between polyisocyanates and amino-functional compounds) or polycondensation reactions (for example between formaldehyde and phenols and/or amines) are allowed to proceed directly in situ in the abovementioned compounds containing hydroxyl groups. Such processes are described, for example, in DE-AS (German Publi~hed specifications) 168,075 and 1,260,142, and DE-OS (German Published Specifications) 2,324,134, 2,423,984, 2,512,385, 2,513,815, 2,550,797, 2,550,833 and 2,550,862.
However, it is also possible, in accordance with U.S.
Patent SpecificatLon 3,869,413 or DE-OS (German Published Le A 29 044 - 16 -Specification) 2,550,860, to mix a finished aqueous polymer dispersion with a polyhydroxy compound and then to remove the water from the mixture.
When choosing the higher molecular weight polyol com-ponent used for the preparation of the polyurethane, it should be remembered that the finished polyurethane should not be swellable in water. The use of an escess of polyhydroxy compounds with ethylene oxide units (poly-ethylene glycol polyethers or polyesters with diethylene glycol or triethylene glycol as the dio component) should therefore be avoided.
The shaped articles according to the invention are suitable for combating parasites and animal pests, such as arthropods, prefereably insects and arachnida, which occur in animal rearing and animal breeding in domestic and stock animals as well as zoo, laboratory and experi-mental animals and pets, and have a favourable toxicity to warm-blooded animals. They are active here against all or individual stages of development of the pests and against resistant and normally sensitive species of pests.
The pests include:
From the order of the Anoplura, for example, Haematopinus spp., Linognathus app., Solenopotes spp., Pediculus spp. and Pthirus spp., from the order of the Mallophaga, for example, Trimenopon spp., Menopon spp., Eomenacanthus spp., Le A 29 044 - 17 -7 ~
Menacanthus spp., Trichodectes spp., Felicola spp., Damalinea spp. and Bovicola spp;
from the order of the Diptera, for example, Chrysops spp., Tabanus spp., Musca spp., Hydrotaea spp., Muscina spp., Haema~obosca spp., Haematobia spp., Stomoxys spp., Fannia spp., Glossina spp.~ Lucilia spp., Calliphora spp., Auchmeromyia spp., Cordylobia 8pp., Cochliomyia spp., Chrysomyia spp., Sarcophaga spp., Wohlfartia ~pp., Gasterophilus spp., Oesteromyia spp., Oedemagena spp., Hypoderma spp., Oestrus spp., RhinoestruY spp., Nelophagus spp. and Hippobosca spp..

From the order of the Siphonaptera, for example, Ctenocephalides spp., Echidnophaga 9pp. and Ceratophyllus spp..

From the order of the Metastigmata, for example, Hyalomma spp., Rhipicephalus spp., Boophilus spp., Amblyomma spp., Haemophysalis spp., Dermacentor spp., Ixodes spp., Argas spp., Ornithodorus spp. and Otobius spp.;
from the order of the Mesastigmata, for example, Dermanyssus spp., Ornithonyssus spp. and Pneumonyssus spp..

From the order of the Prostigmata, for example, Cheyletiella Bpp., Psorergates spp., Nyobia spp., Demodex Bpp. and Neotrombicula spp.;
from the order of the Aetigmata, for example, Acarug 8pp., Myocoptes 8pp., P80ropteg 8pp-, Le A 29 044 - 18 209~770 Chorioptes spp., Otodectes spp., Sarcoptes spp., N o t o e d r e s s p p . , K n e m i d o c o p t e s s p p . , Neoknemidocoptes spp., Lytodites spp. and Laminosioptes spp..

Fleas and ticks may be singled out in particular.

The domestic and stock animals include, mammals, such as, for example, cattle, sheep, goats, horses, pigs, dogs and cats.

The chaped articles according to the invention are preferably employed in the form of collars and collar pendants (medallions) on pets, such as dogs and cats.

Formulation examples:

A) Production of an insecticidal medallion for dogs Composition:

1~ Propoxur 15 2. Flumethrin 3 ~
3. Isopropyl palmitate 8.0 %
4. triethyl citrate 17.0 %

5. PVC homopolymer 62.0 %
100 . O %

Le A 29 044 - 19 -Production:
a) Dissolve 1, 2, 3 and 4, while heating.

b) Initially introduce the PVC into the mixing vessel and mix with solution a) at a high ~peed.

S c) In~ection mould mixture b ~o medallions 16 cm2 in size. (Medallions are understood as meaning pendants which are attached to a usual collar (without insecticide) - for example made of leather - and are comparable to a dog tag.) B) Production of a medallion Composition:

1. Propoxur 10.0 %
2. Flumethrin 2.3 %
3. Dioctyl phthalate 10.0 %
4. Dibutyl adipate 12.0 %
5. Epoxidised soya bean oil 2.7 %

6. Coloured pigment 0.2 %

7. PVC homopolymer 62.8 %
100.0 %

Le A 29 044 - 20 -209a770 Production:

a) 1 to 5 are weighed together and dîssolved, while heating.
b) 6 and 7 are mixed.

c) a) is stirred into b) with the mixture running, and mixing is continued until a powder which is capable of flow has formed.

d) The powder c is extruded on an extruder to a tape, out of which sheets 16 cm2 in size are stamped as medallions.
C) Production of a dog collar Composition:

1. Flumethrin . 2.5 %
2. Propoxur 10.0 ~
3. Triacetin 9.5 %
4. Epoxidised soya oil 20.0 5. Stearic acid 0.5 6. PVC homopolymer 57.5 ~
100.0 %

Le A 29 044 - 21 -209:~770 Production:

a) 1 and ticks are dissolved in 3 and 4, while heating.
b) 6 and 5 are mixed.

c) a) is added to b) with the mixer running, and mixing is carried out until granules which are capable of flow have formed.

d) c) is extruded with an extruder to a tape, which is cut into a length of 50 cm. The tape is also provided with a buckle. Alternatively, however, mixture c) can also be shaped to dog collars on an in~ection moulding machine.
D) Production of a collar based on polyurethane Component I

Flumethrin 2.5 Propoxur 10.0 Trihydroxypolyether (M6 4800) 48.0 Butane-1,4-diol 5.0 Coloured pigment 0.5 Zeolite paste (1:1 in castor oil) 0.5 Isopropyl myristate 8.0 Dibutyltin dilaurate 0.02 Le A 29 044 - 22 -209~770 Component II

Tripropylene glycol-modified 4,4'-diisocyanatodi-phenyl-methane (isocyanate content 23 %) The substances of component I - apart from the catalyst (dibutyltin dilaurate) are mixed together in a tank which can be heated, and are heated up to about 60C. The catalyst is then mixed in.

This component I is mixed intensively with compon-ent II and the mixture is then poured into a box mould. The mixture starts to react 30 seconds after mixing, and has hardened after about 60 seconds.
After cooling, the sheet formed can be cut into tapes.

(E) Example of an insecticidal medallion for dogs Composition 1. Propoxur 10.0 %
2. Flumethrin 2.5 %
3. Triacetin 5.0 %
4. Modifiad polyamide 82.5 %
~~
100 . O %

Le A 29 044 - 23 -209~77~
Production:
a) 1, 2 and 3 are liquefied, while heating.

b) Solution a) is added with the mixer running, and mixing is continued until homogeneous granules have formed.

c) The granules from b) are injection moulded in the form of medallions. It can also be obtained by stamping out of sheets originating from an extrusion process.
Example A 1 Test on ca~ fleas ((Ctenocephalides felis) / collar test in vivo Test sub;ect:
Male and female adults of Ctenocephalides felis 1 to 4 days old Test anLmals:
Dogs with the shortest hair possible (for example beagles) Test method:
Plastic Petri dishes, 0 9 cm, height 1.5 cm, each con-taining 30 to 50 fleas (male and female adults of Ctenocephalide~ felis 1 to 4 day~ old) are placed in dog Le A 29 044 - 24 -209a77~
cages 3 to 5 days after hatching and are opened there, so that the fleas can Lmmediately infest the dog, which i5 on a perforated sheet in the cage.

When infestation of the test dog by the fleas has been demonstrated unambiguously, the collars to be tested are placed around the dogs. At certain times, the collar-wearing dogs with living fleas are examined. At certain tLmes a~ter the start of the te~t, further infestations with C. feli~ are carried out and the corresponding procedure is followed.

Test criteria:
The criterion for the action of the collar is the reduc-tion in the number of living adult fleas on the dogs in comparison with untreated control animals.

Results:
The results obtained with collars of varying composition are contained in the following Tables 1, 2 and 3.

Example A 2 Test on dog ticks (Rhipicephalus sanguineus) / collar test in vivo Test sub~ect:
Male and female fasting adults of Rhipicephalus sanguineu~ 4 to 8 weeks old Le A 29 044 - 25 -. . ,; .

2~ 7 0 Test anLmals:
Dogs with the shortest hair possible tfor example beagles) Test method:
l. Infection: The dogs are in cages, the bases of which are lined completely and the walls of which are lined on the lower two thirds with a plastic trough which fits the cage. The base of the trough is lined with straw. 10 to lS minutes before the infection, the dogs are sedated with Rompun~ 2 ~ strength (1 to 1.5 mg/kg i.m.). The ticks are in glass tubes sealed by a cellulose stopper around which i~ wound gauze. After the dogs have been immobilised, the cellulose stopper is removed from the tick tube, but such that the gauze remains in the opening of the tube. The gauze is now introduced into the tube using tweezers, and is agitated therein such that as far as possible all the ticks are trapped in the gauze. The ticks are now placed with the gauze in the straw on the base of the trough, so that ~hey can infest the sedated dog.

After 3 days, the dog is examined for sucking ticks (predicection sites: ears, eye region, inside of the thigh, axillae).

When infestation of the test dog by ticks has been demonstrated, the collars to be tested are placed around the dogs. The test animals are now checked once daLly for 7 to lO days and the number of living ticks on the Le A 29 044 - 26 -209a770 collar-wearing dogs and on the control animals is determined.

The collar-wearing dog is infested with ticks again at predetermined times, and the procedure followed is as above.

Results:
The results obtained with collars of varying composition are contained in the following Tables 1, 2 and 3.

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Claims (3)

1. Shaped articles for combating ectoparasites on animals, which comprise flumethrin and propoxur as active compounds.

2. Use of flumethin and propoxur as active compounds in shaped articles for combating ectoparasites on animals.

3. Use of flumethrin and propoxur as active compounds for the production of shaped articles for combating ectopara-sites on animals.

Le A 29 044