DE10063864A1 - Molded articles containing pyrazoloxime for dermal control of parasites on animals - Google Patents

Abstract

The invention relates to moulded bodies containing pyrazole oxime for controlling skin parasites on animals. Such moulded bodies include, inter alia, collars, tags for collars, ear-marks, bands to be fixed to limbs or body parts, adhesive strips and films, and removable films. Preferably, pyrazole oximes of general formula (I) are used, especially fenpyroximate.

Description

The present invention relates to pyrazoloxime-containing moldings for dermal Control of parasites on animals.

From the group of pyrazole oximes, compounds are known which are insecticidal, have acaracidal and fungicidal activity. These connections are exemplary as in EP 0 234 045, EP 0 944 319, WO 095 07 615 and WO 095 07 615 wrote. It can also be seen from the literature mentioned that at for example 1,1-dimethylethyl-4- (1,3-dimethyl-5-phenoxy-1H) pyrazole derivatives Combat parasites in animals. The disadvantage of the previously described NEN application techniques is that they have a large application effort require, possibly lead to contamination of the environment and thus to the treatment of Small animals, especially cats and dogs, are not suitable.

There were now new, user-friendly and environmentally friendly moldings in the registration dung called solid formulation for the dermal application of pyrazole oximes found, especially for the dermal control of parasitic arthro suitable for animals. These fixed formulations are particularly against Ectoparasites, normally sensitive and resistant species, as well as against all or some Developmental stages of the animals mentioned are effective.

The invention therefore relates to solid formulations for the dermal control of Parasites on animals containing a pyrazoloxime active against parasites.

The invention further relates to the use of the solid according to the invention Formulations for the dermal control of parasites on animals.  

Suitable pyrazole oximes with insecticidal and acaricidal activity are, for. B. in the EP-A-0 234 045 to which express reference is made.

Pyrazole oximes of the general formula (I) are preferably used

wherein
R ^{1 is} C ₁ -C ₄ alkyl or phenyl,
R ^{2 is} hydrogen, C ₁ -C ₅ alkyl, C ₁ -C ₃ haloalkyl or phenyl,
R ^{3 is} hydrogen, C ₁ -C ₄ alkyl or phenyl,
R ^{4 is} hydrogen, C ₂ -C ₄ alkylcarbonyl, benzoyl, naphthyl or a substituent of the formula

[wherein
X represents hydrogen, halogen;
C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyl substituted with halogen, cyano, hydroxy, C ₁ -C ₅ alkoxy or C ₂ -C ₆ alkoxycarbonyl; C ₃ -C ₈ cycloalkyl; C ₃ -C ₈ cycloalkyl substituted with 1 to 3 substituents selected from the group consisting of: C ₁ -C ₄ alkyl, halogen and cyano; C ₂ -C ₄ alkenyl substituted with halogen, hydroxy, C ₂ -C ₄ alkoxycarbonyl or C ₂ -C ₆ alkylcarbonyl; Phenyl; Hydroxy; C ₁ -C ₆ alkoxy; C ₁ -C ₄ alkoxy substituted with halogen or C ₂ -C ₆ alkoxy carbonyl; Phenoxy optionally substituted with C ₁ -C ₃ halo alkyl; Benzyloxy; C ₁ -C ₃ -alkylenedioxy formed from two neighboring substituents X; Pyridyloxy optionally substituted with halogen or C ₁ -C ₃ haloalkyl; -S (O) _p R ⁵ (wherein R ^{5 is} C ₁ -C ₆ alkyl, C ₁ -C ₅ haloalkyl or phenyl and p is 0, 1 or 2); Cyano; Formyl; Nitro; -COOR ⁶ {wherein R ^{6 is} hydrogen, alkali metal, C ₁ -C ₁₀ alkyl, C ₁ -C ₅ alkyl substituted with halogen, C ₁ -C ₄ alkoxy, phenoxy, C ₂ -C ₄ alkoxycarbonyl or phenoxyphenyl; C ₂ -C ₇ alkenyl; C ₃ -C ₇ alkynyl; C ₃ -C ₈ cycloalkyl; C ₃ -C ₈ cycloalkyl substituted with C ₁ -C ₃ alkyl; Phenyl; -S _n R ⁷ R ⁸ R ⁹ (wherein R ⁷ , R ⁸ and R ^{9 are the} same or different and are C ₁ -C ₄ alkyl or C ₃ -C ₈ cycloalkyl)}; C ₂ -C ₆ alkylcarbonyl; C ₂ -C ₆ alkylcarbonyl substituted with cyano or C ₂ -C ₆ alkoxycarbonyl; Benzoyl optionally substituted with halogen or C ₁ -C ₆ alkyl; C ₂ -C ₆ alkylthiocarbonyl; C ₃ -C ₇ alkoxycarbonylcarbonyl; -C (= O) NR ¹⁰ R ¹¹ (wherein R ¹⁰ and R ^{11 are the} same or different and represent hydrogen, C ₁ -C ₆ alkyl or phenyl); Piperidinocarbonyl; Morpholinocarbonyl, which is optionally mono- or disubstituted by C ₁ -C ₄ alkyl; -NR ¹² R ¹³ (where R ^{12 is} hydrogen or C ₁ -C ₅ alkyl and R ^{13 is} formyl, C ₂ -C ₁₂ alkoxycarbonyl or C ₂ -C ₅ alkoxycarbonyl substituted with halogen or C ₁ -C ₄ - Alkoxy means); a substituent of the formula

(wherein R ^{14 is} hydrogen, C ₁ -C ₄ alkyl or C ₉ -C ₆ alkoxyalkyl); -C (BR ¹⁵ ) (BR ¹⁶ ) (R ¹⁷ ) (wherein R ¹⁵ and R ^{16 may be the} same or different and stand for C ₁ -C ₄ alkyl or together form a C ₁ -C ₄ alkylene radical, R ^{17 represents} C ₁ -C ₅ alkyl, cyano or C ₂ -C ₆ alkoxycarbonyl and B represents oxygen or sulfur; -C (OR ¹⁸ ) R ¹⁹ R ²⁰ (in which R ^{18 is} hydrogen or C ₂ -C ₄ - Alkyl is carbonyl and R ¹⁹ and R ^{20 are} identical or different and are hydrogen or C ₁ -C ₆ alkyl); -SiR ²¹ R ²² R ²³ (in which R ²¹ , R ²² and R ^{23 are} identical or different and C ₁ Is -C ₄ alkyl); or -O-SiR ²⁴ R ²⁵ R ²⁶ (in which R ²⁴ , R ²⁵ and R ^{26 are the} same or different and are C ₁ -C ₄ alkyl), and
n is an integer from 1 to 5, where when n is an integer from 2 to 5, X can be the same or different];
Y hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl, halogen, hydroxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₃ alkylenedioxy, phenoxy, which is optionally substituted by trifluoromethyl, S (O) _q R ²⁷ (in which R ^{27 is} C ₁ -C ₃ alkyl and q is 0, 1 or 2), hydroxycarbonyl, C ₂ -C ₅ alkoxycarbonyl or -NR ²⁸ R ²⁹ (in which R ²⁸ and R ²⁹ are identical or different and represent hydrogen, C ₁ -C ₄ -alkyl or benzyl which is optionally substituted by C ₂ -C ₆ -alkoxycarbonyl);
Z ^{1 represents} oxygen or sulfur;
Z ^{2 represents} oxygen, sulfur or a single bond;
Z ^{3 represents} aryl or heteroaryl
QC ₁ -C ₈ alkylene, C ₁ -C ₈ alkylene substituted with halogen or phenyl, C ₃ -C ₁₂ alkenylene, C ₃ -C ₁₂ haloalkenylene or C ₃ -C ₆ alkynylene means; and
m represents an integer from 1 to 3, where if m represents an integer 2 or 3, Y can be the same or different.

Said compounds can, depending on the substitution pattern in stereoisomeric forms, which are either like image and mirror image (enantiomers), or that do not behave like image and mirror image (diastereomers) exist. The invention relates both to the enantiomers or diastereomers and to theirs respective mixtures. The racemic forms can be just like the diastereomers separate into the stereoisomerically uniform constituents in a known manner.

Furthermore, certain compounds can exist in tautomeric forms. This is known to those skilled in the art, and such compounds are also within the scope of Invention includes.

The compounds of the invention can optionally be both cis and exist as trans isomers. Even if only one of the isomers is shown, are invented according to the cis and the trans isomer always meant.

"Alkyl", "alkenyl" and "alkynyl" stand for one in the context of the invention chain or branched alkyl, alkenyl or alkynyl radical with 1 to 12 carbon atoms. A straight-chain or branched alkyl, alkenyl or Alkynyl radical with 1 to 6, particularly preferably 1 to 4, carbon atoms. As examples for alkyl radicals may be mentioned: methyl, ethyl, n-propyl, isopropyl, t-butyl, n-pentyl and n-hexyl. Examples of alkenyl radicals are: vinyl, allyl, isopropenyl and n-  But-2-en-1-yl. Examples of alkynyl radicals are: ethynyl, n-prop-2-yn-1-yl and n-but-2-in-1-yl.

"Haloalkyl" in the context of the invention represents an alkyl radical as defined above, in which one or more, preferably one, two or three, hydrogen atoms Halogen atoms (same or different) are replaced.

"Halogen" in the context of the invention stands for fluorine, chlorine, bromine and iodine.

In the context of the invention, “aryl” stands for an aromatic radical with 6 to 14, preferably 6 to 10 carbon atoms. Examples are phenyl and naphthyl, which is phenyl particularly preferred.

"Heteroaryl" in the context of the invention stands for 5- to 10-membered, preferably 5- and 6-membered aromatic rings containing heteroatoms with up to 4 hetero atoms selected from O, S and N and includes, for example: pyridyl, furyl, Thienyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, Indolicenyl, indolyl, benzo [b] thienyl, benzo [b] furyl, indazolyl, quinolyl, iso quinolyl, naphthyridinyl, quinazolinyl, etc. Pyridyl is particularly preferred.

Unless otherwise stated, substituted radicals carry one or more before adds one to two or three, identical or different substituents.

Particularly preferred pyrazole oximes are the compounds of the general formula (Ia)

wherein
R ^{30 represents} straight-chain or branched alkyl having up to 6 carbon atoms and
R ^{31 represents} aryl or heteroaryl, which can each be substituted by halogen.

Very particularly preferred examples of pyrazole oximes of the formula (Ia) are in the listed in Table 1 below:  

Table 1

Based on our observations, the solid form according to the invention lations advantageously amounts of active ingredient from 10 to about 300 mg, preferably 20 to 200 mg, particularly preferably 25 to 160 mg per kg of body weight release the animal in the course of at least three months to a to ensure good effectiveness against fleas and ticks.

The solid formulations according to the invention are preferably Molded body. Shapes are u. a. Collars, pendants for collars (medallions), Ear tags, straps for attachment to limbs or body parts, adhesive strips and films, peeling films.  

Collars and medallions deserve special mention.

Thermoplastic and flexible or heat are used to manufacture the molded articles curable plastics as well as elastomers and thermoplastic elastomers in question. As such are called polyvinyl resins, polyurethanes, polyacrylates, epoxy resins, Cellu loose, cellulose derivatives, polyamides and polyesters containing the above active ingredient are sufficiently tolerated. The polymers must have sufficient strength and Have flexibility so as not to crack or become brittle during molding. they must be of sufficient durability to withstand normal wear and tear be. In addition, the polymers must undergo sufficient migration of the active ingredient allow the surface of the molded body.

The polyvinyl resins include polyvinyl 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, such as Polystyrene and polyvinyltoluene. Special mention should be made of polyvinyl chloride.

The plasticizers are used to manufacture the molded articles based on polyvinyl resin suitable, which is usually used to soften solid vinyl resins will. The plasticizer to use depends on the resin and its compatibility with the plasticizer. Suitable plasticizers are, for example, esters of phosphoric acid, such as esters of phthalic acid, such as dimethyl phthalate and Di octyl phthalate, and esters of adipic acid such as diisobutyl adipate. Others can 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, as well complex linear polyesters, polymeric plasticizers and epoxidized soybean oils be used. The amount of the plasticizer is about 10 to 50% by weight, preferably about 20 to 45% by weight of the total composition.  

Further constituents, such as stabilizing agents, Lubricants, mold release agents, fillers and coloring materials can be included without that it changes the basic properties of the composition will. Suitable stabilizers are antioxidants and agents that Bands from ultraviolet radiation and unwanted degradation during the Machining how to protect extrusion. Some stabilizers, such as epoxidized Soybean oils also serve as secondary plasticizers. As a lubricant can, for example, stearates, stearic acid and low polyethylenes Molecular weight can be used. These components can be in one Concentration up to about 5% by weight of the total composition used will.

In the production of the molded articles based on vinyl, the various Components mixed by known methods and by known extrusion or Injection molding process.

The choice of the processing method for the production of the shaped body is directed technically basically according to the rheological properties of the strip material and the shape of the desired band. The processing methods can be according to the Processing technology or according to the type of shape. At In terms of process technology, the processes can be classified according to the ones they run through subdivide rheological conditions. Then come for viscous tape materials Casting, pressing, injection molding and application and for elastoviscous polymer injection casting, extrusion (extrusion), calendering, rolling and possibly edges in question. Divided according to the type of shape, the invention can be Moldings by casting, dipping, pressing, injection molding, extruding, calendering, Manufacture embossing, bending, deep drawing etc.

These processing methods are known and require no further explanation. in the In principle, the explanations given above for other polymers are exemplary for poly vinyl resins were made.  

The polyurethanes used as the carrier material are made in a manner known per se by reacting polyisocyanates with higher molecular weight, at least two against compounds having groups reactive toward isocyanates and optionally low molecular weight chain extenders and / or monofunk tional chain breakers.

The starting components in the production of the polyurethanes are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates in Consider how z. B. by W. Siefken in Liebig's Annalen der Chemie, 562, pages 75 to 136. Examples include: ethylene diisocyanate, 1,4- Tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, Cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any Mixtures of these compounds, 1-isocyanato-3,3,5.-trimethyl-5-isocyanatomethyl cyclohexane (see DE-AS 202 785 and US-PS 3 401 190), 2,4- and 2,6-hexahydro tolylene diisocyanate and any mixtures of these compounds; Hexahydro-1,3- and / or -1,4-phenylene diisocyanate, perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any 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 those produced by aniline-formaldehyde Obtain condensation and subsequent phosgenation and z. B. in GB-PSen 874 430 and 848,671; m- and p-isocyanatophenol sulfonyl isocyanates according to U.S. Patent 3,454,606; perchlorinated aryl polyisocyanates such as e.g. B. are described in DE-AS 11 57 601 and in US Pat. No. 3,277,138; Carbodi polyisocyanates containing imide groups, as described in DE-PS 10 92 007 and in U.S. Patent 3,152,162; Diisocyanates as described in U.S. Patent 3,492,330 to be discribed; Allophanate group-containing polyisocyanates, such as z. B. in the GB-PS 994 890, the DE-PS 76 16 26 and the published Dutch Patent application 7 102 524 can be described; Isocyanurate groups Polyisocyanates such as z. B. in US-PS 3 001 973, in DE-PS 10 22 789,  1 222 067 and 1 027 394 and in DE-OSes 19 29 034 and 2 004 048 will; Polyisocyanates containing urethane groups, such as z. B. in DE-PS 752 261 or described in U.S. Patent No. 3,394,164; acylated urea groups polyisocyanates according to DE-PS 12 30 778; Biuret groups Polyisocyanates such as z. B. in DE-PS 11 01 394, in US-PS 3 124 605 and 3,201,372, and in GB-PS 889,050; through telomerization reactions produced polyisocyanates such as z. B. in U.S. Patent 3,654,106 be ben; Polyisocyanates containing ester groups, such as, for. B. in GB-PSen 965 474 and 1 072 956, in US-PS 3 567 763 and in DE-PS 12 31 688 will; Reaction products of the above isocyanates with acetals according to the DE-PS 10 72 385 and polymeric fatty acid residues containing polyisocyanates according to the U.S. Patent 3,455,883.

It is also possible to use the iso Distillation residues containing cyanate groups, optionally dissolved in one or more of the aforementioned polyisocyanates. It is also possible to use any mixtures of the aforementioned polyisocyanates.

Preferred polyisocyanates are generally the tolylene diisocyanates and Diphenylmethane diisocyanates.

Starting components for the production of the polyurethanes are also compounds with at least two hydrogen atoms reactive towards isocyanates a molecular weight of usually 400-10 000. This means in addition to Compounds containing amino groups, thiol groups or carboxyl groups preferably polyhydroxyl compounds, in particular two to eight hydroxyl group-containing compounds, especially those with a molecular weight of 800 to 10,000, preferably 1,000 to 6,000, e.g. B. at least two, usually 2-8, but preferably 2-4, hydroxyl-containing polyesters, polyethers, Polythioethers, polyacetals, polycarbonates and polyesteramides, such as those for the Her position of homogeneous and cellular polyurethanes are known per se.  

The hydroxyl-containing polyesters are z. B. Reaction products of polyvalent, preferably divalent and given if additionally trivalent, carboxylic acids. Instead of the free polycarboxylic acids can also the corresponding polycarboxylic anhydrides or corresponding Polycarboxylic esters of lower alcohols or their mixtures for the production the polyester can be used. The polycarboxylic acids can be aliphatic, cyclo be aliphatic, aromatic and / or heterocyclic in nature and, if appropriate, e.g. B. by halogen atoms, substituted and / or unsaturated.

Examples include: succinic acid, adipic acid, suberic acid, Azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthal acid anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Tetrachlorophthalic anhydride, endomethylene tetrahydrophthalic anhydride, glutar acid anhydride, maleic acid, maleic anhydride, fumaric acid, dimers and trimer Fatty acids such as oleic acid, optionally in a mixture with monomeric fatty acids, Dimethyl terephthalate and bis-glycol terephthalate.

As polyhydric alcohols such. B. ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol- (1,4) and - (2,3), hexanediol- (1,6), octanediol- (1,8), neopentygly kol, cyclohexanedimethanol (1,4-bis-hydroxy-methylcyclohexane), 2-methyl-1,3- propanediol, glycerin, trimethylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2,4), tri methylethane, pentaerythritol, quinite, mannitol and sorbitol, methyl glycol, further Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropy lenglycol, polypropylene glycols, dibutylene glycol and polybutylene glycols in question. The Polyesters can have a proportion of terminal carboxyl groups. Also made of polyester Lactones, e.g. B. ε-caprolactone or hydroxycarboxylic acids, e.g. B. ω-hydroxycaproic acid, can be used.

Possible polyhydric alcohols are polyethers which have at least two, generally two to eight, preferably two to three, hydroxyl groups. These are known per se and z. B. by polymerization of epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, for. B. in the presence of BF ₃ or by addition of these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as water, alcohols, ammonia or amines, for. B. ethylene glycol, propylene glycol (1,3) or - (1,2), trimethylolpropane, 4,4'-dihydroxydiphenylpropane, aniline, ethanolamine or ethylenediamine. Also sucrose polyethers, such as those e.g. B. are described in DE-ASen 11 76 358 and 10 64 938, come into question. In many cases, those polyethers are preferred which predominantly (up to 90% by weight, based on all the OH groups present in the polyether) have primary OH groups. Also modified by vinyl polymers, polyethers such as z. B. stand by polymerization of styrene and acrylonitrile in the presence of polyethers ent (US Pat. Nos. 3,383,351, 3,304,273, 3,523,093, 3,110,695, German Patent 11 52 536) are suitable, as are OH groups containing polybutadienes .

Among the polythioethers are, in particular, the condensation products on thio diglycol with itself and / or with other glycols, dicarboxylic acids, formaldehyde, Aminocarboxylic acids or amino alcohols listed. Depending on the co-components the products are polythio mixed ethers, polythioether esters or Polythioetheresteramides.

As polyacetals such. B. from glycols, such as diethylene glycol, triethylene glycol, 4,4'-Dioxethoxydiphenyldimethylmethan, hexanediol and formaldehyde Connections in question. It can also be obtained by polymerizing cyclic acetals Produce suitable polyacetals according to the invention.

Polycarbonates containing hydroxyl groups are those which per se known type into consideration, e.g. B. by reacting diols such as propanediol (1,3), Butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol or Tetraethylene glycol with diaryl carbonates, e.g. B. diphenyl carbonate, or phosgene can be put.  

The polyester amides and polyamides include e.g. B. the polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures obtained, mainly linear condensates.

Also polyhydroxyl compounds already containing urethane or urea groups and optionally modified natural polyols, such as castor oil, carbohydrates or starch, can be used. Addition products of alkylene oxides Phenol-formaldehyde resins or also on urea-formaldehyde resins are invented usable according to the invention.

Representatives of these compounds are e.g. B. in High Polymers, Vol. XVI, "Polyurethane, Chemistry and Technology ", written 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, as well as in the plastic manual, volume VII, Vieweg- Höchtlen, Carl Hanser Verlag, Munich, 1966, z. B. on pages 45-71 ben.

Of course, mixtures of the above compounds with min at least two isocyanate-reactive hydrogen atoms with one Molecular weight of 400-10,000, e.g. B. mixtures of polyethers used will.

Connections also come as starting components which may be used with at least two isocyanate reactive hydrogen atoms of a molecular weight of 32-400 in question. In this case, too, this is understood Hydroxyl groups and / or amino groups and / or thiol groups and / or carboxyl group-containing compounds, preferably compounds which are chain ver extenders or crosslinking agents. These connections point in the  Rule 2 to 8 hydrogen atoms reactive towards isocyanates, preferably wise 2 or 3 reactive hydrogen atoms.

Examples of such connections are:
Ethylene glycol, propylene glycol- (1,2) and - (1,3), butylene glycol- (1,4) and - (2,3), pentanediol- (1,5), hexanediol- (1,6), octanediol- (1,8), neopentyl glycol, 1,4-bis hydroxymethyl-cyclohexane, 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, hexanetriol- (1,2,6), trimethylolethane, pentaerythritol, quinite, 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, dibutyllene glycol, polybutylene glycols with a molecular weight of up to 400, 4,4'-dihydroxy-diphenylpropane, di-hydroxymethyl-ethanolamine , Diethanolamine, triethanolamine, 3-aminopropanol, ethylenediamine, 1,3-diamino propane, 1-mercapto-3-aminopropane, 4-hydroxy- or amino-phthalic acid, succinic acid, adipic acid, hydrazine, N, N'-dimethylhydrazine, 4,4'-diaminodiphenylmethane, toluenediamine, methylene-bis-ehloraniline, methylene-bis-anthranile acid ester, diamino benzoic acid ester and the isomer en chlorophenylenediamines.

In this case, too, mixtures of different compounds with min at least two isocyanate-reactive hydrogen atoms with one Molecular weight of 32-400 can be used.

However, polyhydroxyl compounds can also be used, in which high molecular weight polyadducts or polycondensates in finely dispersed or dissolved form are included. Such modified polyhydroxyl compounds are obtained if one carries out polyaddition reactions (e.g. reactions between polyisocyanates and amino functional compounds) or polycondensation reactions (e.g. between Formaldehyde and phenols and / or amines) directly in situ in the above, Connections containing hydroxyl groups can run off. Such procedures are for example in DE-ASen 11 68 075 and 12 60 142, and DE-OSen 23 24 134,  24 23 984, 25 12 385, 25 13 815, 25 50 797, 25 50 833 and 25 50 862 described. However, it is also possible, according to US Pat. No. 3,869,413 or DE-OS 25 50 860 a finished aqueous polymer dispersion with a polyhydroxyl compound to mix and then remove the water from the mixture.

When choosing the higher used for the production of the polyurethane Molecular polyol component should be noted that the finished polyurethane in water should not be swellable. The use of an excess of polyhydroxyl compounds with ethylene oxide units (polyethylene glycol polyether or polyester with diethylene or triethylene glycol as the diol component) should therefore be avoided.

Thermoplastic materials are particularly emphasized for the production of the shaped bodies Elastomers. These are materials that have elastomeric phases in thermoplastic processable polymers either physically mixed in or chemically included included. A distinction is made between polymer blends in which the elastomeric Phases are part of the polymeric framework. By building the Thermoplastic elastomers are hard and soft areas side by side. The hard areas form a crystalline network structure or a continuous one Phase whose gaps are filled with elastomeric segments. Because of With this structure, these materials have rubber-like properties.

There are 5 main groups of thermoplastic elastomers:

• 1. Copolyester
• 2. Polyether Block Amides (PEBA)
• 3. Thermoplastic Polyurethane (TPU)
• 4. Thermoplastic polyolefins (TPO)
• 5. Styrene block copolymers

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

in which
R represents a divalent radical of a dicarboxylic acid which has a molecular weight of less than about 350,
D represents a divalent radical of an organic diol that has a molecular weight below about 250.

The long chain ester units make up about 35-85% by weight of the copolyester and have the formula (III)

in which
R represents a divalent radical of a dicarboxylic acid which has a molecular weight of less than about 350,
G stands for a divalent residue of a long-chain glycol, which has an average molecular weight of about 350 to 6000.

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

The dicarboxylic acids for the preparation of the copolyester can be aromatic, ali be phatic or cycloaliphatic. The preferred dicarboxylic acids are the aromati acids with 8-16 carbon atoms, especially phenylenedicarboxylic acids, such as phthalic, Terephthalic and isophthalic acid.

The low molecular weight diols for the reaction to form the short-chain esters Copolyester units belong to the classes of acyclic, alicyclic and aromatic dihydroxy compounds. The preferred diols have 2-15 C- Atoms such as ethylene, propylene, tetramethylene, isobutylene, pentamethylene, 2,2-di methyltrimethylene, hexamethylene and decamethylene glycols, dihydroxycyclohexane, Cyclohexane dimethanol, resorcinol, hydroquinone and the like. To the bisphenols for the present purpose include bis (p-hydroxy) diphenyl, bis (p-hydroxy) phenyl) methane, bis (p-hydroxyphenyl) ethane and bis (p-hydroxyphenyl) propane.

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

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

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

Long-chain glycols also include polyformals, which are produced by the implementation of Formaldehyde can be obtained with glycols. Polythioether glycols are also suitable. Polybutadiene and polyisoprene glycols, copolymers thereof and saturated  Hydrogenation products of these materials are satisfactory long chain poly mere glycols.

Methods for the synthesis of such copolyesters are known from DOS 2 239 271, DOS 2 213 128, DOS 2 449 343 and US-P 3 023 192 are known.

Suitable copolyesters are e.g. B. under the trade name ®Hytrel from Du Pont, ®Pelpren from Toyobo®, Arnitel from Akzo, ®Ectel from Eastman Kodak and ®Riteflex available from Hoechst.

Suitable polyether block amides are, for example, those which consist of polymer chains which are composed of repeating units corresponding to the formula (IV).

in which
A is the polyamide chain derived from a polyamide with 2 carboxyl end groups by loss of the latter and
B which is derived from a polyoxyalkylene glycol with terminal OH groups by loss of the latter polyoxyalkylene glycol chain and
n is the number of units forming the polymer chain.

The end groups here are preferably OH groups or radicals of compounds which stop the polymerization.  

The dicarboxylic acid polyamides with the terminal carboxyl groups are on get known way, such. B. by polycondensation of one or more lactams or / and one or more amino acids, further by polycondensation of one Dicarboxylic acid with a diamine, each in the presence of an excess of one organic dicarboxylic acid, preferably with terminal carboxyl groups. These Carboxylic acids become part of the polyamide chain during polycondensation and attach themselves in particular to the end of the same, whereby a ∝-ω receives dicarboxylic acid polyamide. Furthermore, the dicarboxylic acid acts as a chain termination medium, which is why it is also used in excess.

The polyamide can be obtained from lactams and / or amino acids with a hydrocarbon chain consisting of 4-14 carbon atoms, such as. B. from Capro lactam, oenantholactam, dodekalactam, undekanolactam, decanolactam, 11-amino undecanoic or 12-aminododecanoic acid.

As examples of polyamides, such as those obtained by polycondensation of a dicarboxylic acid a diamine can be called the condensation products Hexamethylenediamine with adipic, azelaic, sebacic, and 1,12-dodecanedioic acid, and the condensation products of nonamethylene diamine and adipic acid.

In the case of those for the synthesis of the polyamide, that is, on the one hand for fixing each one Carboxyl group at each end of the polyamide chain and on the other hand as chains Dicarboxylic acid used as a demolition agent comes in those with 4-20 C atoms Question, especially alkanedioic acids, such as amber, adipic, cork, azelaic, sebacic, Undecanedioic or dodecanedioic acid, also cycloaliphatic or aromatic di carboxylic acid, such as terephthalic or isopropal or cyclohexane-1,4-dicarboxylic acid.

The polyoxyalkylene glycols containing terminal OH groups are unbranched or branched and have an alkylene radical with at least 2 carbon atoms. In particular  these are polyoxyethylene, polyoxypropylene and polyoxytetramethylene glycol, and copolymers thereof.

The average molecular weight of these OH group terminated polyoxyalkylene Glycole can move in a wide range, advantageously between 100 and 6000, especially between 200 and 3000.

The proportion by weight of the polyoxyalkylene glycol, based on the total weight of the polyoxyalkylene glycol and di used for the production of the PEBA polymer carboxylic acid polyamide is 5-85%, preferably 10-50%.

Processes for the synthesis of such PEBA polymers are known from FR-PS 7 418 913 (No. of Publication 2 273 021), DOS 2 802 989, DOS 2 837 687, DOS 2 523 991, EP-S 0 095 893, DOS 2 712 987 and DOS 2 716 004 are known.

Those PEBA polymers which, in contrast to those previously described, have a statistical structure are particularly suitable. A mixture of is used to produce these polymers

• 1. one or more polyamide-forming compounds from the group of the ω- Aminocarboxylic acids or lactams with at least 10 Carbon atoms,
• 2. a ∝-ω-dihydroxy-polyoxyalkylene glycol,
• 3. at least one organic dicarboxylic acid

in a weight ratio of 1: (2 + 3) between 30:70 and 98: 2, whereby in (2 + 3) hydroxyl and carbonyl groups are present in equivalent amounts, in Presence of 2 to 30 weight percent water, based on the polyamide forming compounds of group 1, under the autogenous pressure  heated to temperatures between 23 ° C and 30 ° C and then after removing the water in the absence of oxygen at normal pressure or further treated under reduced pressure at 250 to 280 ° C.

Such preferably suitable PEBA polymers are e.g. B. in DE-OS 27 12 987 described.

Suitable and preferably suitable PEBA polymers are e.g. B. under the trade names ®PEBAX from Atochem, ®Vestamid from Hüls AG, ®Grilamid from EMS- Chemistry and ®Kellaflex from DSM available.

The solid formulations according to the invention are suitable for inexpensive warmth Blood toxicity to combat parasites used in animal husbandry and breeding in domestic and farm animals as well as zoo, laboratory, experimental and hobby animals come. They are against normally sensitive and resistant species as well as against all or individual stages of development of the animals mentioned are effective.

Parasites are particularly arthropods. Those according to the invention are preferred solid formulations used to fight ectoparasites.

The above-mentioned ectoparasites include: tick ticks, leather ticks, mange mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, featherlings and fleas. These parasites include:
From the order of the Anoplurida z. B. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp ..

From the order of the Mallophagida and the subordinates Amblycerina as well Ischnocerina e.g. B. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., Felicola spp ..  

From the order Diptera and the subordinates Nematocerina as well Brachycerina e.g. B. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp ..

From the order of the Siphonapterida z. B. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp ..

From the order of the Heteropterida z. B. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp ..

From the order of the Blattarida z. B. Blatta orientalis, Periplaneta americana, Blattella germanica, Supella spp ..

From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata e.g. B. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp ..

From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata) z. B. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp ..  

The livestock and breeding animals include mammals such as B. cattle, horses, sheep, Pigs, goats, camels, water buffalos, donkeys, rabbits, fallow deer, reindeer; Fur animals such as B. mink, chinchilla, raccoon; such as B. chickens, geese, turkeys, Ducks.

Laboratory and experimental animals include mice, rats, guinea pigs, gold hamsters, dogs and cats.

The pets include dogs and cats.

The agents according to the invention are particularly suitable for the treatment of beef, Dog and cat, preferably to control ticks and / or Fleas.

The application can be prophylactic as well as therapeutic.

The moldings contain active compound in concentrations of 1 to 30% by weight, preferably from 5 to 20% by weight, particularly preferably from 7.5 to 12.5% by weight, based on the total mass of the solid formulation.

In the case of collars, the concentration of the active substances is preferably 1 to 15%; in the case of medallions, pendants and ear tags, preferably 5 to 20%, in the case of foils, adhesive strips are preferably 0.1 to 5%.

The new solid formulations can also contain other active ingredients, such as Insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides etc. included. Insecticides include, for example, phosphoric acid esters, Carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms u. a ..

Cheap co-active ingredients are e.g. B. the following:  

Insecticides / acaricides / nematicides

Abamectin, Acephate, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb, Alphacypermethrin, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azamethiphos, Azinphos A, Azinphos M, Azocyclotin,
Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Betacyfluthrin, Bifenazate, Bifenthrin, Bioethanomofufoxin, Bethentomomufhrin, Bethanomethuphrin Butyl pyridaben
Cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, Chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, Chlovaporthrin, cis-resmethrin, Cispermethrin, Clocythrin, cloethocarb, clofentezine, cyanophos, Cycloprene, cycloprothrin, cyfluthrin , Cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlorvos, Diflubenzuron, Dimethoat, Dimethylvinphos, Diofenolan, Disulfoton, Docusatsodium, Dofenapyn,
Eflusilanate, Emamectin, Empenthrin, Endosulfan, Entomopfthora spp., Eprinomectin, Esfenvalerate, Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos,
Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flubrocythrinate, Flucycloxuron, Flucythrinate, Futhronate, Fumenzoxin, Flutenzhonate, Flumenzhrinate, Fumenzhrinate, Fumenzhonate, Fumenzhonate, Fumenzhonate, Fumenzhonate, Fumenzhonate, Fumenzhonate, Fumenzoxin, Fuminoxin, Fuminoxin , Furathiocarb,
Granulosis viruses
Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene,
Imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,
Nuclear polyhedron viruses
Lambdacyhalothrin, Lufenuron
Malathion, mecarbam, metaldehyde, methamidophos, metharhilic anisopliae, metharhilic flavoviride, methidathione, methiocarb, methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, monocrotophos, moxidectin,
Naled, Nitenpyram, Nithiazine, Novaluron
Omethoate, oxamyl, oxydemethone M
Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propoxur, Prothiofos, Prothoat, Pyromhrhridosine, Pymmethrofinos, Pymmethrofinos , Pyridathione, pyrimidifen, pyriproxyfen,
Quinalphos,
Ribavirin
Salithion, Sebufos, Selamectin, Silafluofen, Spinosad, Sulfotep, Sulprofos,
oxalate hydrogen Taufluvalinate, tebufenozide, tebufenpyrad, Tebupirimiphos, teflubenzuron, tefluthrin, temephos, Temivinphos, terbufos, tetrachlorvinphos, Thetacypermethrin, thiamethoxam, Thiapronil, Thiatriphos, thiocyclam, thiodicarb, thiofanox, thuringiensin, Tralocythrin, tralomethrin, triarathene, Triazamate, triazophos, triazuron, Trichlophenidines, trichlorfon, triflumuron, trimethacarb,
Vamidothion, Vaniliprole, Verticillium lecanii
YI 5302
Zetacypermethrin, zolaprofos
(1R-cis) - [5- (phenylmethyl) -3-furanyl] methyl-3 - ((dihydro-2-oxo-3 (2H) - furanylidene) methyl] -2,2-dimethylcyclopropane carboxylate
(3-phenoxyphenyl) methyl 2,2,3,3-tetramethylcyclopropane decarboxylate
1 - ((2-Chloro-5-thiazolyl) methyl] tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2 (1H) - imine
2- (2-chloro-6-fluorophenyl) -4- [4- (1,1-dimethylethyl) phenyl] -4,5-dihydro-oxazole
2- (acetyloxy) -3-dodecyl-1,4-naphthalenedione
2-Chloro-N - [[[4- (1-phenylethoxy) phenyl] amino] carbonyl] benzamide
2-Chloro-N - [[[4- (2,2-dichloro-1,1-difluoroethoxy) phenyl] amino] carbonyl] benzamide 3-methylphenyl propyl carbamate
4- [4- (4-ethoxyphenyl) -4-methylpentyl] -1-fluoro-2-phenoxy-benzene
4-chloro-2- (1,1-dimethylethyl) -5 - [[2- (2,6-dimethyl-4-phenoxyphenoxy) ethyl] thio] - 3 (2H) pyridazinone
4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) - pyridazinone
4-chloro-5 - [(6-chloro-3-pyridinyl) methoxy] -2- (3,4-dichlorophenyl) -3 (2H) pyridazinone
Bacillus thuringiensis strain EG-2348
Benzoic acid [2-benzoyl-I- (1,1-dimethylethyl) hydrazide
Butanoic acid 2,2-dimethyl-3- (2,4-dichlorophenyl) -2-oxo-1-oxaspiro [4.5] dec-3-en-4-yl ester
[3 - [(6-chloro-3-pyridinyl) methyl] -2-thiazolidinylidene] cyanamide
Dihydro-2- (nitromethylene) -2H-1,3-thiazine-3 (4H) carboxaldehyde
Ethyl [2 - [[1,6-dihydro-6-oxo-1- (phenylmethyl) -4-pyridazinyl] oxy] ethyl] carbamate
N- (3,4,4-trifluoro-1-oxo-3-butenyl) glycine
N- (4-chlorophenyl) -3- [4- (difluoromethoxy) phenyl] -4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide
N - [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N "-nitroguanidine
N-methyl-N '- (1-methyl-2-propenyl) -1,2-hydrazinedicarbothioamide
N-methyl-N'-2-propenyl-1,2-hydrazinedicarbothioamide
O, O-Diethyl- [2- (dipropylamino) -2-oxoethyl] ethyl phosphoramidothioate

Fungicides

Aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,
Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylisobutyl, bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
Calcium polysulfide, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazon, chlorfenazol, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanazol, cyofuraminol, cyproamaminol, cyproamaminil, cyproaminol, cyprodinol
Debacarb, dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithorphoxin, dithorphononodine,
Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,
Famoxadone, Fenapanil, Fenarimol, Fenbuconazol, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzon, Fluazinam, Flumetover, Fluoromid, Fluquinconazol, Flurprimolol, Flusulfosolutol, Flusulfosolutol, Flusulfazolutol, Flusulfazolutol, Flusulfazolutol, Flusulfazolutol, Flusulfazolutol, Flusulfazolutol, Flusulfosolutol, Flusulfazolutol, Flusulfazolutol, Flusulfazolutol, Flusulfosolutol, Flusulfazolutol, Flusulfosolutol, Flusulfazolutol, Flusulfosolutol, Flusulfidol, Flusilazolutol, Flusulfazolutol, Flusulfosilutol, Flusulfosilutol, Flusulfidol, Flusilazolutol Fosetyl sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazoleis, furmecyclox,
Guazatin,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovaledione,
Kasugamycin, Kresoximmethyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Metrifuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,
Nickel dimethyldithiocarbamate, nitrothalisopropyl, Nuarimol,
Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
Paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone, propamocarb, propanosine sodium, propiconazole, propineb, pyrazophos, pyrifen, pyifenox, pyrroyilonil
Quinconazole, quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, Tetcyclacis, tetraconazole, thiabendazole, Thicyofen, Thifluzamide, thiophanate-methyl, thiram, Tioxymid, Tolclofosmethyl, tolylfluanid, triadimefon, triadimenol, Triazbutil, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Uniconazole,
Validamycin A, vinclozolin, viniconazole,
Zarilamid, Zineb, Ziram as well
Dagger G,
OK-8705,
OK-8801,
α- (1,1-dimethylethyl) -β- (2-phenoxyethyl) -1H-1,2,4-triazole-1-ethanol,
α- (2,4-dichlorophenyl) -β-fluoro-b-propyl-1H-1,2,4-triazole-1-ethanol,
α- (2,4-dichlorophenyl) -β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,
α- (5-methyl-1,3-dioxan-5-yl) -β - [[4- (trifluoromethyl) phenyl] methylene] -1H-1,2,4-triazol-1-ethanol,
(5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (1H-1,2,4-triazol-1-yl) -3-octanone,
(E) -a- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide,
{2-Methyl-1 - [[[1- (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid 1-isopropyl ester
1- (2,4-dichlorophenyl) -2- (1H-1,2,4-triazol-1-yl) -ethanone-O- (phenylmethyl) oxime,
1- (2-methyl-1-naphthalenyl) -1H-pyrrole-2,5-dione,
1- (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-pyrrolidinedione,
1 - [(diiodomethyl) sulfonyl] -4-methyl-benzene,
1 - [[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1H-imidazole,
1 - [[2- (4-chlorophenyl) -3-phenyloxiranyl] methyl] -1H-1,2,4-triazole,
1- [1- [2 - [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] -1H-imidazole,
1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,
2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide,
2,2-dichloro-N- [1- (4-chlorophenyl) ethyl] -1-ethyl-3-methyl-cyclopropanecarboxamide,
2,6-dichloro-5- (methylthio) -4-pyrimidinyl-thiocyanate,
2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide,
2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl benzamide,
2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,
2 - [(1-methylethyl) sulfonyl] -5- (trichloromethyl) -1,3,4-thiadiazole,
2 - [[6-Deoxy-4-O- (4-O-methyl-β-D-glycopyranosyl) -α-D-glucopyranosyl] amino] -4- methoxy-1H-pyrrolo [2,3-d] pyrimidine-5-carbonitrile,
2-aminobutane,
2-bromo-2- (bromomethyl) pentandinitrile,
2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl) -3-pyridinecarboxamide,
2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) acetamide,
2-phenylphenol (OPP),
3,4-dichloro-1 - [4- (difluoromethoxy) phenyl] -1H-pyrrole-2,5-dione,
3,5-dichloro-N- [cyan [(1-methyl-2-propynyl) oxy] methyl] benzamide,
3- (1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,
3- [2- (4-chlorophenyl) -5-ethoxy-3-isoxazolidinyl] pyridine,
4-chloro-2-cyan-N, N-dimethyl-5- (4-methylphenyl) -1H-imidazole-1-sulfonamide,
4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one,
8- (1,1-dimethylethyl) -N-ethyl-N-propyl-1,4-dioxaspiro [4.5] decane-2-methanamine,
8-hydroxyquinoline sulfate,
9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide,
bis- (1-methylethyl) -3-methyl-4 - ((3-methylbenzoyl) -oxy] -2,5-thiophene dicarboxylate,
cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol,
cis-4- [3- [4- (1,1-dimethylpropyl) phenyl-2-methylpropyl] -2,6-dimethyl-morpholine hydrochloride,
Ethyl - [(4-chlorophenyl) azo] cyanoacetate,
Potassium hydrogen carbonate,
Methane tetrathiol sodium salt,
Methyl 1- (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) -1H-imidazole-5-carboxylate,
Methyl N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate,
Methyl N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate,
N- (2,3-dichloro-4-hydroxyphenyl) -1-methyl-cyclohexane carboxamide,
N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide,
N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide,
N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide,
N- (4-cyclohexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,
N- (4-hexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,
N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) acetamide,
N- (6-methoxy) -3-pyridinyl) cyclopropanecarboxamide,
N- [2,2,2-trichloro-1 - [(chloroacetyl) amino] ethyl] benzamide,
N- [3-chloro-4,5-bis (2-propynyloxy) phenyl] -N'-methoxymanimidamide,
N-formyl-N-hydroxy-DL-alanine sodium salt,
O, O-diethyl- [2- (dipropylamino) -2-oxoethyl] ethyl phosphoramidothioate,
O-methyl-5-phenyl-phenylpropylphosphoramidothioate,
5-methyl-1,2,3-benzothiadiazole-7-carbothioate,
spiro [2H] -1-benzopyran-2,1 '(3'H) -isobenzofuran] -3'-one,

Bactericides

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, Octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Tecloftalam, copper sulfate and other copper preparations.

Their amounts in the formulations according to the invention can range from 0.01 to 25% by weight. vary widely based on the total mass

The use of the co-active substances mentioned and synergists such as piperonyl butoxide with the pyrazole oximes mentioned is known and is described, for example, in WO 00/02453, WO 95/33380, WO 95/07615 and EP 0 736 252.

Other co-active substances are ureas, in particular benzoylureas and Synergists like PBO (piperenyl butoxide) mentioned.

Benzoylureas include compounds of the formula (V):

in which
R ^{1 represents} halogen,
R ^{2 represents} hydrogen or halogen,
R ^{3 represents} hydrogen, halogen or C _1-4 alkyl,
R ⁴ represents halogen, 1-5-halogen-C _1-4 -alkyl, C _1-4 -alkoxy, 1-5-halogeno-C _1-4 alkoxy, C _{1- 4} alkylthio, 1-5-halogen -C _1-4 alkylthio, phenoxy or pyridyloxy which may optionally be substituted by halogen, C _1-4 alkyl, 1-5 haloC _1-4 alkyl, Q alkoxy, 1-5 halogen C _1-4 alkoxy, C _1-4 alkylthio, 1-5 haloC ₁ -C ₄ alkylthio.

The solid formulations according to the invention which can be applied dermally are suitable excellent for performing dermal treatments on dogs and cats. They are characterized by their excellent storage stability of 3-5 Years in all climates. They have a wall thickness of 250-2500 µm, preferably have 750-1500 µm. They are still characterized by their simple Applicability, very good biological long-term effectiveness of several months as well as the environment - especially water bodies - and warm-blooded animals.

In the following examples, 1,1-dimethylethyl {[[[(1,3-dimethyl- 5-phenoxy-1-pyrazol-4-yl) methylene] amino] oxy] methyl} benzoate (Cas No .: 134098- 61-6) (common name Fenpyroximate / see Tab. 1, No. 1).  

Examples example 1 composition

Fenpyroximate 10.00 g Di-n-butyl adipate 21.10 g Diethylhexyl phthalate 9.10 g Epoxidized soy 2.30 g Stearic acid 0.80 g PVC 51.70 g urea 5.00 g

Manufacturing

The homogeneous mixture of fenpyroximate and PVC is combined in one Mixer with the mixture of di-n-butyl adipate, diethylhexyl phthalate and epoxidized soy. You mix until the Mixture is homogeneous. It promotes warming, e.g. B. as a result of Increase the number of revolutions of the mixer, the retraction of the switch maker mix into the PVC. After the subsequent homogeneous Distribution of the stearic acid becomes the mixture by injection molding into dogs shaped collars.

Example 2 composition

Fenpyroximate 10.00 g Epoxidized soy 2.30 g Stearic acid 0.80 g Acetyltributyl citrate 25.20 g PVC 56.70 g Diphenylurea 5.00 g

Manufacturing

The mixture of acetyl tributyl citrate and epoxidized soybean oil is in a mixer on the homogeneous mixture of imidacloprid and PVC applied. Warming up helps to draw in of the plasticizer mixture in the PVC; you mix until the Mixture is homogeneous. The mixture is added in a conventional manner Extruded dog collars.

Example 3 composition

Fenpyroximate 20.00 g Epoxidized soy 2.30 g Stearic acid 0.80 g Acetyltributyl citrate 30.20 g PVC 51.70 g urea 5.00 g

Manufacturing

like example 2

Example 4 composition

Fenpyroximate 7.50 g Epoxidized soy 10.00 g Stearic acid 0.80 g Acetyltributyl citrate 15.00 g PVC 61.70 g urea 5.00 g

Manufacturing

like example 2  

Example 5 composition

Fenpyroximate 10.00 g Epoxidized soy 2.30 g Stearic acid 0.80 g Triacetin 10.00 g PVC 71.90 g Diphenylurea 5.00 g

Manufacturing

The mixture of triacetin and epoxidized soy is in a mixer on the homogeneous mixture of PVC and imidacloprid applied. It promotes warming, e.g. B. due to an increase in the number of revolutions of the mixer that Pull the plasticizer into the PVC. After more homogeneous The mixture is mixed on a stearic acid Extruder extruded into sheets from which medallions (= Pendant for collars) are punched out.

Example 6 composition

Fenpyroximate 5.00 g Polyether block amide (Pebax®) 84.50 g urea 10.50 g

Manufacturing

The active ingredient is applied to the carrier in an intensive mixer applied and the mixture injection molded to dog's neck ribbons shaped.  

Example 7 composition

Fenpyroximate 10.00 g Medium chain triglycerides 15.00 g highly disperse silicon dioxide 0.50 g Polyether block amide (Pebax®) 64.50 g Diphenylurea 10.00 g

Manufacturing

Medium chain triglycerides are mixed in a mixer homogeneous mixture of imidacloprid and polyether block amide upset. Heating promotes the absorption of the agents chain triglycerides in the polyether block amide. For improvement The flowability is checked before the mixture is extruded highly disperse silicon dioxide mixed homogeneously. It plates are extruded from which medallions (= pendants for Collars) are punched out.

Example 8 composition

Fenpyroximate 10.00 g Styrene-butylene block copolymer (Thermoplast®K) 80.00 g Diphenylurea 10.00 g

Manufacturing

The active ingredient is applied to the carrier in an intensive mixer applied and the mixture injection molded into collars shaped.  

Example 9 composition

Fenpyroximate 5.00 g Copolyester (Hytrel®) 90.00 g Diphenylurea 5.00 g

Manufacturing

The mixture becomes dog's neck in a conventional manner tapes extruded.

Example 10 composition

Fenpyroximate 10.00 g Polyether block amide (Pebax®) 85.00 g Diphenylurea 5.00 g

Manufacturing

The homogeneous mixture is turned into plates on an extruder extruded from which medallions (= pendants for collars) be punched out.  

Trials of effectiveness

To carry out efficacy tests against fleas and ticks Dogs treated with collars according to Examples 1, 2, 3, 4, 6, 8 and 9. The Treatment was carried out by attaching a shaped body in the form of a Collar (approx. 1.4 cm wide stripe) on the neck of the animals. The stripes were as close as possible (with a finger-wide gap) to the neck of the animals customized. The medallions (Examples 5, 7 and 10) were perforated and attached to one normal collar not loaded with active substance. The medallion was placed so that it was in contact with the animal's fur in the front of the neck.

Example A Efficacy against fleas (Ctenocephalides felis) in dogs

On days -4 and -1, dogs with around 100 adult, fasted dogs Ctenocephalides felis infested per dog. The fleas are on the neck of the animal.

On day 0, the success of the infestation on the dog is checked by the awake animal looking for fleas. The number of living fleas is recorded.

After the fleas have been counted, the animals are treated. The dogs of control group are not treated. The drugs to be tested are given to the animals as Collar or administered as a medallion. Collars and medallion remain on Animal until the end of the experiment on day 170. There is only 1 collar per animal or 1 medallion applied. Only clinically healthy animals are used.

On day 1 and day 2, all dogs are checked for live fleas. The results are recorded in the raw data.  

On days 14, 28, 56, 84, 112, 140 and 168 all dogs with approx. 100 adult, sober Ctenocephalides felis reinfestiert per dog. One and each two days after reinfestation, all dogs are checked for live fleas. The Results are logged in the raw data.

A modified Abbott formula is used to calculate the effectiveness:

With Fenpyroximate in formulation examples 1, 2, 3, 4, 6, 8 and 9 as Collar and applied as medallion in formulation examples 5, 7 and 10, efficacies <90% against Ctenocephalides felis can be achieved over 3-6 months will.  

Example B Efficacy against ticks (Ixodes ricinus) in dogs

On day -1 dogs with 2% Rompun® (Bayer AG) (0.1 ml / kg body weight) sedated. After all dogs are sedated (after about 10-15 minutes) they will be in Transport boxes transferred and 50 Ixodes ricinus (25♀, 25♂) per dog to the Neck of the animal spread. The animals will be out after about 1½ hours the transport box placed in the cage.

On day 0, the success of the infestation on the dog is checked by the awake animal is searched for ticks. The head and ears are searched intensively including ear fold, in the area of the neck, on the lower abdomen, on the lower chest, on the side flank as well as between the toes and on the limbs. The number of sucked live ticks are logged. Dead ticks are removed.

After the ticks have been counted, the animals are treated. The dogs of control group are not treated. The drugs to be tested are given to the animals as Collar or administered as a medallion. Collars and medallion remain on Animal until the end of the experiment on day 170. There is only 1 collar per animal or 1 medallion applied. Only clinically healthy animals are used.

On day 1 and day 2, all dogs are sucked on live and dead ticks checked. The results are recorded in the raw data. Be on day 2 all living and dead ticks away from the dog.

On days 14, 28, 56, 84, 112, 140 and 168 all dogs with 50 each Ixodes ricinus (25♀, 25♂) reinfested per dog. One and two days after each Reinfestation, all dogs are checked for live and dead sucked ticks liert. The results are logged in the raw data. On the 2nd day after Reinfestation removes all living and dead ticks from the dog.  

A modified Abbott formula is used to calculate the effectiveness:

KG: control group
BG: treatment group

With Fenpyroximate in formulation examples 1, 2, 3, 4, 6, 8 and 9 as neck band and applied as medallion in formulation examples 5, 7 and 10, efficacies <85% against Ixodes ricinus can be achieved over 3-6 months.

Claims (2)

1. Solid formulation for dermal control of parasites on animals containing a pyrazoloxime effective against parasites. 2. Use of the solid formulations according to claim 1 for dermal loading fighting parasites on animals.