WO2002078443A1 - Corps moules renfermant des substances actives, a base de polyurethannes thermoplastiques, servant a lutter contre des parasites - Google Patents

Corps moules renfermant des substances actives, a base de polyurethannes thermoplastiques, servant a lutter contre des parasites Download PDF

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Publication number
WO2002078443A1
WO2002078443A1 PCT/EP2002/002961 EP0202961W WO02078443A1 WO 2002078443 A1 WO2002078443 A1 WO 2002078443A1 EP 0202961 W EP0202961 W EP 0202961W WO 02078443 A1 WO02078443 A1 WO 02078443A1
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Prior art keywords
spp
tert
tpu
butyl
mol
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PCT/EP2002/002961
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German (de)
English (en)
Inventor
Olaf Hansen
Hanns-Peter Müller
Horst Gruttmann
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Bayer Ag
Mueller Hanns-Peter
Olaf Hansen
Horst Gruttmann
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Publication of WO2002078443A1 publication Critical patent/WO2002078443A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Definitions

  • 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
  • plastics are required which have a tendency to crystallize so that extrudable, sprayable and blowable products with rapid crystallization are obtained on cooling.
  • 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.
  • Active ingredients and plasticizers are excellently suitable, and that these formulations can be processed on conventional plastic processing machines in fast cycles.
  • 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:
  • 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.
  • the biodegradable polyester urethane elastomer mixture TPU Y / TPU X
  • 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.
  • Biodegradable polymers are those that meet the test conditions described in the draft DIN 54 900-1.
  • thermoplastic polyester urethanes as composable plastics is described in EP-A 0 593 975.
  • 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
  • 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
  • UV stabilizers D 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),
  • 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,
  • thermoplastic polyurethane 1 to 20% by weight
  • HDI hexamethylene diisocyanate
  • 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.
  • diisocyanates A 1,6-hexamethylene diisocyanate
  • 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
  • cycloaliphatic diisocyanates such as l-isocyanate-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (_PDI) and perhydro-2,4 ⁇ - and or -4,4 , -diphenylmethane diisocyanates , are preferred (ß u MDI).
  • isocyanurate from HDI (Desmodur® N 3300, Bayer AG) or the trimere from IPDI (Desmodur® Z 4300, Bayer AG) can also be used.
  • HDI Desmodur® N 3300, Bayer AG
  • trimere from IPDI (Desmodur® Z 4300, Bayer AG)
  • Suitable monofunctional isocyanates are, for example, stearyl isocyanate and cyclohexyl isocyanate.
  • 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.
  • 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.
  • polyhydric alcohols are e.g. Ethylene glycol, propylene glycol- (1,2) and
  • polyesters can have a proportion of terminal carboxyl groups.
  • Polyesters of lactones for example ⁇ -caprolactone, or of hydroxycarboxylic acids, for example ⁇ -hydroxycaproic acid, can also be used.
  • the hydroxy-functional polyesters known from fat chemistry such as castor oil and its transesterification products, can also be used.
  • 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),
  • polyester polyols and the polycarbonate diols 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.
  • 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.
  • Alkylene oxides can be used individually alternately in succession or as mixtures.
  • 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
  • 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 ⁇ -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.
  • 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).
  • monofunctional compounds can also be used in small amounts, e.g. as a chain terminator or mold release.
  • 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.
  • 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
  • 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).
  • 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.
  • 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
  • Preferred catalysts are organic metal compounds, in particular titanium acid esters, iron or tin compounds. Dibutyltin dilaurate is very particularly preferred.
  • UV stabilizers and catalysts used according to the invention 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
  • 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.
  • 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
  • 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
  • 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.
  • 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.
  • the TPUs according to the invention can be used as a sinterable powder for producing flat structures and hollow bodies.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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,
  • R represents hydrogen, optionally substituted radicals from the group acyl, alkyl,
  • Aryl, aralkyl, heterocyolyl or heterocyclyl 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
  • 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.
  • 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.
  • N, O, S in particular N as heteroatoms N, O, S in particular N as heteroatoms.
  • thienyl, furyl, tetrahydrofuryl, thiazolyl, imidazolyl, pyridyl, benzthiazolyl may be mentioned.
  • heterocyclyl examples include heterocyclylmethyl, heterocyclylethyl having up to 6 ring atoms and N, O, S, in particular N, as heteroatoms.
  • 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 al
  • 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
  • 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.
  • heterocyclic ring examples include 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,
  • 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.
  • heterocyclic ring examples include pyrrolidine, piperidine, piperazine, hexamethyleneimine, morpholine and N-methylpiperazine.
  • n 1 or 2
  • the phosphoric or phosphonic acid esters include:
  • the carbamates include:
  • the synthetic pyrethroids include compounds of the formula B.
  • 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
  • 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
  • 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
  • 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
  • amidines include:
  • 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.
  • 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 -,
  • n and n independently of one another represent 0, 1, 2, 3 but their sum is equal to or greater than 2.
  • 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
  • Z represents O, CH 2 or -C (CH 3 ) 2 -
  • n 1,
  • n 1
  • the benzoylureas include compounds of the formula (D):
  • 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.
  • the triazines include compounds of the formula (E)
  • Ri represents cyclopropyl or isopropyl
  • R 2 is hydrogen, halogen, Cyclopropylcarbonyl, Cj-C 12 -
  • R 3 for hydrogen, Cyclopropyl, C 2 -C 6 alkenyl, C r C ⁇ 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.
  • 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
  • R 8 and R 9 are identical or different and represent hydrogen or (C1-C4) alkyl
  • 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) -
  • a very particularly preferred example is the compound of the formula (AI)
  • Another example of a particularly preferred arylpyrazole is the compound fipronil of the formula disclosed in EP-A-295 117
  • 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.
  • the moldings according to the invention can furthermore contain the additives customary for plastics.
  • additives are, for example, pigments, stabilizers, flow agents, lubricants, mold release agents and fillers.
  • Antioxidants these include
  • 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- ( ⁇ -methylcyclohexyl) -4 , 6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert.butyl-4-methoxymethylphenol.
  • 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.
  • 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).
  • alkylidene bisphenols e.g. 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol),
  • 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.
  • 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_ninkladylester.
  • 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.
  • UV absorbers and light stabilizers these include
  • 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.
  • 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.
  • benzoic acids e.g. 4-tert.butylphenylsalicylate, phenylsalicylate, octylphenylsalicylate, dibenzoylresorcinol, bis- (4-tert.butylbenzoyl) -resorcinol, benzoylre
  • acrylates e.g. ⁇ -cyano-ß, ß-diphenylacrylic acid ethyl ester or isooctyl ester, ⁇ -carbomethoxy-cinnamic acid methyl ester, ⁇ -cyano-ß-methyl-p-methoxy-cinnamic acid methyl ester or -butyl ester, ⁇ -carbomethoxy-p-methoxy-cinnamic acid methyl N- (ß-carbomethoxy-ß-cyanovinyl) -2-methyl-_t_dolin.
  • 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 ⁇ 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.
  • 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-tte
  • 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.
  • 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.
  • N, N'-diphenyloxalic acid diamide 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) -
  • 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.buty
  • Peroxide-destroying compounds such as, for example, esters of ⁇ -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.
  • Polyamide stabilizers such as copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.
  • 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.
  • 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.
  • Nucleating agents e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.
  • 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.
  • additives such as Lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents.
  • Components are dry mixed according to known mixing processes and compression molded according to known extrusion or injection molding processes.
  • 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.
  • 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.
  • the moldings according to the invention can be produced by casting, dipping, pressing, injection molding, extruding, calendering, embossing, bending, deep drawing, spinning, etc.
  • 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.
  • 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
  • the pests include:
  • 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.,
  • Cochliomyia spp. Chrysomyia spp., Sarcophaga spp., Wohlfartia spp., Gasterophilus spp., Oesteromyia spp., Oedemagena spp., Hypoderma spp., Oestrus spp.,
  • Rhinoestrus spp. Melophagus spp., Hippobosca spp ..
  • the pests that occur in the areas mentioned include:
  • Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber. From the order of the Diplopoda e.g. Blaniulus guttulatus.
  • Thysanura e.g. Lepisma saccharina.
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
  • Trialeurodes vaporariorum Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis,
  • Conoderus spp. Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • 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.
  • Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp .. From the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans.
  • Example 3 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
  • Example 4 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.
  • tapes or medallions are obtained on injection molding machines for use on, on or in the vicinity of warm-blooded animals.
  • Example A Efficacy against fleas (Ctenocephalides felis) in dogs
  • 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.
  • Example B Efficacy against ticks (Rhipicephalus sanguineus) in dogs
  • 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.
  • control group BG treatment group
  • Rhipicephalus sanguineus can be achieved over 3-6 months.

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
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Abstract

La présente invention concerne de nouveaux corps moulés renfermant des substances actives, à base de mélanges élastomères de polyuréthannes aliphatiques, thermoplastiques, biodégradables, qui sont principalement constitués de polyuréthannes thermoplastiques à hauts poids moléculaires et de faibles masses de polyuréthannes thermoplastiques à faibles poids moléculaires. La présente invention concerne également la production et l'utilisation de ces corps moulés dans la lutte contre des parasites présents sur des êtres humains et des animaux, à proximité d'eux et dans leur environnement.
PCT/EP2002/002961 2001-03-28 2002-03-18 Corps moules renfermant des substances actives, a base de polyurethannes thermoplastiques, servant a lutter contre des parasites WO2002078443A1 (fr)

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DE2001115225 DE10115225A1 (de) 2001-03-28 2001-03-28 Wirkstoffhaltige Formkörper auf Basis thermoplastisch verarbeitbarer Polyurethane zur Bekämpfung von Parasiten

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Cited By (7)

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WO2003051112A1 (fr) * 2001-12-19 2003-06-26 Exosect Limited Dispositif de controle d'animaux nuisibles comportant un materiau biodegradable integrant un materiau pesticide
EP1701617A1 (fr) * 2004-01-09 2006-09-20 Fmc Corporation Compositions insecticides de lutte contre des parasites domestiques generaux
US7910122B2 (en) 2004-06-29 2011-03-22 Bayer Animal Health Gmbh Active compound-containing solid moulded bodies for external use against parasites on animals
AU2005231132B2 (en) * 2004-03-25 2011-06-09 Fmc Corporation Liquid termiticide compositions of pyrethroids and a neonicitinoids
JP2015096534A (ja) * 2003-01-17 2015-05-21 バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＢａｙｅｒ Ｉｎｔｅｌｌｅｃｔｕａｌ Ｐｒｏｐｅｒｔｙ ＧｍｂＨ 忌避剤
CN108271775A (zh) * 2018-03-23 2018-07-13 南京新安中绿生物科技有限公司 挥发性亲水化合物的控制释放系统及应用
WO2022211994A1 (fr) * 2021-04-01 2022-10-06 Covestro Llc Mélanges de polymères thermoplastiques

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DE102004026745B4 (de) 2004-05-28 2013-06-20 Justus-Liebig-Universität Giessen Verfahren und Vorrichtung zur Ausbringung von nanoskaligen Polymerfasern als Träger für landwirtschaftliche Wirkstoffe

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US4543247A (en) * 1980-10-22 1985-09-24 Bayer Aktiengesellschaft Ectoparasiticide-containing collars for pets
EP0470467A2 (fr) * 1990-08-10 1992-02-12 Bayer Ag Agent de lutte contre les puces
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DE2715596A1 (de) * 1977-04-07 1978-10-19 Bayer Ag Tierhalsbaender mit insektizider wirksamkeit
US4543247A (en) * 1980-10-22 1985-09-24 Bayer Aktiengesellschaft Ectoparasiticide-containing collars for pets
EP0470467A2 (fr) * 1990-08-10 1992-02-12 Bayer Ag Agent de lutte contre les puces
WO1998019532A2 (fr) * 1996-11-07 1998-05-14 Bayer Aktiengesellschaft Corps moules contenant un principe actif, a base de polymeres biodegradables pouvant subir des traitements thermoplastiques

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003051112A1 (fr) * 2001-12-19 2003-06-26 Exosect Limited Dispositif de controle d'animaux nuisibles comportant un materiau biodegradable integrant un materiau pesticide
JP2017125042A (ja) * 2003-01-17 2017-07-20 バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＢａｙｅｒ Ｉｎｔｅｌｌｅｃｔｕａｌ Ｐｒｏｐｅｒｔｙ ＧｍｂＨ 忌避剤
JP2015096534A (ja) * 2003-01-17 2015-05-21 バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＢａｙｅｒ Ｉｎｔｅｌｌｅｃｔｕａｌ Ｐｒｏｐｅｒｔｙ ＧｍｂＨ 忌避剤
US8092816B2 (en) 2004-01-09 2012-01-10 Fmc Corporation Insecticidal compositions for control of general household pests
EP1701617A4 (fr) * 2004-01-09 2009-05-13 Fmc Corp Compositions insecticides de lutte contre des parasites domestiques generaux
JP2007518737A (ja) * 2004-01-09 2007-07-12 エフ　エム　シー　コーポレーション 一般家庭害虫の駆除のための殺虫剤組成物
EP1701617A1 (fr) * 2004-01-09 2006-09-20 Fmc Corporation Compositions insecticides de lutte contre des parasites domestiques generaux
AU2005231132B2 (en) * 2004-03-25 2011-06-09 Fmc Corporation Liquid termiticide compositions of pyrethroids and a neonicitinoids
US8133499B2 (en) 2004-03-25 2012-03-13 Fmc Corporation Liquid termiticide compositions of pyrethroids and neonicitinoids
US9585395B2 (en) 2004-03-25 2017-03-07 Fmc Corporation Liquid termiticide compositions of pyrethroids and neonicitinoids
US7910122B2 (en) 2004-06-29 2011-03-22 Bayer Animal Health Gmbh Active compound-containing solid moulded bodies for external use against parasites on animals
CN108271775A (zh) * 2018-03-23 2018-07-13 南京新安中绿生物科技有限公司 挥发性亲水化合物的控制释放系统及应用
WO2022211994A1 (fr) * 2021-04-01 2022-10-06 Covestro Llc Mélanges de polymères thermoplastiques

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