WO2002078443A1

WO2002078443A1 - Moulded bodies made from thermoplastically-workable polyurethanes comprising active agents for the control of parasites

Info

Publication number: WO2002078443A1
Application number: PCT/EP2002/002961
Authority: WO
Inventors: Olaf Hansen; Hanns-Peter Müller; Horst Gruttmann
Original assignee: Bayer Ag; Mueller Hanns-Peter; Olaf Hansen; Horst Gruttmann
Priority date: 2001-03-28
Filing date: 2002-03-18
Publication date: 2002-10-10
Also published as: DE10115225A1

Abstract

The invention relates to novel moulded bodies made from thermoplastically-workable, biologically-degradable, aliphatic polyurethane elastomer mixtures containing active agents, which overwhelmingly comprise thermoplastic polyurethanes of high molecular weight and small amounts of thermoplastic polyurethanes of low molecular weight, the production thereof and the use thereof for the control of parasites on or in the vicinity of humans and animals.

Description

Molded articles containing active ingredients based on thermoplastically processable polyurethanes for combating parasites

The present invention relates to new active substance-containing molded articles based on thermoplastically processable, biodegradable aliphatic polyurethane elastomer mixtures, their production and their use for controlling parasites on, on and in the environment of humans and animals. The moldings according to the invention can optionally be used after use to control plant-damaging insects on plants.

Shaped bodies containing active substances for controlling pests are known. They are based on the slow release of active substances from an active substance-containing matrix of plastics. As a rule, PNC is used almost exclusively for molded articles in practice. This is not surprising. PNC is inexpensive and easily accessible. It can also be mixed in a wide range with other substances, especially plasticizers. With PNC bodies containing active ingredients, these plasticizers have the function of keeping the active ingredient dissolved in the carrier and slowly transporting it to the surface of the molded body. There the active ingredient evaporates or it is removed together with the plasticizer

Rubbed surface. The interaction of the three components PNC carrier, plasticizer and active ingredient determines whether and to what extent the molded body can be used in practice. If a component of the overall system is changed, it can no longer be predicted whether the system will still work in practice. This is particularly true if the plasticizer, which plays a key role in drug delivery, is changed or omitted.

For various reasons, it is desirable to replace PNC as a carrier material. Active substance-containing molded articles based on biodegradable, thermoplastically processable polymers have already been described in WO 98/19 532. Moldings that can be used in practice must combine numerous properties: they must have sufficient mechanical stability and flexibility, the active ingredient should be released in sufficient quantities, the effect should last as long as possible and the used moldings should be able to be disposed of in a cost-effective and environmentally friendly manner.

For the production of the molded articles on an industrial scale, plastics are required which have a tendency to crystallize so that extrudable, sprayable and blowable products with rapid crystallization are obtained on cooling.

This requirement is not optimally met by the polyester urethane plastics described in WO 98/19 532.

The object of the present invention was therefore to provide new active substance-containing molded articles which, based on the procedures described above, are based on known ones

Plastic processing machines can be produced and have good properties in parasite and pest control.

It has surprisingly been found that the mixtures of lightfast, thermoplastic polyurethanes described in more detail below for the incorporation of

Active ingredients and plasticizers (as carriers) are excellently suitable, and that these formulations can be processed on conventional plastic processing machines in fast cycles. In addition, it was found that the shaped bodies obtained in this way release the active substances in targeted doses so that they can be used for long-term control of parasites in warm-blooded animals.

The present invention relates to:

1. Containing molded articles a) a biodegradable polyurethane elastomer mixture b) at least one insecticidal and / or acaricidal active ingredient. c) plasticizer, the polyurethane elastomer mixture a) consisting of ai) 80 to 98% by weight of an aliphatic thermoplastic polyurethane

(TPU Y) with a number average molecular weight of 20,000 g / mol to 100,000 g / mol and aii) 2 to 20% by weight of a low molecular weight aliphatic thermoplastic polyurethane (TPU X) with a number average molecular weight of 462 g / mol to 6 000 g / mol.

2. A process for the production of the moldings according to 1, in which the biodegradable polyester urethane elastomer mixture (TPU Y / TPU X) with one or more insecticidal and / or acaricidal active ingredient, the plasticizer and, if appropriate, customary additives at 100 to 200 ° C., preferably 120 up to 180 ° C, mixed and processed in the usual way to shaped bodies.

3. Use of the shaped body according to 1, for controlling parasites in warm-blooded animals.

Biodegradable polymers are those that meet the test conditions described in the draft DIN 54 900-1.

The production and use of thermoplastic polyester urethanes as composable plastics is described in EP-A 0 593 975.

The mixtures of biodegradable thermoplastic aliphatic polyurethanes that can be used according to the invention are Polyurethane elastomer mixtures consisting of 80 to 98% by weight of an aliphatic, thermoplastic polyurethane (TPU Y), optionally obtainable with the addition of catalysts

A) 100 to 60 mol%, preferably 100 to 80 mol%, hexamethylene diisocyanate

(HDI) and 0 to 40 mol%, preferably 0 to 20 mol% of other aliphatic diisocyanates,

B) polyols, preferably difunctional polyester diols with a number average molecular weight from 600 to 5000 g / mol, preferably from 700 to 4200 g / mol, and

C) chain extenders with an average molecular weight of 60 to 500 g / mol

optionally with the addition of UV stabilizers D) in an amount of 0.4 to 0.9% by weight, preferably 0.4 to 0.8% by weight, based on [A) + B) + C)] , and other usual auxiliaries and additives (F),

where the equivalence ratio of A) to) is between 1.5: 1.0 and 6.0: 1.0 and the characteristic number (formed from the quotient of the equivalent ratio of isocyanate groups multiplied by 100 and the sum of the hydroxyl groups from polyol and chain extender ) Is 95 to 105,

and 2 to 20% by weight of a low molecular weight thermoplastic polyurethane

(TPU X) available from

G) hexamethylene diisocyanate (HDI),

H) diols with a number average molecular weight of 62 to 300 g / mol and I) monofunctional alcohols as chain terminators with a molecular weight of 32 to 300 g / mol,

wherein the molar ratio of G) to H) between 2: 1 and 1.05: 1, preferably 1.7: 1 to

1.2: 1 and the characteristic number (formed from the quotient of the equivalent ratio of isocyanate groups from G multiplied by 100) and the sum of the hydroxyl groups from H) and I) is 99 to 101.

The TPU Y preferably has a number average molecular weight of 20,000 g / mol to 100,000 g / mol. The TPU X preferably has a number average molecular weight of 462 g / mol to 6,000 g / mol.

The TPU Y particularly preferably contains 13 to 21% by weight, preferably 14 to 18% by weight, of hard segment (calculated from the amount of diisocyanate A used) and chain extender C), based on the total mass of TPU Y).

The light-stable, thermoplastic polyurethane elastomer mixtures described above can be prepared by continuously or discontinuously mixing B) and C) and then intensively mixing them with A) and before, during or preferably after the reaction of components A), B) and C ) the separately produced TPU X is added in an extruder and the product thus obtained is optionally granulated.

The process according to the invention is preferably carried out in such a way that the reaction for producing the TPU Y is carried out continuously in the presence of a catalyst.

The TPU X is preferably produced without a catalyst. The polyurethane elastomer mixtures described are generally suitable for the production of moldings, extrudates, films and injection molded parts. The polyurethane elastomer mixtures can be used excellently as sinterable and well-running powders for the production of flat structures and hollow bodies.

In addition to 1,6-hexamethylene diisocyanate, other aliphatic and / or cycloaliphatic diisocyanates can be used as diisocyanates A) (cf. HOUBEN-WEYL "Methods of Organic Chemistry, Volume 20, Macromolecular Substances", Georg Thieme Verlag, Stuttgart, New York 1987) , Pp. 1587 - 1593). examples are

Ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane diisocyanate, cyclohexane-1,3 and -1,4-diisocyanate as well as any mixtures of these isomers, l-isocyanato-3,3,5-trimethyl- 5-isocyanatomethyl-cyclohexane, 2,4- and 2,6-hexahydrotoluylene-diisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or -1,4-phenylene diisocyanate, perhydro-2,4 ^Λ - and / or -4.4 ^Λ - diphenylmethane diisocyanate and norbornane diisocyanates (e.g. US-A 3,492,330). In addition to 1,6-hexamethylene diisocyanate (HDI), cycloaliphatic diisocyanates, such as l-isocyanate-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (_PDI) and perhydro-2,4 ^Λ - and or -4,4 ^, -diphenylmethane diisocyanates ^{, are} preferred (ß _u MDI).

If necessary, higher-functional isocyanates such as e.g. the isocyanurate from HDI (Desmodur® N 3300, Bayer AG) or the trimere from IPDI (Desmodur® Z 4300, Bayer AG) can also be used. However, care must be taken that an average functionality of two is not significantly exceeded so that the polyurethanes can be processed thermoplastically. You may have to

Reaction partners with higher functionality can be compensated for by using other reaction partners with a lower functionality than two. Suitable monofunctional isocyanates are, for example, stearyl isocyanate and cyclohexyl isocyanate. As component B), polyester polyols with a number average molecular weight between 600 and 5000 g / mol, preferably between 700 and 4200 g / mol, are preferably used.

Suitable polyesters are e.g. Reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably dihydric carboxylic acids or their derivatives capable of esterification. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature, e.g. by halogen atoms, substituted and / or unsaturated.

Examples of such carboxylic acids and their derivatives are: succinic acid, adipic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endo-methylene tetrahydrophthalic anhydride, maleic anhydride

Fumaric acid, dimerized and trimerized unsaturated fatty acids, optionally in a mixture with monomeric unsaturated fatty acids, dimethyl terephthalate and bisglycol terephthalate.

As polyhydric alcohols are e.g. Ethylene glycol, propylene glycol- (1,2) and

- (1,3), butylene glycol (1,4) and - (2,3), hexanediol (1,6), octanediol (1,8), neopentyl glycol, 1,4-bis (hydroxymethyl) Cyclohexane, trimethylolpropane, trimethylolethane, further di-, tri-, tetra- and higher polyethylene glycols, di- and higher polypropylene glycols as well as di- and higher polybutylene glycols in question. The polyesters can have a proportion of terminal carboxyl groups. Polyesters of lactones, for example ε-caprolactone, or of hydroxycarboxylic acids, for example ω-hydroxycaproic acid, can also be used. However, the hydroxy-functional polyesters known from fat chemistry, such as castor oil and its transesterification products, can also be used. If necessary, other polyols can be used in addition to polyester diols, for example polycarbonate diols, polyether diols and mixtures thereof.

Suitable polycarbonates containing hydroxyl groups are those of the type known per se, which, for example, by reacting diols such as propanediol- (l, 3),

Butanediol- (1,4) and / or hexanediol- (1,6), diethylene glycol, triethylene glycol, tetraethylene glycol or thiodiglycol with diaryl carbonates, e.g. Diphenyl carbonate or phosgene can be produced (DE-A 1 694 080, 2221 751).

In addition to the polyester polyols and the polycarbonate diols, mixtures of polyether polyols and polyester polyols and mixtures of polyether polyols and polycarbonate diols each having a number average molecular weight between 600 and 5,000 g / mol, preferably 700 and 4,200 g / mol, can also be used.

Suitable polyether diols can be prepared by reacting one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical with a starter molecule which contains two active hydrogen atoms bonded. As alkylene oxides e.g. called: ethylene oxide, 1,2-popylene oxide, epichlorohydrin and 1,2-butylene oxide and 2,3-butylene oxide. Ethylene oxide, propylene oxide and mixtures of 1,2-propylene oxide and ethylene oxide are preferably used. The

Alkylene oxides can be used individually alternately in succession or as mixtures. Examples of suitable starter molecules are: water, amino alcohols such as N-alkyl-diethanolamines, for example N-methyl-diethanolamine and diols such as ethylene glycol, 1,3 propylene glycol, 1,4-butanediol and 1,6-hexanediol. If appropriate, mixtures of starter molecules can also be used.

Suitable polyether diols are also the hydroxyl-containing polymerization products of tetrahydrofuran. Functional polyethethers can also be used in proportions of 0 to 30% by weight, based on the bifunctional polyethers, but at most in such an amount that a thermoplastically processable one Product is created. The essentially linear polyether diols have molecular weights from 600 to 5,000, preferably from 700 to 4,200 g / mol. They can be used both individually and in the form of mixtures with one another. Polymerization products of tetrahydrofuran and polyether diols based on ethylene oxide and / or propylene oxide, for example containing hydroxyl groups, are preferred

Impact® polyether from Bayer AG.

Polyesters of adipic acid, butanediol, hexanediol and neopentyl glycol with an average molecular weight between 700 and 4,200 g / mol are particularly preferred.

Chain extenders C) used are aliphatic diols and / or diamines with a molecular weight of 60 to 500 g / mol, preferably aliphatic diols with 2 to 14 carbon atoms, such as e.g. Ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol and in particular 1,4-butanediol, or (cycloaliphatic

Diamines, such as isophoronediamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, N-methyl-propylene-1,3-diamine, N, N ^Λ -dimethyl-ethylenediamine. Diesters of terephthalic acid with glycols having 2 to 4 carbon atoms and hydroxyalkylene ether of hydroquinone are also suitable. Mixtures of the chain extenders mentioned above can also be used. In addition, smaller amounts of triplets can be added, but at most in such an amount that a thermoplastic processed product is formed. 1,4-Butanediol and 1,6-hexanediol are particularly preferred as chain extenders C).

Conventional monofunctional compounds can also be used in small amounts, e.g. as a chain terminator or mold release.

Examples include alcohols such as octanol and stearyl alcohol or amines such as butylamine and stearylamine. Chain extenders H) used are aliphatic diols with a molecular weight of 62 to 300 g / mol, preferably aliphatic diols with 2 to 14 carbon atoms, such as, for example, ethanediol, 1,6-hexanediol, 1,4-butanedione and 1,2-propanediol , Particularly preferred as chain extenders H) are 1,4-butanediol and 1,6-hexanediol, optionally in admixture with up to 20% by weight of chain extenders with an average molecular weight of 62 to 300 g / mol.

All chain terminators J) use monofunctional alcohols with a molecular weight of 32 to 300 g / mol, preferably methanol, ethanol, propanol, 1-butanol, 1-hexanol, 2-ethylhexanol-1, cyclohexanol and 1-octadecanol.

When carrying out the process according to the invention, the procedure is preferably such that the polyol / polyol mixture B) and the chain extender C) are mixed continuously and then mixed intensively with the diisocyanate / diisocyanate mixture A) (one shot process) and before, during or preferred after the

Reaction of these components to the TPU Y in an extruder, the separately produced low molecular weight additive TPU X is fed to the melt and the product thus obtained is optionally granulated.

The reaction to the TPU Y is preferably carried out in the presence of a catalyst.

Static mixers are preferably used for continuous mixing (cf. DE-C 23 28 795).

The thermoplastic polyurethanes TPU Y used according to the invention can also be produced by the prepolymer process, the diisocyanate / diisocyanate mixture being first mixed with the polyol / polyol mixture and reacted to obtain a prepolymer, and the chain extension is then carried out continuously. A catalyst is preferably used in the continuous production of the thermoplastic polyurethanes in accordance with the extruder or belt process. Suitable catalysts are conventional tertiary amines known in the prior art, such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, NjN'-dimethylpiperazine, 2- (dimethylaminoethyl) ether, diazabicyclo- [2,2,2] - Octane and the like, and in particular organic metal compounds such as titanium acid esters, iron compounds, tin compounds, for example tin diacetate, tin dioctoate, tin dilaurate or the tin diacyl salts of aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate or the like.

Preferred catalysts are organic metal compounds, in particular titanium acid esters, iron or tin compounds. Dibutyltin dilaurate is very particularly preferred.

In addition to the reaction components, UV stabilizers and catalysts used according to the invention, other auxiliaries and additives can also be added. Lubricants such as fatty acid esters, their metal soaps, fatty acid amides and silicone compounds, antiblocking agents, inhibitors, stabilizers against hydrolysis, heat and discoloration, flame retardants, dyes, pigments, inorganic fillers and reinforcing agents which are named after the

State of the art are produced and can also be applied with a size. Further information on the auxiliaries and additives mentioned can be found in the specialist literature, for example JH Saunders, K. C Frisch: "High Polymers", Volume XVI, Polyurethanes, Parts 1 and 2, Interscience Publishers 1962 and 1964, R. Gächter, H. Müller (Ed.): Taschenbuch der Kunststoff-Additive, 3rd edition, Hanser Verlag, Munich 1989 or DE-A-29 01 774.

The lubricants are preferably added in amounts of 0.1 to 1.0% by weight, based on A) + B) + C). The antioxidants are preferably used in amounts of 0.1 to 0.7% by weight, based on A) + B) + C). The additive TPU X used according to the invention is preferably prepared separately in a suitable stirring apparatus. The procedure is as follows:

Hexamethylene diisocyanate (HDI) G) is initially introduced and the chain terminator I) is first added dropwise at elevated temperature. After the reaction has ended (the exothermic reaction has subsided), the chain extender H) is metered in and, if appropriate, the temperature is increased. The mixture is stirred until the melt is free of NCO (TR control). In general, the end phase of the reaction is carried out at 150 to 200 ° C. and the proportions are chosen so that 0.5 to 0.95 mol of the chain extender H) are added to one mole of the diisocyanate G).

The low-viscosity melt is poured out of the reaction vessel and solidifies on cooling with crystallization. The product is crushed and can also be ground.

Another possibility is to deposit the thin melt on a cooling belt or a cooling roller and to comminute, granulate and / or grind it after solidification.

The TPU Y used according to the invention is preferably produced continuously, the polyol / polyol mixture B) and the chain extender C) being continuously mixed (for example using a static mixer) and this mixture being mixed with HDI A) (for example using a static mixer) and being reacted. In a further step, the second diisocyanate (if present) A) other than HDI is mixed in. The second diisocyanate can be mixed in, for example, by means of a static mixer, tubular mixer or else in the extruder. The proportions are chosen so that soft, light-stable TPU Y are preferably obtained, preferably with 13-21% by weight, particularly preferably with 14-18% by weight of hard segment portions. The hard segment in the TPU is usually made up of the amount used Diisocyanate and chain extender calculated based on the total mass of the TPU.

The polyol chain extender mixture [B) + C)] and the diisocyanate A) should preferably have a temperature difference of <20 ° C., preferably before the mixture

<10 ° C, particularly preferably <5 ° C. The absolute raw material temperatures should preferably be between 60 ° C and 150 ° C, particularly preferably between 80 ° C and 120 ° C. The second diisocyanate A) other than HDI, if present, can also be reacted first with the polyol chain extender mixture [B) + C)]. Then HDI A) is mixed in and also added

Brought reaction.

The additive TPU X can be added after the polymerization by compounding or also during the polymerization. Antioxidants and UV stabilizers, which are preferably previously dissolved in polyol B), can also be metered in during the polymerization. However, lubricants and stabilizers can also be added in the extruder process, for example in the second part of the screw.

The light-stable TPU blends described can generally be used for the production of

Shaped bodies, in particular for the production of extrudates (e.g. films) and injection molded parts. Furthermore, the TPUs according to the invention can be used as a sinterable powder for producing flat structures and hollow bodies.

The light-stable blends made of thermoplastic polyurethane elastomers, consisting of 80 to 98% by weight of an aliphatic TPU Y, preferably with a number average molecular weight of 20,000 g / mol to 100,000 g / mol and 2 to 20% by weight of a separately produced additive TPU X, preferably with a number average molecular weight of 462 g / mol to 6,000 g / mol, are distinguished by a whole series of advantageous properties compared to previously known products: 1. In the mixtures according to the invention, the tendency towards crystallization is accelerated in such a way that extrudable, sprayable and blowable products with rapid crystallization are obtained on cooling. Crystallization usually begins at 140 ° C.

2. The TPU mixtures according to the invention have a reduced MFI (melt flow index) compared to the TPU not modified according to the prior art.

3. The TPU mixtures according to the invention have an increased heat resistance and an increased modulus of elasticity compared to the TPU according to the prior art.

4. By mixing the TPU Y with the TPU X, the hardness of the TPU

Mixture hardly changed, so that overall soft, light-fast TPU mixtures with excellent processability from the melt and quick release from the mold are obtained.

5. The light-stable TPU blends according to the invention can also be found in new ones

Applications, e.g. after foaming with active ingredients to combat parasites on, on or in the vicinity of animals.

The moldings according to the invention contain one or more insecticides and / or acaricidal active ingredients.

Insecticides and / or acaricides, in particular parasiticides, for use on animals may be mentioned as active ingredients for the moldings according to the invention. Insecticides include agonists or antagonists of the nicotinergic

Acetylcholine receptors of insects, phosphorus-containing compounds such as phosphorus or phosphonic acid esters, natural and synthetic pyrethroids, carbamates, amidines, juvenile hormones and juvenile hormone-like substances. Arylpyrazole derivatives may also be mentioned

Agonists or antagonists of the nicotinic acetylcholine receptors of insects are known e.g. from European Offenlegungsschriften No. 580 553, 464 830, 428 941, 425 978, 386 565, 383 091, 375 907, 364 844, 315 826, 259 738, 254 859, 235 725, 212 600, 192 060, 163 855, 154 178, 136 636, 303 570, 302 833, 306 696, 189 972, 455 000, 135 956, 471 372, 302 389; German Offenlegungsschriften No. 3 639 877, 3 712 307; Japanese Patent Laid-Open No. 03 220 176, 02 207 083,

63 307 857, 63 287 764, 03 246 283, 04 9371, 03 279 359, 03 255 072; U.S. Patent Nos. 5,034,524, 4,948,798, 4,918,086, 5,039,686, 5,034,404; PCT applications no. WO 91/17 659, 91/4965; French Application No. 2 611 114; Brazilian application No. 88 03 621.

Reference is hereby expressly made to the compounds described in these publications and their preparation.

These compounds can preferably be represented by the general formula (A)

(A)

R-N. ((ZZ))

II (A),

X-E

in which

R represents hydrogen, optionally substituted radicals from the group acyl, alkyl,

Aryl, aralkyl, heterocyolyl or heterocyclyl; A stands for a monofunctional group from the series hydrogen, acyl, alkyl, aryl or stands for a bifunctional group which is linked to the radical Z;

E represents an electron withdrawing group;

X stands for the radicals -CH = or = N-, where the radical -CH = can be linked to the radical Z instead of an H atom;

Z for a monofunctional group from the series alkyl, -O-R, -S-R,

/ .R

- N. stands

or represents a bifunctional group which is linked to the radical A or the radical X.

Compounds of the formula (A) in which the radicals have the following meaning are particularly preferred:

R represents hydrogen and also optionally substituted radicals from the series acyl, alkyl, aryl, aralkyl, heterocyclyl, heterocyclyl.

Formyl, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, (Al__yl -) - (aryl -) - phosphoryl, which in turn may be substituted, may be mentioned as acyl radicals.

As alkyl may be mentioned

in particular methyl, ethyl, i-propyl, sec- or t-butyl, which in turn can be substituted. Phenyl, naphthyl, in particular phenyl, may be mentioned as aryl.

Phenylmethyl and phenethyl may be mentioned as aralkyl.

Heterocycles with up to 10 ring atoms and

N, O, S in particular N as heteroatoms. In particular, thienyl, furyl, tetrahydrofuryl, thiazolyl, imidazolyl, pyridyl, benzthiazolyl may be mentioned.

Examples of heterocyclyl are heterocyclylmethyl, heterocyclylethyl having up to 6 ring atoms and N, O, S, in particular N, as heteroatoms.

Examples of preferred substituents are:

Alkyl having preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methyl, ethyl, n- and i-propyl and n-, i- and t-butyl; Alkoxy with preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methoxy,

Ethoxy, n- and i-propyloxy and n-, i- and t-butyloxy; Alkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio, n- and i-propylthio and n-, i- and t-butylthio; Haloalkyl with preferably 1 to 4, in particular 1 or 2, carbon atoms and preferably 1 to 5, in particular 1 to 3, halogen atoms, where the halogen atoms are identical or different and are halogen atoms, preferably fluorine, chlorine or bromine, in particular fluorine, such as trifluoromethyl ; hydroxy; Halogen, preferably fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine; cyano; nitro; amino; Monoalkyl- and dialkylamino - with preferably 1 to 4, in particular 1 or 2, carbon atoms per alkyl group, such as methylamino, methylethylamino, n- and i-propylamino and methyl-n-butylamino; carboxyl; Carbalkoxy preferably having 2 to 4, in particular 2 or 3, carbon atoms, such as carbomethoxy and carboethoxy; Sulfo (-SO ₃ H); Alkylsulfonyl preferably having 1 to 4, in particular 1 or 2, carbon atoms, such as methylsulfonyl and ethylsulfonyl; Arylsulfonyl with preferably 6 or 10 aryl carbon atoms, such as phenylsulfonyl and Heteroaryla ino and heteroarylalkylamino such as chlorpyridylarnino and chlorpyridylmethylamino.

A particularly preferably represents hydrogen and also optionally substituted radicals from the series acyl, alkyl, aryl, which preferably have the meanings given for R. A also represents a bifunctional group. Substituted alkylene with 1-4, in particular 1-2, carbon atoms may be mentioned, where the substituents listed above are mentioned as substituents and the alkylene groups can be interrupted by heteroatoms from the N, O, S series.

A and Z, together with the atoms to which they are attached, can form a saturated or unsaturated heterocyclic ring. The heterocyclic ring can contain a further 1 or 2 identical or different heteroatoms and / or hetero groups. The preferred heteroatoms are

Oxygen, sulfur or nitrogen and, as hetero groups, N-alkyl, alkyl of the N-alkyl group preferably containing 1 to 4, in particular 1 or 2, carbon atoms. Alkyl, methyl, ethyl, n- and i-propyl and n-, i- and t-butyl may be mentioned. The heterocyclic ring contains 5 to 7, preferably 5 or 6, ring members.

Examples of the heterocyclic ring are imidazolidine, pyrrolidine, piperidine, piperazine, hexamethylleriimine, hexahydro-l, 3,5-triazine, hexahydrooxodiazine, morpholine, which may optionally be substituted by methyl.

E stands for an electron-withdrawing radical, in particular NO ₂ , CN,

Haloalkylcarbonyl as l _j S-halo-C ^ -carbonyl, in particular COCF be mentioned. ₃

X stands for -CH = or -N = stands for optionally substituted radicals alkyl, -OR, -SR, -NRR, where R and the substituents preferably have the meaning given above.

can apart from the ring mentioned above together with the atom to which

it is bound and the rest

form a saturated or unsaturated heterocyclic ring at the position of X. The heterocyclic ring can contain a further 1 or 2 identical or different heteroatoms and / or hetero groups. The heteroatoms are preferably oxygen, sulfur or nitrogen and the hetero groups are N-alkyl, the alkyl or N-alkyl group preferably containing 1 to 4, in particular 1 or 2, carbon atoms. Alkyl, methyl, ethyl, n- and i-propyl and n-, i- and t-butyl may be mentioned. The heterocyclic ring contains 5 to 7, preferably 5 or 6 ring members.

Examples of the heterocyclic ring are pyrrolidine, piperidine, piperazine, hexamethyleneimine, morpholine and N-methylpiperazine.

Compounds of the general formulas (H) and (HI) may be mentioned as very particularly preferred compounds which can be used according to the invention:

noun,

^N 4J— - j πl (A)

(HI),

XE in which

n represents 1 or 2,

Subst stands for one of the substituents listed above, in particular for halogen, very particularly for chlorine,

A, Z, X and E have the meanings given above,

The following connections are mentioned in detail:

ch

CI

CH,

1 ³

The following connections are particularly emphasized:

Imidacloprid Nitenpyram

acetamiprid

The phosphoric or phosphonic acid esters include:

0-ethyl-0- (8-quinolyl) phenylthiophosphate (Quintiofos),

0,0-diethyl-0- (3-cUoro-4-methyl-7-coumarinyl) thiophosphate (Coumaphos),

0,0-diethyl-0-phenylglyoxyloni l-oxime thiophosphate (phoxime),

0.0-diethyl-O-cyanochlorobenzaldoxime thiophosphate (chlorophoxime),

0,0-diethyl-0- (4-bromo-2,5-dichlorophenyl) phosphorothionate (bromophos-ethyl), 0.0.0 ^ 0'-tetraethyl-S, S'-memylene-di (phosphorodite ionate) (ethion),

2,3-p-Dioxanedithiol-S, S-bis (0,0-diethylphosphorodithionat,

2-chloro-1 - (2,4-dichlorophenyl) vinyl diethyl phosphate (chlorfenvinphos),

0.0-Dimethyl-0- (3-methyl-4-methylthiophenyl) thionophosphoric acid ester (fenthion).

The carbamates include:

2-isopropoxyphenylmethyl carbamate (propoxur),

1-naphthyl-N-methyl carbamate (carbaryl).

The synthetic pyrethroids include compounds of the formula B.

in which

R ¹ and R ^{2 represent} halogen, optionally halogen-substituted alkyl, optionally halogen-substituted phenyl,

R ^{3 represents} hydrogen or CN, R ^{4 represents} hydrogen or halogen,

R ^{5 represents} hydrogen or halogen,

Synthetic pyrethroids of the formula B in which are preferred

R ^{1 represents} halogen, in particular fluorine, chlorine, bromine,

R ^{2 represents} halogen, in particular fluorine, chlorine, bromine, trihalomethyl, phenyl, chlorophenyl,

R ^{3 represents} hydrogen or CN,

R ^{4 represents} hydrogen or fluorine,

R stands for hydrogen.

Synthetic pyrethroids of the formula B in which are particularly preferred

R ^{1 represents} chlorine,

R ^{2 represents} chlorine, trifluoromethyl, p-chlorophenyl,

R ^{3 represents} CN,

R ^{4 represents} hydrogen or fluorine,

R ^{5 represents} hydrogen.

Compounds of the formula B may be mentioned in particular R ^{1 represents} chlorine,

R ^{2 represents} chlorine or p-chlorophenyl,

R ^{3 represents} CN,

R ^{4 represents} fluorine in the 4-position,

R stands for hydrogen.

The following may be mentioned in detail:

3- [2- (4-CUθhenyl) -2-chlorovinyl] -2,2-dimethyl-cyclopropanecarboxylic acid [(α-cyano-4-fluoro-3-phenoxy) benzyl] ester (flumethrin),

2,2-dimethyl-3- (2,2-dicMorvinyl) -cyclopropanecarboxylic acid-α-cyano (4-fluoro-3-phenoxy) -benzyl ester (cyfluthrin) and its enantiomers and stereoisomers,

α-cy ano-3-phenoxybenzyl (+) - cis, trans-3 - (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate (deltamethrin),

2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid-α-cyano-3-phenoxybenzyl ester (cypermethrin),

3-phenoxybenzyl () -cis, trans-3- (2,2-dic orvinyl) -2,2-dimethylcyclopropane carboxylate (permethrin),

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

2-Cy ano-3-phenoxybenzyl-2- (2-chloro-α, α, α-trifluoro-p-toluidino) -3-methylbutyrate

(Fluvalinate). The amidines include:

3-Methyl-2- [2,4-dimethyl-phenylimino] -thiazoline

2- (4-CUOR-2-memylphenylimino) -3-methylthiazolidine

2- (4-C_üor-2-memylphenylimino) -3- (isobutyl-l-enyl) -thiazolidine

1,5-bis- (2,4-dimethylphenyl) -3-methyl-1,3,5-triazaρenta- 1,4-diene (amitraz).

Juvenile hormones or juvenile hormone-like substances include substituted diaryl ethers, benzoyl ureas and triazine derivatives. Juvenile hormones and juvenile hormone-like substances include in particular compounds of the following formulas:

The substituted diaryl ethers include, in particular, substituted alkoxydiphenyl ethers or diphenyl methanes of the general formula C.

in which

R ^{1 represents} hydrogen, halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, dioxyalkylene, dioxyhalogenalkylene, CN, NO ₂ , alkenyl, alkynyl, alkoxyalkyl, alkoxyalkoxy, hydroxyalkoxy,

R ^{2 represents} the radicals specified for R ¹ ,

R ^{3 represents} the radicals specified for R ¹ ,

R ^{4 represents} hydrogen, alkyl, haloalkyl or halogen,

R ^{5 represents} the radicals indicated for R ⁴ ,

Het represents optionally substituted heteroaryl which is not bound to the rest of the group via the hetero atom,

X, Y independently of one another represent -O-, -S-

Z represents -O-, -S-, -CH ₂ -, -CHCH ₃ -, -C (CH ₃ ) ₂ -,

m and n independently of one another represent 0, 1, 2, 3 but their sum is equal to or greater than 2.

Compounds of the formula C are particularly preferred in which

R ^{1 is} hydrogen, methyl, trifluoromethyl, methoxy, trifluoromethoxy, chlorine, fluorine

R ^{2 represents} hydrogen,

R ^{3 represents} hydrogen, fluorine, chlorine, methyl,

R ^{4 represents} hydrogen or methyl,

R ^{5 represents} methyl, ethyl, trifluoromethyl or hydrogen,

Het is pyridyl or pyridazinyl which are optionally substituted by

Fluorine, chlorine, methyl, NO ₂ , methoxy, methylmercapto,

X stands for O,

Y stands for O,

Z represents O, CH ₂ or -C (CH ₃ ) ₂ -,

m represents 1,

n stands for 1.

The following connections are mentioned in detail:

The benzoylureas include compounds of the formula (D):

in which

R ^{1 represents} halogen,

R ^{2 represents} hydrogen or halogen,

R ^{3 represents} hydrogen, halogen or C ₁ alkyl. R ^{4 is} halogen, l-5-halo-C _M -alkyl, C _H - alkoxy, l-5-halo-C ₁ -alkoxy, C _w - alkylthio, l-5-halo-C _M -alkylthio, phenoxy or Pyridyloxy which may optionally be substituted by halogen, C _M -alkyl, 1-5-halo-C _1-4 -alkyl, C _M -alkoxy, 1-5-halo-C ^ -alkoxy, C ^ -alkylthio, 1-5 haloC ^ alkylthio.

In particular, the following should be mentioned:

W ^• CONHCONH

The triazines include compounds of the formula (E)

embedded image in which

Ri represents cyclopropyl or isopropyl;

R _{2 is} hydrogen, halogen,

Cyclopropylcarbonyl, Cj-C ₁₂ -

Alkylcarbamoyl, -C ^ alkylthiocarbamoyl or C ₂ -C ₆ alkenylcarbamoyl; and

R ₃ for hydrogen,

Cyclopropyl, C ₂ -C ₆ alkenyl, C _r Cι ₂ -Al__yl- carbonyl, cyclopropylcarbonyl, -C ^ alkylcarbamoyl, C _j -C ^ alkylthio carbamoyl or C ₂ -C ₆ alkenylcarbamoyl and their acid addition salts, the are non-toxic to warm-blooded animals. In particular, the following should be mentioned:

Arylpyrazole derivatives with insecticidal activity are e.g. disclosed in WO 98/24 769 or in EP-A-295 117, reference is expressly made to the documents mentioned.

Thiocarbamoyl derivatives of the formula (F) may be mentioned (cf. WO 98/24 769)

in which

Ar represents in each case optionally substituted phenyl or pyridyl, particularly preferably in each case optionally up to three times the same or different by fluorine, chlorine, trifluoromethyl, trifluoromethylthio, trifluoromethoxy, methoxy, hydrazino, dimethylhydrazino, amino, methylamino, dimethylamino, iminomethyl, cyano, methylthio or the grouping

wherein

R ⁸ and R ^{9 are} identical or different and represent hydrogen or (C1-C4) alkyl,

substituted phenyl or pyridyl.

R ^{2 represents} haloalkyl, haloalkenyl or haloalkynyl, particularly preferably (Ct-C4) haloalkyl having 1 to 9 identical or different halogen atoms from the series fluorine, chlorine and bromine, (C2-C4) -

Haloalkenyl with 1 to 5 identical or different halogen atoms from the series fluorine, chlorine and bromine or (C2-C4) haloalkynyl with 1 to 5 identical or different halogen atoms from the series fluorine, chlorine and bromine, n stands for 0, 1 or 2.

A very particularly preferred example is the compound of the formula (AI)

called.

Another example of a particularly preferred arylpyrazole is the compound fipronil of the formula disclosed in EP-A-295 117

fipronil

directed.

The active ingredients with the common names Propoxur, Cyfluthrin, Flumethrin, Pyri proxyfen, Methoprene, Diazinon, Amitraz, Fenthion,

Imidacloprid and the aiylpyrrazoles of the formula (AI) and fipronil. The active compounds can be present in the moldings alone or in a mixture with one another.

The active substances are present in the shaped bodies in concentrations of 0.1 to 20% by weight, preferably 1 to 10% by weight. The total proportion of active substance or mixture of active substances is not higher than 30% by weight, preferably not higher than 25% by weight.

The moldings according to the invention optionally contain plasticizers. Plasticizers for biodegradable polymers that are suitable for use in animals belong, for example, to the classes of substances: glycerol esters, citric acid esters, lactic acid esters, glycerol, myristic acid esters, adipic acid esters and optionally phthalic acid esters.

The plasticizers are in the moldings in concentrations of max.

40% by weight, preferably between 0 and 30% by weight.

The moldings according to the invention can furthermore contain the additives customary for plastics. Common additives are, for example, pigments, stabilizers, flow agents, lubricants, mold release agents and fillers.

Examples of common additives are:

1. Antioxidants, these include

1.1 Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di -tert.butyl-4-n-butylphenol, 2,6-di-tert.butyl-4-i-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4 , 6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert.butyl-4-methoxymethylphenol. 1.2 Alkylated hydroquinones, e.g. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4 -octa-decyloxyphenyl.

1.3 Hydroxylated thiodiphenyl ethers, for example 2,2'-thio-bis- (6-tert-butyl-4-methylphenol), ^2,2-thiobis (4-octylphenol), 4,4'-thio bis- (6-tert.butyl-3-methylphenol), 4,4'-thio-bis- (6-tert.butyl-2-methylphenol).

1.4 alkylidene bisphenols, e.g. 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol),

2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol), 2,2 * -methylene-bis- (4-methyl- 6- (α-methylcyclohexyl) phenol), 2,2 ' -Methylene-bis- (4-methy_-6-cyclohexylphenol), 2,2'-methylene-bis- (6-nonyl-4-methylphenol), 2,2'-methylene-bis- (4,6- di-tert.butylphenol), 2,2'-ethylidene-bis- (4,6-di-tert.butylphenol), 2,2'-ethylidene-bis- (6-tert.butyl-4-isobutylphenol) , 2,2'-methylene-bis- [6- (α ~ methylbenzyl) -4-nonylphenol], 2,2'-methylene-bis- [6- (, -dimethylbenzyl) -4-nonylphenol] , 4,4'-methylene-bis- (2,6-di-tert-butylphenol), 4,4'-methylene-bis- (6-tert-butyl-2-methylphenol), 1, 1-bis ( 5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-di- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1, 3-tris - (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol - bis- [3,3-bis- (3 ^, -tert.butyl-4'-hydroxyphenyl) butyrate], di- (3-tert.butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, di - [2- (3'-tert-butyl-2'-hydroxy-5'-methy lbenzyl) -6-tert-butyl-4-methyl-phenyl] terephthalate.

1.5 benzyl compounds, e.g. 1,3,5-tri- (3,5-di-tert-butyl-4-hydroxybenzyl) - 2,4,6-trimethylbenzene, di- (3,5-di-tert-butyl-4-hydroxybenzyl) - sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic acid, bis- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -dithiol-terephthalate, 1,3, 5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-

2,6-dimethylbenzyl) isocyanurate, 3, 5-di-tert-butyl-4-hydroxybenzyl-phospho- Phonic acid dioctadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, calcium salt.

1.6 acylaminophenols, e.g. 4-hydroxylauric anilide, 4-hydroxystearic anilide, 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine, N- (3, 5 -di-tert-butyl-4-hydroxyphenyl) -ca_: ba_ninsäureoctylester.

1.7 esters of ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, e.g. Methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol,

Pentaerythritol, tris-hydroxyethyl isocyanurate, di-hydroxyethyl oxalic acid diamide.

1.8 esters of ß- (5-tert.butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, e.g. with methanol, octadecanol, 1.6-

Hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl-isocyanurate, di-hydroxyethyl-oxy-acid diamide.

1.9 Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, e.g.

N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine, N, N '- (3,5- (tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamine, N , N'-Di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

2. UV absorbers and light stabilizers, these include

2.1 2- (2'-hydroxyphenyl) benzotriazoles, such as 5'-methyl-, 3 ', 5'-di-tert-butyl-, 5'-tert-butyl-, 5' - (l, l, 3, 3-tetramethylbutyl) -, 5-chloro-3 ', 5'-di-tert-butyl-, 5-chloro-3 ^, -tert.butyl-5'-methyl-, S'-sec.butyl-S' -tert.butyl, 4'-octoxy, 3 ', 5'-di-tert-amyl (α, α-dimethylbenzyl) ^3, 5'-bis- derivative. 2.2 2-hydroxybenzophenones, such as, for example, the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydoxy, 2 '-Hydroxy-4,4'-dimethoxy derivative.

2.3 esters of optionally substituted benzoic acids, e.g. 4-tert.butylphenylsalicylate, phenylsalicylate, octylphenylsalicylate, dibenzoylresorcinol, bis- (4-tert.butylbenzoyl) -resorcinol, benzoylresorcinol, 3,5-di-tert.butyl-4-hydroxy-benzoic acid-2,4-di- tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.

2.4 acrylates, e.g. α-cyano-ß, ß-diphenylacrylic acid ethyl ester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano-ß-methyl-p-methoxy-cinnamic acid methyl ester or -butyl ester, α-carbomethoxy-p-methoxy-cinnamic acid methyl N- (ß-carbomethoxy-ß-cyanovinyl) -2-methyl-_t_dolin.

2.5 Nickel compounds, such as nickel complexes of 2,2'-thio-bis- [4- (l, 1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or l: 2 complex, optionally with additional ones Ligands, such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyl _τ dithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl or ethyl ester, Nickel complexes of ketoximes, such as of 2-hydroxy-4-methyl-phenyl-undecylketone oxime, nickel complexes of l-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additional ligands.

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

2.7 oxalic acid diamides, such as 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert.butyl-oxanilide, 2.2 ^l -di-dodecyloxy-5.5 ^, -di-tert.butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert.butyl- 2'-ethyloxanilide and its mixture with 2-ethoxy-2'-et__y_- 5,4'-di-tert.butyl-oxanihd mixtures of o- and p-methoxy- and of o- and p-ethoxy-disubstituted oxanilides.

3. Metal deactivators, e.g. N, N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis-salicyloylhydrazine, N, N'-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) - hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis-benzyüden-oxalic acid dihydrazide.

4. Phosphites and phosphonites such as e.g. Triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tri- (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di- tert.butylphenyl) phosphite, diisodechritol -di- tert.butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrahydis (2,4-di-tert.butylphenyl) -4,4'-biphenylene diphosphonite, 3,9-bis (2, 4-di-tert.butylphenoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane.

5. Peroxide-destroying compounds, such as, for example, esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercapto-benzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc-dibutyl-dithiocarbamate, dioctadeca-tetrakis-disulfide ( ß-dodecylmer capto) propionate. 6. Polyamide stabilizers, such as copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

7. Basic co-stabilizers such as e.g. Melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate, K palmitate, Antimony catecholate or tin catecholate.

8. Nucleating agents, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.

9. Fillers and reinforcing agents such as e.g. Calcium carbonate, silicates, glass fibers, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

10. Other additives, such as Lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents.

The various

Components are dry mixed according to known mixing processes and compression molded according to known extrusion or injection molding processes.

It is also possible to mix the individual components by dissolving them in a common solvent and then to precipitate them in a suitable non-solvent, or to remove the solvent from the solution using an evaporation extruder. During the precipitation, the solution is preferably pressed through a nozzle into a precipitation bath, and the coagulating material formed is drawn off as threads (wet spinning process). The precipitation is preferably carried out by means of the known dry and wet spinning processes. Technically, the choice of the processing method for the production of the shaped bodies according to the invention is fundamentally based on the theological properties of the shaped body material and the shape of the desired structure. The processing methods can be set according to the processing technology or the type of shaping. In process technology, the processes can be subdivided according to the theological states they have undergone. Thereafter, casting, pressing, spraying and application are possible for viscous molded body materials, and injection molding, extrusion (extrusion), calendering, rolling and optionally kneading are suitable for elastoviscose polymers. Divided according to the type of shaping, the moldings according to the invention can be produced by casting, dipping, pressing, injection molding, extruding, calendering, embossing, bending, deep drawing, spinning, etc.

These processing methods are known and require no further explanation.

Shaped bodies according to the present invention are collars, collar pendants (medallions), ear, tail, foot bracelets, bracelets, ear tags, foils, peel-off foils, adhesive strips, strips, plates, granules. Collars and medallions are preferred.

The moldings are used to combat parasites on or on warm-blooded animals and in their surroundings.

The term warm-blooded animals encompass in particular humans as well as domestic, hobby and farm animals.

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

The shaped bodies according to the invention are particularly preferred in dogs and

Cats used. The pests include:

From the order of the anoplura e.g. Haematopinus spp., Linognathus spp.,

Solenopotes spp., Pediculus spp., Pthirus spp .; from the order of the Mallophaga e.g. Trimenopon spp., Menopon spp.,

Eomenacanthus spp., Menacanthus spp., Trichodectes spp., Felicola spp., Damaünea spp., Bovicola spp; from the order of the Diptera e.g. Aedes spp., Culex spp., Simulium spp.,

Phlebotomus spp., Chrysops spp., Tabanus spp., Musca spp., Hydrotaea spp., Muscina spp., Haematobosca spp., Haematobia spp., Stomoxys spp., Fannia spp.,

Glossina spp., Lucilia spp., Calliphora spp., Auchmeromyia spp., Cordylobia spp.,

Cochliomyia spp., Chrysomyia spp., Sarcophaga spp., Wohlfartia spp., Gasterophilus spp., Oesteromyia spp., Oedemagena spp., Hypoderma spp., Oestrus spp.,

Rhinoestrus spp., Melophagus spp., Hippobosca spp ..

From the order of the Siphonaptera e.g. Ctenocephalides spp., Echidnophaga spp.,

Ceratophyllus spp. imd Pulex spp ..

From the order of the metastigmata e.g. Hyalomma spp., Rhipicephalus spp., Boophilus spp., Amblyomma spp., Haemaphysalis spp., Dermacentor spp., Ixodes spp., Argas spp., Ornithodorus spp., Otobius spp .; from the order of the mesostigmata e.g. Dermanyssus spp., Ornithonyssus spp., Pneumonyssus spp ..

From the order of the prostigmata, for example Cheyletiella spp., Psorergates spp., Myobia spp., Demodex spp., Neotrombicula spp .; from the order of the Astigmata e.g. Acarus spp., Myocoptes spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Neoknemidocoptes spp. Cytodites spp., Laminosioptes spp .. Another advantage of the moldings according to the invention is that they are granulated and ground after use and the material obtained in this way is used to control insects which damage crops in the field of agriculture or garden and ornamental plant cultivation.

The pests that occur in the areas mentioned include:

From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber. From the order of the Diplopoda e.g. Blaniulus guttulatus.

From the order of the Chilopoda e.g. Geophilus carpophagus, Scutigera spec.

From the order of the Symphyla e.g. Scutigerella immaculata.

From the order of the Thysanura e.g. Lepisma saccharina.

From the order of the Collembola e.g. Onychiurus armatus. From the order of the Dermaptera e.g. Forficula auricularia.

From the order of the Isoptera e.g. Reticulitermes spp ..

From the order of the Mallophaga e.g. Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.

From the order of the Heteroptera e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of the Homoptera e.g. Aleurodes brassicae, Bemisia tabaci,

Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis,

Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuh, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatataidia, aphantum lidium aphidata, aphidella, aphidata, pseudo aphid, sap , Psylla spp.

From the order of the Lepidoptera, for example Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera sppi, Trichoplapsia s., Trichoplusia n. , Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselhella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona viridima, Homona magnidana.

From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephususpp sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psioloides , Agriotes spp.,

Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp. From the order of the Diptera e.g. Aedes spp., Anopheles spp., Culex spp.,

Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tabanus spp. Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp .. From the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans.

The following examples give insecticidal moldings and their preparation based on biodegradable polymers which are intended to explain the invention without restricting it: When carrying out the process according to the invention, the procedure is generally such that the components are mixed with one another in the desired amounts in any order and then opened with stirring or kneading

Temperatures between 100 ° C and 200 ° C, preferably heated between 120 ° C and 180 ° C. The resulting paste-like mass or liquid mixture can be converted into moldings or films by means of nozzles, presses or other suitable devices using the methods customary for thermoplastic polymer.

Examples

Example 1 (TPU X)

84 g (0.5 mol) of hexamethylene diisocyanate were introduced and 18.4 g (0.4 mol) of ethanol (chain terminator) are added dropwise at 80 to 90 ° C. in the course of 1 hour. Then 27 g (0.3 mol) of 1,4-butanediol were added dropwise in the course of 1 hour. The temperature was raised to 160 ° C. The mixture was stirred at 160 ° C. (about 30 minutes) until the melt no longer contained any NGO (IR spectroscopy). After pouring onto a Teflon sheet, the melt solidified very quickly. The melting point was 150 to 156 ° C.

Example 2 (TPU Y)

216.68 g (0.127 mol) of a polyester composed of adipic acid and 1,6-hexanediol and neopentyl glycol (in a molar ratio of 0.65: 0.35) with an average molecular weight of 1706 g / mol and 2% by weight of OH groups and 107.16 g (0.054 mol) of a polyester of adipic acid and ethylene glycol with an average molecular weight of 1984 g / mol and 1.7% by weight of OH groups were mixed and dried at 120 ° C. and 15 mbar for 30 minutes. The mixture was heated to 160 ° C. under nitrogen and 8.91 g (0.099 mol) of 1,4-butanediol and 47.12 g (0.28 mol) of hexamethylene diisocyanate were added in succession. The

The reaction was exothermic and warmed up to 180 ° C. 10 minutes after the addition of isocyanate, the melt was poured onto a Teflon sheet and reheated at 80 ° C. in a drying cabinet for 20 hours. The product was free of NCO (TR spectroscopy). In this way, a soft, moisture-stable TPU Y with a Shore A hardness of approx. 72 was obtained (test method DIN 53505). Example 3 ((TPU blend)

1900 g of the TPU Y from Example 2 were dry premixed with 100 g of the TPU-X from Example 1 after crushing to give irregular granules and homogenized at 120-140 ° C. on a HZSK laboratory extruder from HAAKE. The strand emerging from the extruder was worked up underwater cooling by means of strand granulation to give approximately 2 mm long cylindrical granules and then dried in a vacuum drying cabinet at 60 ° C. for 1 h.

Example 4

The procedure was as described in Example 3, with the difference that 750 g of the TPU Y from Example 2 with 50 g of the TPU X from Example 1, 100 g of imidacloprid, 50 g of flumethrin and 50 g of phthalate dioctyl ester were used for homogenization on the extruder , The extruder was equipped with a flat die with an opening of 170 x 2 mm. The flat strand emerging from the extruder was in the

Airflow cooled. In this way, endless tapes were obtained which were adapted as collars for testing on experimental animals.

Example 5

The procedure was as described in Example 4, with the difference that 750 g of the TPU Y from Example 2 with 50 g of the TPU X from Example 1, 100 g of imidacloprid, 50 g of flumethrin and 50 g of triacetin were used for homogenization on the extruder , The extruder was provided with a round hole die of 2 mm diameter and the strand emerging from the extruder was cooled after air cooling

Strand granulation worked up to about 2 mm long cylinder granulate and then dried in a vacuum drying cabinet at 40 ° C. for 1 h. By re-melting the granules, depending on the injection mold used, tapes or medallions are obtained on injection molding machines for use on, on or in the vicinity of warm-blooded animals.

Example 6

200 g of the granules obtained according to Example 5 are introduced into a heatable press and the mixture is pressed at 120 ° C. and 200 bar within 2 minutes to form a 1 mm thick test plate. A 180 x 50 x 1 mm strip was stored open, the released active ingredients were wiped from time to time with methanol from the surface and determined quantitatively by HPLC.

mg imidacloprid / flumethrin W = weeks [storage time]

efficacy trials To carry out efficacy tests against fleas and ticks, dogs were treated with collars according to Example 4. The treatment was carried out by attaching a shaped body in the form of a collar (approx. 1.4 cm wide strip) to the neck of the animals. The strips were adjusted as closely as possible (with a finger-wide space) to the neck of the animals. The medallions (Example 5) were perforated and attached to a normal collar not loaded with active ingredient. 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 are infested with approx. 100 adult, fasting Ctenocephalides felis per dog. The fleas are spread on the neck of the animal.

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

After the fleas have been counted, the animals are treated. The dogs in the control group are not treated. The medicinal products to be tested are administered to the animals as collars or medallions. Collars and medallions remain on the animal until the end of the experiment on day 170. Only 1 collar or 1 medallion is applied to each animal. Only clinically healthy animals are used.

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

On days 14, 28, 56, 84, 112, 140 and 168 all dogs are reinfested with approx. 100 adult, sober Ctenocephalides felis 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:

0 number of fleas KG - 0 number of fleas BG effectiveness% = X 100

0 number of fleas KG

Applied with flumethrin and imidacloprid in the example 4 as a collar and in the example 5 as a medallion, efficacies> 90% against Ctenocephalides felis can be achieved over 3-6 months.

Example B: Efficacy against ticks (Rhipicephalus sanguineus) in dogs

On day -1 dogs with 2% Rompun ^® (Bayer AG, active ingredient:

Xylazine hydrochloride) (0.1 ml / kg body weight). After all dogs are sedated (after approx. 10-15 minutes) they are transferred to transport boxes and 50 Rhipicephalus sanguineus ($ 25, 25c?) Per dog are spread on the neck of the animal. The animals are put back into the cage from the transport box after about 1½ hours.

On day 0, the success of the infestation on the dog is checked by searching for ticks on the awake animal. Intensive searches are carried out in the head and ear area including the ear fold, in the area of the neck, on the lower abdomen, on the lower chest, on the side flank and between the toes and on the gum measurements. The number of sucked live ticks is recorded. Dead ticks are removed. After the ticks have been counted, the animals are treated. The dogs in the control group are not treated. The medicinal products to be tested are administered to the animals as collars or medallions. Collars and medallions remain on the animal until the end of the experiment on day 170. Only 1 collar or 1 medallion is applied to each animal. Only clinically healthy animals are used.

On day 1 and day 2, all dogs are checked for live and dead sucking ticks. The results are recorded in the raw data. On day 2, all living and dead ticks are removed from the dog.

On days 14, 28, 56, 84, 112, 140 and 168, all dogs are reinfested with 50 Rhipicephalus sanguineus ($ 25, 25c) per dog. One and two days after reinfestation, all dogs are checked for live and dead sucked ticks. The results are logged in the raw data. On the second day after reinfestation, all living and dead ticks are removed from the dog.

A modified Abbott formula is used to calculate the effectiveness:

0 number of ticks KG - 0 number of ticks BG

Efficacy% = X 100

0 number of ticks KG

KG: control group BG: treatment group

With flumethrin and imidacloprid applied in formulation example 4 as a collar and in formulation example 5 as a medallion, efficacies can be achieved

> 85% against. Rhipicephalus sanguineus can be achieved over 3-6 months.

Claims

Patentansprflche

1. Containing molded articles

a) a biodegradable polyurethane elastomer mixture b) at least one insecticidal and / or acaricidal active ingredient. c) plasticizer, the polyurethane elastomer mixture a) consisting of ai) 80 to 98% by weight of an aliphatic thermoplastic polyurethane (TPU Y) with a number average molecular weight of

20,000 g / mol to 100,000 g / mol and aii) 2 to 20% by weight of a low molecular weight aliphatic thermoplastic polyurethane (TPU X) with a number average molecular weight of 462 g / mol to 6,000 g / mol.

2. A process for the production of the moldings according to claim 1, in which the biodegradable polyurethane elastomer mixture (TPU Y / TPU X) with one or more insecticidal and / or acaricidal active ingredient, the plasticizer and, if appropriate, customary additives at 100 to 200 ° C. is preferred 120 ° C to 180 ° C, mixed and processed into moldings in the usual way.

3. Use of the shaped body according to claim 1 for combating parasites in warm-blooded animals.