US 4,544,547 AGrant

Ectoparasiticide-Containing Polyurethanes

Issue Date:1985-10-01

•17 Claims

•3 Drawing Sheets

Abstract

The invention relates to ectoparasiticide-containing polyurethanes which contain spreading agents and ectoparasiticides or mixtures of ectoparasiticides and to said ectoparasiticide-containing polyurethanes in the form of sheets, films, shaped articles, coatings or impregnations. Also included in the invention is the use of said polyurethane compositions for combating ectoparasiticides.

Metadata

Assignee

Bayer Aktiengesellschaft

Inventors

Miklos von Bittera
Hubert Dorn
Dietmar Schapel
Wilhelm Stendal
Herbert Voege
Manfred Federman
Ulrich von Gizyoki

Application Information

Application Number:US 475008&

Filing Date:1983-03-14

Priority Date:1980-10-22

Art Unit:123

Classifications

IPC:

A01N 2534A01N 2500

Field of Search:

42411914;16;27;28;78106;156

Patent Drawings (3 sheets)

Description

This application is also related to copending application Ser. No. 456,141, filed Jan. 6, 1983, which is a continuation of application Ser. No. 308,718, filed Oct. 5, 1981, now abandoned.

Background of Invention

The present invention relates to new ectoparasiticide-containing polyurethanes which contain spreading agents and ectoparasiticides or mixtures of ectoparasiticides, and to sheets, films, shaped articles, coatings or impregnations consisting of such polyurethanes and the use thereof in combating ectoparasites.

The commercially available PVC systems which have an ectoparasiticidal action and have hitherto been described, for example in the form of collars for small animals, generally consist of thermoplastic polyvinyl chloride into which an insecticidal or ectoparasiticidal active compound, for example O,O-dimethyl dichlorovinyl phosphate, has been incorporated by co-extrusion. PVC systems having this formulation occasionally lead to damage to the skin of the animal; another disadvantage is the short effective life of the collar formed of such PVC systems as a result of the relatively high vapour pressure of O,O-dimethyl dichlorovinyl phosphate (1.2.times.10.sup.-1 mm Hg).

Animal collars which are based on plasticised, thermoplastic polymers, preferably plasticised polyvinyl chloride, and which contain, as insecticidal active compounds, carbamates which have a lower volatility are described in U.S. Pat. No. 3,852,416. Whilst highly volatile active compounds, such as O,O-dimethyl dichlorovinyl phosphate rapidly pass directly into the gas phase from the ectoparasiticidally active plastic collars known hitherto, insecticides with a lower volatility, such as the carbamates mentioned, diffuse slowly out of the collar and form a white, dust-like layer on its surface. Some of the active compound passes into the vapour phase by sublimation and is effective in this phase, and another portion is distributed as a dust over the animal to be treated.

The said effluorescence or exudation of the active compound at the surface of the PVC system has a number of disadvantages.

If the PVC system is stored for a prolonged period before use, a relatively large amount of the active compound diffuses to the surface and becomes concentrated there. When the collar is used, there is then a very high dose of the insecticide on the surface, which indeed ensures a good immediate action but may already be at the limit of toxicity for the animal.

The active compound present on the surface is rapidly rubbed off. However, the active substance within the lower layers of the collar subsequently diffuses to the surface only very slowly. Release of the insecticide thus does not take place in the desired manner, that is to say uniformly over as long a period as possible.

The dust-like, whitish active compound present on the surface of the PVC system further imparts an extremely unattractive, dusty or mouldy appearance to the latter.

In the case of O,O-dimethyl dichlorovinyl phosphate and in the case of carbamates, the release of active compound is influenced by the plasticisers customary in PVC, such as phthalates and adipates.

The abovementioned difficulties can be avoided if polyurethanes which cannot be swollen in water and which contain certain amounts of spreading agents are used as carriers for the various ectoparasiticides or combinations thereof.

Spreading oils are understood as those oily liquids which spread particularly well on the skin. They are known as such in the cosmetics industry. According to a proposal by R. Keymer, Pharm. Ind. 32, 577, (1970), they can be characterised, for example, by their surface tension towards air and this should be between 20 and less than 30 dynes/cm.

Summary of the Invention

According to the present invention there are provided polyurethanes which consists of a hydrophobic polyurethane which cannot be swollen in water (as hereinafter defined) and which comprises, relative to the polyurethane, 2 to 30% by weight, preferably 5 to 20% by weight, of an ectoparasiticide or of a combination of ectoparasiticides and, relative to the polyurethane, 5 to 35% by weight, preferably 8 to 25% by weight, of a spreading agent.

By "hydrophobic" or "cannot be swollen" there are understood, according to the invention, polyurethanes which, when immersed in water at 20.degree. C., absorb less than 2% by weight, preferably less than 0.5% by weight, of water in the course of 24 hours as a result of swelling.

As well as being produced by a technically uncomplicated manufacturing process, the polyurethane/spreading agent systems according to the invention have the advantage, above all, that the active compound is released continuously and in an essentially linear manner over a period of some months.

In particular, surprisingly, the active compound diffuses out of the polyurethane onto the surface in a gradated manner such that from there it is uniformly released into the environment by sublimation or by a mechanical route. No noticeable effluorescence forms on the surface, and when the collar is stored for a prolonged period, its pleasant appearance is preserved and no toxicity problems arise. The period of activity is significantly increased, and can be influenced by the controlled use of spreading agents.

The active compound is not deposited on the surface of the polyurethane in visible crystals, so that the polyurethanes according to the invention, for example in the form of sheets or films, do not have a dusty appearance either on the upper side or on the underside. Nevertheless, the polyurethanes are effective over a period of more than 4 months, as is illustrated in more detail in the following Examples. The in vitro release experiments show that the active compound is released continuously from the polyurethanes according to the invention even after prolonged storage, whilst most of the active compound has already diffused out of a comparable formulation based on polyvinyl chloride after a short time. Thereafter, only a very small amount of the ectoparasiticide is released per unit time.

Brief Description of the Drawings

FIG. 1 is a sectional view taken along the line 1--1 of FIG. 2 of a prior art ear tag.

FIG. 2 is a front elevational view of the ear tag depicted in FIG. 1.

FIG. 3 is a side view of another ear tag in accordance with the present invention.

FIG. 4 is a front elevational view of the ear tag depicted in FIG. 3.

FIG. 5 is a side view of a depot for attachment to the tag depicted in FIGS. 3 and 4.

FIG. 6 is a front elevational view of the depot depicted in FIG. 5.

FIG. 7 is a side elevational view of the tag depicted in FIGS. 3 and 4 prior to insertion in an ear (at left of FIG. 7). The top portion of the tag being bent 90.degree. so as be inserted in a tube having a pointed edge.

FIG. 8 is a side elevational view of the tag depicted in FIGS. 3 and 4 inserted through an ear (tube removed and top portion bent back into place).

FIG. 9 depicts a series of curves for the release of active compound in mg plotted as the ordinate against time in days as the abscissa.

Detailed Description of the Invention

Possible ectoparasiticides are carbamates with a vapour pressure of between about 10.sup.-4 and 10.sup.-6 mm Hg at 20.degree. C. Such compounds are mentioned, for example, in U.S. Pat. No. 3,852,416; their preparation is described in U.S. Pat. Nos. 2,903,478 and 3,203,853.

2-Isopropoxyphenyl N-methyl-carbamate with a vapour pressure of 6.5.times.10.sup.-6 mm Hg is preferably employed according to the invention as the ectoparasiticidal component.

Other carbamates which are suitable for incorporation in polyurethanes according to the invention are, for example, 3-tolyl N-methylcarbamate, 3,4-xylyl N-methylcarbamate, m-(1-methylbutyl)-phenyl N-methylcarbamate, 2-ethylthiomethyl-phenyl N-methylcarbamate, 4-dimethylamino-m-tolyl N-methylcarbamate, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate, 2-dimethylcarbamoyl-3-methyl-5-pyrazolyl-dimethylcarbamate and 2-dimethylamino-5,5-dimethylpyrimidin-4-yl-N,N-dimethylcarbamate.

Further possible ectoparasiticides are in particular, synthetic pyrethroids, for example those of DE-OS (German Published Specification) No. 2,730,515 (corresponding to Ser. No. 916,163, filed June 16, 1978 of which Ser. No. 195,025, filed Oct. 8, 1980 is a division), but preferably 3-phenoxy-4-fluoro-.alpha.-cyanobenzyl 2,2-dimethyl-3[2-(4-chlorophenyl)-2-chlorovinyl]-cyclopropanecarboxylate and isomers thereof, and permethric acid pentafluorobenzyl ester.

The ectoparasiticides can be used individually or in combination. Thus preferred ectoparasiticides for use in polyurethanes according to the invention are an insecticidally active carbamate or synthetic pyrethroid or a mixture of such active compounds. The content of ectoparasiticides is 2 to 30% by weight, preferably 5 to 20% by weight, relative to the polyurethane. Combined ectoparasiticides are used in a ratio of 1:10 to 1:1, preferably 3:10 to 1:2.

The polyurethanes according to the invention are prepared in a manner which is in itself known, by reaction of polyisocyanates with higher-molecular compounds which contain at least two groups which are reactive towards isocyanates, and, if appropriate, with low-molecular chain-lengtheners and/or monofunctional chain-stoppers.

Possible starting components in 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, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (see DE-AS (German Published Specification) No. 1,202,785 and U.S. Pat. No. 3,401,190), hexahydrotoluylene 2,4- and 2,6-diisocyanate and any desired mixtures 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"-triisocyanate, polyphenyl-polymethylene polyisocyanates, such as are obtained by aniline/formaldehyde condensation and subsequent phosgenation and as are described, for example, in British Patent Specification Nos. 874,430 and 848,671; m- and p-isocyanatophenyl-sulphonyl isocyanates according to U.S. Pat. No. 3,454,606; perchlorinated aryl polyisocyanates, such as are described, for example, in DE-AS (German Published Specification) No. 1,157,601 and in U.S. Pat. No. 3,277,138; polyisocyanates containing carbodiimide groups, such as are described in German Patent Specification No. 1,092,007 and in U.S. Pat. No. 3,152,162; diisocyanates such as are described in U.S. Pat. No. 3,492,330; polyisocyanates containing allophanate groups, such as are described, for example, in British Patent Specification No. 994,890, German Patent Specification No. 761,626 and Published Dutch Patent Application No. 7,102,524; polyisocyanates containing isocyanurate groups, such as are described, for example, in U.S. Pat. No. 3,001,973, in German Patent Specification Nos. 1,022,789, 1,222,067 and 1,027,394 and in DE-OSen (German Published Specification) Nos. 1,929,034 and 2,004,048; polyisocyanates containing urethane groups, such as are described, for example, in German Patent Specification No. 752,261 or in U.S. Pat. No. 3,394,164; polyisocyanates containing acylated urea groups, according to German Patent No. 1,230,778; polyisocyanates containing biuret groups, such as are described, for example, in German Patent Specification 1,101,394, in U.S. Pat. Nos. 3,124,605 and 3,201,372, and in British Patent Specification No. 889,050; polyisocyanates which have been prepared by telomerisation reactions and such as are described, for example, in U.S. Pat. No. 3,654,106; polyisocyanates containing ester groups, such as are mentioned, for example, in British Patent Specifications Nos. 965,474 and 1,072,956, in U.S. Pat. No. 3,567,763 and in German Patent Specification No. 1,231,688; reaction products of the abovementioned isocyanates with acetals, according to German Patent Specification No. 1,072,385; and polyisocyanates containing polymeric fatty acid radicals, according to U.S. Pat. No. 3,455,883.

It is also possible to use the distillation residues which are obtained in the industrial preparation of isocyanates and contain isocyanate groups, these distillation residues being dissolved, if appropriate, in one or more of the abovementioned polyisocyanates. It is furthermore possible to use any desired mixtures of the abovementioned polyisocyanates.

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

Further starting components for the preparation of the polyurethanes are compounds which have at least two hydrogen atoms which are reactive towards isocyanates and have as a rule a molecular weight from 400 to 10,000. By these compounds there are understood, in addition to compounds containing amino groups, thiol groups or carboxyl groups, preferably polyhydroxy compounds, in particular compounds containing two to eight hydroxyl groups, and especially those with a molecular weight of 800 to 10,000, preferably 1,000 to 6,000, for example polyesters, polyethers, polythioethers, polyacetals, polycarbonates and polyester-amides containing at least two, as a rule 2 to 8 but preferably 2 to 4, hydroxyl groups, such as are in themselves known for the preparation of homogeneous and cellular polyurethanes.

The possible polyesters containing hydroxyl groups are, for example, reaction products of polyhydric, preferably dihydric and optionally additionally trihydric, alcohols and polybasic, preferably dibasic, 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 can optionally be substituted, for example by halogen atoms, and/or unsaturated.

Examples of these compounds 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, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimeric and trimeric fatty acids, such as oleic acid, optionally mixed with monomeric fatty acids, terephthalic acid dimethyl ester and terephthalic acid bis-glycol ester.

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, neopentylglycol, cyclohexanedimethanol(1,4-bis-hydroxymethylcyclohexane), 2-methyl-propane-1,3-diol, glycerol, trimethylolpropane, hexane-1,2,6-triol, butane-1,2,4-triol, trimethylolethane, pentaerythritol, quinitol, mannitol, and sorbitol, methyl glycoside, and furthermore diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols. The polyesters can contain a proportion of terminal carboxyl groups. Polyesters from lactones, for example .epsilon.-caprolactone, or hydroxycarboxylic acids, for example .omega.-hydroxycaproic acid, can also be employed.

The polyethers which are possible according to the invention and which contain at least two, as a rule two to eight and preferably two or three, hydroxyl groups are also those of a type which is in itself known, and they are prepared, for example, by self-polymerisation of epoxides, such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, for example in the presence of BF.sub.3, or by addition of these epoxides, optionally as mixtures or successively, onto starting components with reactive hydrogen atoms, such as water, alcohols, ammonia or amines, for example ethylene glycol, propylene 1,3- or 1,2-glycol, trimethylolpropane, 4,4'-dihydroxy-diphenylpropane, aniline, ethanolamine or ethylenediamine. Sucrose polyethers such as are described, for example, in DE-Asen (German Published Specifications) Nos. 1,176,358 and 1,064,938, are also possible according to the invention. Those polyethers which predominantly (to the extent of up to 90% by weight, relative to all the OH groups present in the polyether) contain primary OH groups are frequently preferred. Polyethers which have been modified by vinyl polymers and such as are formed, for example, by polymerisation of styrene and acrylonitrile in the presence of polyethers (U.S. Pat. Nos. 3,383,351, 3,304,273, 3,523,093 and 3,110,695 and German Patent Specification No. 1,152,536) are also suitable, as are polybutadienes containing OH groups.

Polythioethers which may be mentioned are, in particular, the condensation products of thiodiglycol with itself and/or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or aminoalcohols. The products are mixed polythioethers, 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 as diethylene glycol, triethylene glycol, 4,4'-dihydroxyethoxydiphenyldimethylmethane or hexanediol, and formaldehyde. Polyacetals which are suitable according to the invention can also be prepared by polymerisation of cyclic acetals.

Possible polycarbonates containing hydroxyl groups are those of the type which is in itself known and which can be prepared, for example, by reacting diols, such as 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 predominantly linear condensates obtained from polybasic saturated or unsaturated carboxylic acids or anhydrides thereof and polyhydric saturated or unsaturated aminoalcohols, diamines, polyamines or mixtures thereof.

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. It is also possible to employ, according to the invention, products obtained by adding alkylene oxides onto phenol/formaldehyde resins or onto urea/formaldehyde resins.

Representatives of these compounds to be used according to the invention are described, for example, in High Polymers, Volume XVI, "Polyurethanes, Chemistry and Technology", edited 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 Kunststoff-Handbuch (Plastics Handbook), Volume VII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Munich, 1966, for example on pages 45-71.

It is, of course, also possible to employ mixtures of the abovementioned compounds which have at least two hydrogen atoms which are reactive towards isocyanates and a molecular weight of 400-10,000, for example mixtures of polyethers and polyesters.

Further starting components which are optionally to be employed according to the invention are compounds which have at least two hydrogen atoms which are reactive towards isocyanates and a molecular weight of 32-400. In this case also, by these compounds there are understood compounds which contain hydroxyl groups and/or amino groups and/or thiol groups and/or carboxyl groups, preferably compounds which contain hydroxyl groups and/or amino groups, and which serve as chain-lengtheners or cross-linking agents. These compounds as a rule have 2 to 8 hydrogen atoms which are reactive towards isocyanates, preferably 2 or 3 reactive 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-propane-1,3-diol, glycerol, trimethylolpropane, hexane-1,2,6-triol, trimethylolethane, pentaerythritol, quinitol, mannitol and sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols with a molecular weight of up to 400, dipropylene glycol, polypropylene glycols with a molecular weight of up to 400, dibutylene glycol, polybutylene glycols with a molecular weight of up to 400, 4,4'-dihydroxy-diphenylpropane, di-hydroxymethyl-hydroquinone, ethanolamine, diethanolamine, 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 isomeric chlorophenylenediamines.

In this case also, it is possible to use mixtures of different compounds which have at least two hydrogen atoms which are reactive towards isocyanates and a molecular weight of 32-400.

However, it is also possible to employ, according to the invention, polyhydroxy compounds containing high-molecular polyadducts or polycondensates in finely dispersed or dissolved form. Such modified polyhydroxy compounds are obtained when polyaddition reactions (for example reactions between polyisocyanates and compounds containing amino functional groups) 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-ASen (German Published Specifications) Nos. 1,168,075 and 1,260,142 and DE-OSen (German Published Specifications) Nos. 2,324,134, 2,423,984, 2,512,385, 2,413,815, 2,550,796, 2,550,797, 2,550,833 and 2,550,862. However, it is also possible, according to U.S. Pat. No. 3,869,413 and DE-OS (German Published Specification) No. 2,550,860, to mix a finished aqueous polymer dispersion with a polyhydroxy compound and then to remove the water from the mixture.

When modified polyhydroxy compounds of the abovementioned type are used as the starting component in the polyisocyanate polyaddition process, polyurethane plastics with substantially improved mechanical properties are formed in many cases.

When choosing the relatively high-molecular polyol component used for the preparation of the polyurethane, it must be taken into consideration that the finished polyurethane should not be swellable in water. The use of relatively large amounts of polyhydroxy compounds with ethylene oxide units (polyethylene glycol polyethers or polyesters with diethylene glycol or triethylene glycol as the diol component) should thus be avoided.

Hydrophobic polyesters, in particular those based on adipic acid and ethylene glycol and/or butanediol and/or neopentylglycol and/or hexanediol, polycarbonate-diols and polyether-polyols based on propylene oxide or tetrahydrofuran are preferably employed. In order to render the polyurethane hydrophobic, it is also expedient in some cases (especially if relatively large amounts of mineral fillers are incorporated into the polyurethane) to co-use castor oil as the polyol component.

Catalysts are frequently also used in the preparation of the polyurethanes. Possible catalysts which are also to be used are those of the type which is in itself known, for example tertiary amines, such as triethylamine, tributylamine, N-methyl-morpholine, N-ethyl-morpholine, N-(coconut alkyl)-morpholine, N,N,N',N'-tetramethyl-ethylenediamine, 1,4-diaza-bicyclo-[2,2,2]-octane, N-methyl-N'-dimethylaminoethyl-piperazine, N,N-dimethylbenzylamine, bis-(N,N-diethylaminoethyl)adipate, N,N-diethylbenzylamine, pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N-dimethyl-.beta.-phenylethylamine, 1,2-dimethylimidazole and 2-methylimidazole. Mannich bases, which are in themselves known, obtained from secondary amines, such as dimethylamine, and aldehydes, preferably formaldehyde, or ketones, such as acetone, methyl ethyl ketone or cyclohexanone, and phenols, such as phenol, nonylphenol or bisphenol, can also be used as the catalysts.

Tertiary amines which contain hydrogen atoms which are active towards isocyanate groups and can be used as catalysts are, for example, triethanolamine, triisopropanolamine, N-methyl-diethanolamine, N-ethyldiethanolamine and N,N-dimethylethanolamine, and reaction products thereof with alkylene oxides, such as propylene oxide and/or ethylene oxide.

Further possible catalysts are sila-amines with carbon-silicon bonds, such as are described, for example, in German Patent Specification No. 1,229,290 (corresponding to U.S. Pat. No. 3,620,984), for example 2,2,4-trimethyl-2-silamorpholine and 1,3-diethylaminomethyl-tetramethyldisiloxane.

Nitrogen-containing bases, such as tetraalkylammonium hydroxides, as well as alkali metal hydroxides, such as sodium hydroxide, alkali metal phenolates, such as sodium phenolate, or alkali metal alcoholates, such as sodium methylate, are also possible catalysts. Hexahydrotriazines can also be employed as catalysts.

Organic metal compounds, in particular organic tin compounds, can also be used, according to the invention, as catalysts.

Possible organic tin compounds are, preferably, tin-II salts of carboxylic acids, such as tin-II acetate, tin-II octanoate, tin-II ethylhexanoate and tin-II laurate, and tin-IV compounds, for example dibutyl-tin oxide, dibutyl-tin dichloride, dibutyl-tin diacetate, dibutyl-tin dilaurate, dibutyl-tin maleate or dioctyl-tin diacetate. All the abovementioned catalysts can, of course, be employed in the form of mixtures.

Further representatives of the catalysts to be used according to the invention and details of the mode of action of the catalysts are given in Kunststoff-Handbuch (Plastics Handbook), Volume VII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, for example on pages 96 to 102.

The catalysts are as a rule employed in an amount of between about 0.001 and 10% by weight, relative to the amount of compounds which have at least two hydrogen atoms which are reactive towards isocyanates and a molecular weight of 400 to 10,000.

Possible spreading agents (or "spreading oils") are the following substances; silicone oils of various viscosities; fatty acid esters, of saturated fatty acids of the chain length C.sub.8 -C.sub.18 and linear or branched alcohols of, the chain length C.sub.2 -C.sub.8, for example lauric acid hexyl ester, ethyl stearate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, dipropylene glycol pelargonate, butyl stearate; fatty acid esters of unsaturated fatty acids of the chain length C.sub.16 -C.sub.20 and linear or branched alcohols of the chain length C.sub.2 -C.sub.12 for example oleic acid decyl ester; fatty acid esters of saturated dicarboxylic acids of the chain length C.sub.2 -C.sub.16 for example diisopropyl adipate, dibutyl sebacate, diisodecyl adipate, dibutyl adipate; triglycerides of fatty acids of the chain length C.sub.7 -C.sub.18 for example caprylic/capric acid triglyceride, stearic acid triglyceride; partial glycerides of saturated or unsaturated fatty acids; fatty alcohols such as isotridecyl, fatty alcohols, such as isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol and oleyl alcohol; and fatty acids, such as oleic acid and stearic acid. Mixtures of one or more of these classes of spreading agents may also be used.

Spreading agents which are particularly suitable are isopropyl myristate, isopropyl stearate, isopropyl palmitate, lauric acid hexyl ester, oleic acid decyl ester, dibutyl stearate, dibutyl sebacate, paraffin oil, ethylhexyl palmitate/stearate and isotridecyl stearate.

The content of spreading agents is 5 to 35% by weight, preferably 8 to 25% by weight, relative to the polyurethane.

By fillers and additives which the polyurethanes according to the invention optionally contain there are to be understood the substances which are in themselves known in polyurethane chemistry, such as fillers and short fibres on an inorganic or organic basis, colouring agents, such as dyestuffs and coloured pigments, water-binding agents, surface-active solid substances or pH stabilisers.

Inorganic fillers which may be mentioned are, for example baryte, titanium dioxide, quartz sand, kaolin, carbon black and glass microbeads. Of the organic fillers, for example, powders based on polystyrene or polyvinyl chloride can be employed.

Possible short fibres are, for example, glass fibres 0.1 to 1 mm in length or fibres of organic origin, such as, for example, polyester fibres or polyamide fibres. The dyestuffs or coloured pigments on an organic or inorganic bases which are in themselves known for colouring polyurethanes, such as iron oxide pigments or chromium oxide pigments and phthalocyanine pigments or monoazo pigments, can be used in order to impart the desired coloration to the polyurethanes according to the invention. Zeolites are the preferred water-binding agent. Solid surface-active substances which may be mentioned are, for example, cellulose powder, active charcoal, silica products and chrysotile asbestos.

It is also possible to add pH-regulating substances, such as stearic acid or buffer systems based on inorganic phosphoric acid salts, to stabilise the ectoparasiticides against too rapid a decomposition.

The ectoparasiticide-containing polyurethanes according to the invention can be produced by the processes which are in themselves known in polyurethane chemistry, it being possible to obtain the polyurethanes according to the invention by thermoplastic processing methods or by the reactive process.

Thermoplastic polyurethanes such as are formed by reacting diisocyanates with higher-molecular dihydroxy compounds and low-molecular glycols as chain-lengtheners at a NCO/OH ratio of between about 0.97 and 1.05, are described, for example, in British Patent Specifications Nos. 1,210,737, 1,270,836, 1,075,274, 1,110,118, 1,025,970, 1,057,018, 1,087,743 and 849,136, German Patent Specifications Nos. 1,189,268, 1,103,024, 1,106,958 and 1,106,959 and DE-OS (German Published Specifications) Nos. 2,323,393 and 2,418,075.

The parasiticidal active compound can be added to these thermoplastic polyurethanes, which can be, for example, in granular form, together with the spreading agents in suitable mixing devices, for example in drums or in an extruder; however, it is also possible to add the active compound and spreading agent directly during the preparation of the polyurethane, if appropriate as a mixture with one of the starting components, for example in a process according to DE-OS (German Published Specification) No. 2,302,564 (largely equivalent to U.S. Pat. No. 3,963,679), the polyisocyanates and polyhydroxy compounds being reacted with one another continuously in a twin-screw extruder. In this process, however, care should be taken that the reaction temperature does not exceed the decomposition point of the active compound used as the ectoparasiticide.

Of the production methods which are in themselves known in polyurethane chemistry and are possible according to the invention and which use reactive mixtures, such as the casting process, spraying process or reactive injection-moulding process, the casting process is the procedure which is preferred according to the invention. In this procedure, the polyurethanes according to the invention can be produced in a manner which is in itself known, either by the one-stage process or by the prepolymer or semi-prepolymer process.

Of the process variants of the casting process, the one-stage process is particularly preferred according to the invention. In this case, the higher-molecular polyols, ectoparasiticidal active compound, spreading agent and, if appropriate, crosslinking agent and fillers and additives, and, finally, the catalyst are mixed together, and the isocyanate component is then mixed in.

In the procedures for the casting process, the conveying, metering and mixing of the individual components or component mixtures can be effected with the devices which are in themselves known to the expert.

The polyurethanes according to the invention can be prepared continuously or discontinuously. The procedure depends on the desired shape of the ectoparasiticide-containing polyurethanes according to the invention. For example, if shaped articles are to be produced, the discontinuous procedure should be used. However, if the polyurethane according to the invention is to be prepared, for example, in thin pieces of suitable dimensions, a continuous procedure is more advantageous. In this case, an endless web is first produced, which can then be divided into individual pieces, for example sheets or films.

In the case of continuous production, the ectoparasiticide-containing reactive mixture can also be sprayed or spread with a blade before it solidifies as a result of the reaction. In this case, the reactive mixture can be applied to diverse materials based on naturally occurring or synthetic raw materials, for example to mats, fleeces, knitted fabrics, mesh fabrics, foamed films or woven fabrics.

The conditions during the reaction can also be varied in a manner such that either compact or foamed polyurethanes are obtained. For example, if air is whipped into the reactive mixture, foams are obtained.

According to the invention, the ectoparasiticidal active compounds can also be added to solvent-free reactive systems which contain spreading agents and consist of a higher-molecular polyisocyanate component and a polyamine component, such as are described, for example, in DE-OS (German Published Specification) No. 2,448,133.

It is, of course, also possible, according to the invention, to introduce the active compound into a solution of a polyurethane or polyurethane-urea and then to evaporate off the solvent. In this case also, higher temperatures must be avoided, so that no decomposition of the active compound occurs. It is therefore expedient to use solutions of polyisocyanate polyaddition products in weakly polar, highly volatile solvents or solvent mixtures. Such so-called "soft solvent" systems are described, for example, in U.S. Pat. No. 2,957,852, British Patent Specification No. 1,040,055, German Patent Specification No. 643,811, U.S. Pat. Nos. 3,609,112, 3,752,786 and 3,936,409 and DE-OSen (German Published Specifications) Nos. 1,694,277, 2,221,750, 2,221,751 and 2,221,798 (largely equivalent to U.S. Pat. Nos. 3,734,894, 3,912,680, 3,867,350 and 3,857,809, respectively). Polar solvent systems (for example containing dimethylformamide or N-methylpyrrolidone) can also be used if the devolatilisation temperature is kept sufficiently low.

It is possible, according to the invention, to prepare the polyurethanes of the invention using a polyurethane as such, for example by injection-moulding or reactive injection-moulding of one of the thermoplastics mentioned, or to prepare the polyurethanes of the invention in situ by allowing a reactive casting system to react in a suitable mould. However, in many cases it is desirable to impregnate and/or coat a suitable carrier material (for example a woven fabric of natural and/or synthetic fibres, leather, imitation leather or a porous or homogeneous plastic film) with one of the abovementioned thermoplastic polyurethanes, two-component casting systems or one-component polyurethanes, dissolved in solvents which can be evaporated off easily, which contain the active compound. In general, this carrier material, for example in the case of an animal tag, is worn on the outside, and the coating with the ectoparasiticide-containing polyurethane is on the inside. In this manner, it is possible, for example, to give an animal tag virtually any desired appearance.

The polyurethanes according to the invention can be employed in the most diverse ways and in the most diverse forms, for example as granules, sheets, films, webs, blocks, rods or shaped articles.

The ectoparasiticide-containing polyurethanes according to the invention can be used in the most diverse fields, for example in the form of sheets, strips or shaped articles which are attached to animals, such as cattle, in a suitable manner, and in particular to the tail, horns or ears (ear tags). The polyurethanes according to the invention can also be applied, or placed or hung, in stalls and living quarters; especially in stalls, the polyurethanes according to the invention can be scattered in the form of granules, applied to the walls in the form of a sprayed film or attached to the walls or placed over the animal as mats in the form of sprayed fleeces. A further possible use comprises using the ectoparasiticide-containing polyurethanes according to the invention in the form of granules, for combating infestation of horses by Gastrophilus. In a use which is preferred according to the invention, the insecticide-containing polyurethanes are spread out or are stood in kitchens or other rooms in order to combat cockroaches.

The polyurethanes according to the invention can be successfully employed against numerous harmful animal parasites (ectoparasites) from the class of Arachnida and the class of insects.

Examples which may be mentioned of ectoparasites from the class of Arachnida which are of significance in the tropical, sub-tropical and temperate latitudes are, from the family of the Ixodidae: the Australian and South American one-host cattle tick (Boophilus microplus), the African one-host cattle tick (Boophilus decoloratus), the multi-host parasitic ticks which attack livestock and pets in all parts of the world, such as Rhipicephalus appendiculatus, Thipicephalus evertsi, Amblyomma variegatum, Amblyomma hebraeum, Amblyomma cayennense, Hyalomma truncatum, Dermacentor variabilis and Ixodes ricinus, and from the family of Gamasidae: the red poultry mite (Dermanyssus gallinae).

Examples which may be mentioned of ectoparasites from the class of insects are: Mallophaga, such as, for example, the dog-biting louse (Trichodectes canis), the cattle-biting louse (Damalinea bavis), the sheet-biting louse (Damalinea ovis) and the poultry-biting louse (Eomenacanthus stramineus); Anoplura, such as, for example, the cattle louse (Haematopinus erysternus) and the pig louse (Haematopinus suis); Diptera, such as, for example, the sheet ked (Melophagus ovinus); and Aphaniptera, such as, for example, the dog flea (Ctenocephalides canus).

The following examples illustrate the present invention. Unless otherwise indicated, the parts given in the examples are parts by weight.

The following ectoparasiticidal active compounds are employed in the examples below:

"Active Compound 1"=2-isopropoxyphenyl N-methylcarbamate (propoxur)

"Active Compound 2"=3-phenoxy-4-fluoro-.alpha.-cyano-benzyl 2,2-dimethyl-3-[2-(4-chlorophenyl)-2-chlorovinyl]-cyclopropanecarboxylate

"Active Compound 3"=permethric acid pentafluorobenzyl ester.

Example 1

An ectoparasiticidal polyurethane was produced from the immediately following components A and B;

Example 2

An ectoparasiticidal polyurethane was produced from the immediately following components A and B.

Example 3

An ectoparasiticidal polyurethane was produced from the immediately following components A and B.

Example 4

An ectoparasiticidal polyurethane was produced from the immediately following components A and B.

Example 5

An ectoparisiticidal polyurethane was produced from the immediately following components A and B.

Example 6

An ectoparasiticidal polyurethane was produced from the immediately following components A and B.

The following table indicates the number of parts by weight of the items of components A and B from which the ectoparasital polyurethanes of Examples 7 to 13 were formed.

The polyurethanes according to Examples 1 to 13 were produced continuously by the casting process with the aid of a belt installation. The polyether, active compound or active compound combination, colour paste, zeolite paste, spreading agent and butane-1,4-diol were mixed together in a kettle which could be heated and the mixture was warmed to 60.degree. C. The catalyst (dibutyl-tin dilaurate) was then admixed.

The resulting mixture was component A, which was mixed with the respective component B by means of a mixing unit. The mixing head was attached to a sideways traversing device which moved to and fro. The reaction mixture flowed continuously out of the mixing head onto the imitation leather (for example coating) or onto a web of plastic. The reaction mixture started to react 30 seconds after leaving the mixing head and had hardened after about 60 seconds.

The temperature in the polyurethane material rose to about 90.degree. C. within 2 minutes and remained at 90.degree. C. for a period of 1 minute.

The web then passed through a cooling zone. The product had solidified to such an extent that it could be passed over a system of slowly revolving V-belts to the cutting device.

Polyurethane compositions were cast, by the prepolymer process (via isocyanate prepolymers), from each of the combinations of polyurethane components, spreading agents and active compounds listed in the following Examples 14 to 16 and were then granulated. The granules were converted to strands by the injection-moulding process.

Example 14

40.4 parts of a polyester obtained from butane-1,4-diol and adipic acid (m.w. 2,000)

5.14 parts of 1,4-butanediol and diphenylmethane 4,4'-diisocyanate in an amount corresponding to a NCO/OH ratio of 1.03,

15 parts of active compound 1 and

18 parts of isopropyl myristate.

Example 15

43.5 parts of a polyester obtained from ethylene glycol, butanediol and adipic acid (m.w. 2,000),

5.65 parts of butane-1,4-diol and diphenylmethane 4,4'-diisocyanate in an amount corresponding to a NCO/OH ratio of 1.03,

10 parts of active compound 1,

2.5 parts of active compound 2 and

15 parts of lauric acid hexyl ester.

Example 16

25 parts of a polypropylene glycol ether (m.w. 2,000)

25 parts of a polyester obtained from butane-1,4-diol and adipic acid (m.w. 2,000)

4.5 parts of butane-1,4-diol and diphenylmethane 4,4'-diisocyanate in an amount corresponding to a NCO/OH ratio of 1.03,

10 parts of active compound 1,

5 parts of active compound 2, and

16 parts of isopropyl myristate.

Iron oxide pigment was employed as the dyestuff. All the polyurethane systems prepared according to Examples 14 to 16 released the active compound uniformly to the environment over a period of several months.

Example 17

20 g of active compound were dissolved in 50 g of methyl ethyl ketone at room temperature, with occasional stirring. 25 g of N-methylpyrrolidone and 15 parts of isopropyl myristate were then added and 25 g of a granular thermoplastic polyurethane were dissolved in the mixture thus obtained.

The solution was cast to a film 1 mm thick and the solvents were removed in a drying cabinet at 100.degree. to 150.degree. C. in the course of 60 minutes. A homogeneous, transparent film from which the active compound did not effluoresce even on prolonged storage, was formed.

The polyurethane was prepared by reacting 100 parts of a polyester of butanediol, ethylene glycol and adipic acid (OH number: 51.7), 7.5 parts of butane-1,4-diol and 31.3 parts of 4,4'-diisocyanatodiphenylmethane (NCO/OH=0.97) in a reaction screw in accordance with the method of DE-OS (German Published Specification) No. 2,302,564.

Comparison Experiment

The in vitro release (release of active compound) of active compound 1 from the polyurethane system according to the invention prepared as in Examples 1 and 2 was compared as follows with the result obtained with a conventional PVC system containing propoxur (see FIG. 1).

The in vitro release of the active compound 1 was determined over a period of weeks by standardised and gentle rubbing with fur rollers, which permitted differentiated evaluation of various systems.

These tests imitated mechanical rubbing off of the active compound on the animal.

In FIG. 9, the release of active compound in mg was plotted as the ordinate against the time in days as the abscissa. Curves A, B, C, D and E were as follows:

A denotes a PVC system, stored for 6 months

B denotes a PVC system, stored for 1 month

C denotes a PUR system according to Example 1

D denotes a PUR system according to Example 2

E denotes a PUR system without a spreading agent

Our copending patent application corresponding to U.S. patent application Ser. No. 308,718, filed Oct. 5, 1981, now abandoned, which was continued as U.S. patent application Ser. No. 456,141, filed Jan. 6, 1983, now pending. describes and claims animal collars comprising polyurethanes of the present invention and the terms "shaped articles", "coatings" and "impregnations" used herein accordingly exclude such animal collars.

Claims

What is claimed is:

1. An ectoparasiticide-containing polyurethane, comprising a hydrophobic polyurethane which cannot be swollen in water and which contains, relative to the polyurethane, 2 to 30% by weight of an ectoparasiticide, said ectoparasiticide selected from the group consisting of an insecticidally active carbamate having a vapor pressure of between about 10.sup.-4 and 10.sup.-6 mm Hg measured at 20.degree. C., and an insecticidally active synthetic pyrethroid, and combinations thereof and, relative to the polyurethane, 8 to 25% by weight of a spreading agent, said speading agent selected from the group consisting of silicone oils, fatty acid esters, fatty alcohols, fatty acids and combinations thereof.

2. An ectoparasiticide-containing polyurethane according to claim 1, characterized in that it contains, relative to the polyurethane, 5 to 20% by weight of the ectoparasiticide or of a combination of ectoparasiticides.

3. An ectoparasiticide-containing polyurethane according to claim 1 wherein the ectoparasiticide is 2-isopropoxyphenyl N-methyl carbamate, 3-phenoxy-4-fluoro-.alpha.-cyano-benzyl-2,2-dimethyl-3-[2-(4-chlorophenyl) -2-chlorovinyl]cyclopropane carboxylate, permethric acid pentafluorobenzyl ester or a mixture of said ectoparasiticides.

4. An ectoparasiticide-containing polyurethane according to claim 1, characterized in that the polyurethane has been prepared by the casting process.

5. An ectoparasiticide-containing polyurethane according to claim 1, characterized in that the polyurethane is a polyurethane which when stored in water at 20.degree. C. for 24 hous, absorbs less than 0.5% by weight of water as a result of swelling.

6. A sheet or film, or shaped article, coating or impregnation comprising a polyurethane according to claim 1.

7. In a sheet, film, shaped article, coating, or impregnation for combating ectoparasites, the improvement comprising the inclusion into said sheet, film, shaped article, coating or impregnation a polyurethane according to claim 1.

8. An ectoparasiticide-containing polyurethane according to claim 1, wherein said spreading agent is a fatty acid ester selected from the group consisting of fatty acid esters of saturated fatty acids of the chain length C.sub.8 -C.sub.18 and linear or branched alcohols of the chain length C.sub.2 -C.sub.8, fatty acid esters of unsaturated fatty acids of the chain length C.sub.16 -C.sub.20 and linear or branched alcohols of the chain length C.sub.2 -C.sub.12 and fatty acid esters of saturated dicarboxylic acids of the chain length C.sub.2 -C.sub.16.

9. An ectoparasiticide-containing polyurethane according to claim 9, wherein said fatty acid ester of saturated fatty acids of the chain length C.sub.8 -C.sub.18 and linear or branched alcohols of the chain length C.sub.2 -C.sub.8 are selected from the group consisting of lauric acid hexyl ester, ethyl stearate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, dipropylene glycol pelargonate and butyl stearate.

10. An ectoparasiticide-containing polyurethane according to claim 8 wherein said fatty acid ester of unsaturated fatty acids of the chain length C.sub.16 -C.sub.20 and linear or branched alcohols of the chain length C.sub.2 -C.sub.12 is oleic acid decyl ester.

11. An ectoparasiticide-containing polyurethane according to claim 8 wherein said fatty acid esters of saturated dicarboxylic acids of the chain length C.sub.2 -C.sub.16 are selected from the group consisting of diisopropyl adipate, dibutyl sebacate, diisodecyl adipate and dibutyl adipate.

12. An ectoparasiticide-containing polyurethane according to claim 1, wherein said spreading agent is selected from the group consisting of triglycerides of fatty acids of the chain length C.sub.7 -C.sub.18 and partial glycerides of saturated or unsaturated fatty acids.

13. An ectoparasiticide-containing polyurethane according to claim 1, wherein said spreading agent is a fatty alcohol selected from the group consisting of isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol and oleyl alcohol.

14. An ectoparasiticide-containing polyurethane according to claim 1, wherein said spreading agent is a fatty acid which is selected from the group consisting of oleic acid and stearic acid.

15. A shaped article according to claim 6, wherein said shaped article is an ear tag for attachment to an animal's ear.

16. In a process for the production of ectoparasiticide-containing polyurethane sheets, films, shaped articles, coatings or impregnations including forming sheets, films, shaped articles, coatings or impregnations from an ectoparasiticide-contining polyurethane, the improvement wherein said polyurethane is a polyurethane according to claim 1.

17. In a method of combating ectoparasites including applying to a habitat containing ectoparasites or to an animal a sheet, film, shaped article, coating or impregnation of an ectoparasiticide-containing material, the improvement wherein said material is an ectoparasiticide-containing polyurethane according to claim 1.

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Abstract

Description