MXPA99011969A - Formulations containing an insecticide - Google Patents

Abstract

The invention relates to polymer-based insecticidal formulations and to a method for the production and the use thereof for the control of insects indoors. The novel formulations are characterized in that they contain at least one type of insecticide which is incorporated into a suitable polymer. The formulations are capable of releasing the insecticide at a given temperature in a controlled manner, without changing their form and macroscopic appearance.

Description

Formulations containing insecticide Description of the invention: The invention relates to formulations containing insecticides, to a process for the preparation of these formulations and to their use to combat insects. Systems for combating insects based on heating devices are increasingly preferred. They are based on the principle of impregnating suitable materials such as cellulose or cotton, asbestos or ceramic cardboard with an insecticidal active substance. These impregnated support materials can then be cut into shaped bodies of a discretional type, preferably plates (hereinafter referred to as "vaporization plates"), which release the active substance at an elevated temperature. The insecticides are volatilized by the action of a heating device that generates a temperature of 105-190 ° C. The gel vaporizer is based on a similar principle and in it the insecticide is incorporated into a gel formulation. DE-OS 196 05 581 discloses insecticidal compositions based on polymers that release the active substance at elevated temperatures. As possible active substances, various pyrethroids are mentioned. Although these compositions meet many demands of practice, a need for improvement persists. In particular, it is desirable that the consumption of the formulations take longer, so that the consumer must change the shaped bodies of late into REF .: 32325 afternoon. For prolonged lifetimes of the compositions the materials - active substance and polymer - must also be able to withstand, however, the thermal loads associated therewith; besides, polymers must be able to absorb a greater quantity of active substance without them. ooze at room temperature undesirably. It has thus been the object of the invention to provide formulations containing insecticides with the characteristic of an emission of the active substance uniform and with a duration of effect as long as possible. Surprisingly, it has been found that formulations in which the insecticide is included in a polymer solve this task excellently if they contain inorganic additives and / or if the polymer is poly-4-methylpentene. The object of the invention is therefore formulations based on A. at least one pyrethroid insecticide that is shed at high temperature, and B. at least one polymer with a softening range between 100 and 300, preferably between 150 and 250, especially between 150 and 200 ° C, characterized in that they contain additive inorganic and / or because the polymer is poly-4-methylpentene. The softening range is checked in the amorphous thermoplastic polymers by the glass transition temperature and in the partially crystalline polymers by the melting temperature. In addition, other additives, such as stabilizers, colorants or aromatic substances, as well as customary inorganic or organic adjuvants can be incorporated into the mixtures. As pyrethroid active substances, the following are preferably used: 1) d / 1-cis / trans-chrysanthemate 3-allyl-2-methyl-cyclopent-2-en-4-one-l-yl (Allethrin / Pynamin®1), ) 3-allyl-2-methyl-cyclopent-2-en-4-one-l-yl d-cis / trans-chrysanthemate (Pynamin forte®), 3) 3-allyl-2-d-trans-chrysanthemate methyl-cyclopent-2-en-4-one-l-yl (Bioallethrin6 '), 4) (+) -IR- trans-2, 2-dimethyl-3- (2, 2-dichlorovinyl) -cyclopropanecarboxylate 2, 3, 5, 6-tetrafluorobenzyl (Transfluthrin, Bayothrin®), 5) (IR) -cis / trans-chrysanthemate of (S) -3-propargyl-2-methyl-cyclopent-2-en-4-one-l -ilo (Prallethrin / Etoc®), or mixtures of these active substances. Preferably, the active substances d-cis / trans-chrysanthemate 3-allyl-2-methyl-cyclopent-2-en-4-one-l-yl (Pynamin forte'-) and (+) -lR- are used trans-2, 2-dimethyl-3- (2, 2-dichlorovinyl) -cyclopropanecarboxylic acid 2,3,5,6-tetrafluorobenzyl ester (Transfluthrin). Amorphous and partially crystalline polymers and mixtures of both which can be processed thermoplastically are preferably used as polymer materials., that is to say as viscous melts and whose softening range is below the boiling point at normal pressure of the active substances to be incorporated. The polymers for the corresponding active substance are selected so that the active substance is at least partially mixed with the polymers. Suitable polymers are preferably: PVC (BLANDO), polystyrene, styrene / butadiene, styrene / acrylonitrile, acrylobutadiene / styrene, poly (methyl acrylate), amorphous polycycloolefins, cellulose esters, aromatic polycarbonates, amorphous aromatic polyamides, polyphenylene ethers, poly (ether) sulfones, polyimides, polyethylene, polypropylene, polybutylene, polymethylpentene, PVC (DURO), polyamide, polyetherramides, polyesteramides, polyoxymethylene, poly (ethylene terephthalate), poly (butylene terephthalate), polyimide, polyether (ether) ) ketone and polyurethanes. Preferred mixtures are, for example: Mixtures of polycarbonates with polybutylene terephthalate, mixtures of polyamide-6 and styrene / acrylonitrile, mixtures of polypropylene and polymethylpentene. Polypropylene, poly-4-methyl-1-pentene and their mixtures are especially preferred. A preferred object of the invention are formulations of mixtures containing A. 0.1 to 80, preferably 0.2 to 40, especially 0.5 to 20, in particular 1 to 12% by weight of transfluthrin. and B. 99.9 to 20, preferably 99.8 to 60, especially 99.5 to 80, in particular 99 to 88% by weight of poly-4-methyl-1-pentene, which in turn can be replaced up to in the middle, preferably up to one third, especially up to a quarter of its weight, by another poly-α-olefin, the percentage data being respectively referred to the sum of the components A + B. The transfluthrin and a process for its preparation they are known from DE-OS 37 05 224 (= EP-PS 279 325). Poly-4-methyl-1-pentene B is a polymer, preferably with a vitreous transition temperature of 50 to 60 ° C, a softening temperature, measured according to Vicat (ASTM D 1525) of 140 to 180, preferably 170 at 175 ° C and a melt index (260 ° C / 5 kg), measured according to ASTM D 1238, from 20 to 200, preferably from 22 to 35 [g / 10 min], which can be obtained in a known manner by polymerization of 4-methyl-1-pentene. As poly-α-olefins which can partially replace poly-4-methyl-1-pentene, polyethylenes, polypropylenes, polybutenes and polyisobutenes, as well as copolymers of the o-olefins on which the aforementioned polymers are based, are considered, for example ethylene / propylene copolymers. Preferred polypropylenes include iso- and / or syndiotactic polypropylenes, preferably with a softening temperature, measured according to 'Vicat (ISO 306), from 130 to 170, preferably from 140 to 160 ° C and a melt index (230 ° C / 2 kg), measured according to ISO 1133, from 20 to 40, preferably from 25 to 35 [g / 10 min]. In the case where "other" poly-α-olefins are used, the weight ratio poly-4-methyl-1-pentene / poly-α-olefins can reach from 70:30 to 99: 1, preferably from 80:20 to 95: 5. The formulations according to the invention may contain, in addition to the components A and B, other organic or inorganic additives, such as p. fillers, colorants, stabilizers, aromatic substances. The formulations according to the invention can be stabilized with the aid of antioxidants when a UV absorber is added to the mixture as a formulation additive. All known UV absorbers can be used as UV absorbers. Preference is given to using phenolic derivatives, such as, for example, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), bisphenol derivatives, arylamines, such as, for example, phenyl-a-naphthylamine, phenyl-β-naphthylamine, a condensate of phenethidine and acetone. or similar or benzophenones. Dyes can be used, such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyanic blue and dyes, such as, for example, alizarin, azo and metalophthalocyanine dyes. Synthetic aromatic substances can be added to the formulations according to the invention: pinene, limonene and similar hydrocarbons; 3,3,5-trimethylcyclohexanol, linalool, geraniol, nerol, citronellol, menthol, borneol, borneylmethoxy-cyclohexanol, benzyl alcohol, anisic alcohol, cinnamic alcohol, β-phenylethyl alcohol, cis-3-hexanol, terpineol and similar alcohols; anethole, xylene musk, isoeugenol, methyleugenol and similar phenols; a-amylcinnamaldehyde, anisaldehyde, n-butyraldehyde, cumin aldehyde, cyclamenaldehyde, decyl aldehyde, isobutyraldehyde, hexylaldehyde, heptylaldehyde, n-nonylaldehyde, nonadienol, citral, citronellal, hydroxycitronellal, benzaldehyde, methyl onylacetaldehyde, cinnamic aldehyde, dodecanol, a-hexylcinnamaldehyde, undecanal , heliotropin, vanillin, ethylvanillin and similar aldehydes, methylacetone, methyl-ß-naphthyl ketone, methylnonyl ketone, ketone musk, diacetyl, acetylpropionyl, acetylbutyryl, carvone, methane, camphor, acetophenone, p-methylacetophenone, yonone, metilyonone and similar ketones; amyl-butyrylactone, diphenyloxide, methylphenylglycidate, nonyl ketone, coumarin, cineole, ethylmethylphenylglycidate and lactones or similar oxides, methyl formate, isopropyl formate, linalyl formate, ethyl acetate, octyl acetate, methyl acetate, benzyl acetate, cinnamyl acetate, butyl propionate, isoamyl acetate, isopropyl isobutyrate, geranyl isovalerate, allyl caprynanate, butyl heptylate, octyl caprylate, methylheptin carboxylate, methyloctin carboxylate, isoamyl caprylate, methyl laurate, ethyl myristate, methyl myristate, ethyl benzoate, benzyl benzoate, methylcarbinyl phenylacetate, isobutyl phenylacetate, methyl cinnamate, styrazine, methyl salicylate, ethyl anisate, methyl anthranilate, ethyl pyruvate, a-butylbutyrate ethyl, benzyl propionate, butyl acetate, butyl butyrate, p-tert-butylcyclohexyl acetate, cetyl acetate, citronellyl acetate, citronellyl formate, p-cresyl acetate, ethyl butyrate, ethyl caproate, cinnamate ethyl, ethyl phenylacetate, ethylene brasilate, geranyl acetate, geranyl formate, isoamyl salicylate, isoamyl valerate, isobornyl acetate, linalyl acetate, anthranilate lime, methyl dihydrojazmonate, nonyl acetate, β-phenylethyl acetate, trichloromethylenephenylcarbinyl acetate, terpinyl acetate, vetyveryl acetate and similar esters. The formulations generally contain between 0.1 and 80, preferably between 0.2 and 40, particularly preferably between 1.0 and 20% by weight of active substance. As additives, modifiers and / or fillers and reinforcing agents and / or processing aids such as, for example, coadjuvants, plasticizers, demolding agents, flame retardants, impact resistance modifiers, stabilizers, or other additives customary in the art can be used. the thermoplastics. Preferably, fillers such as those described in the "Encyclopedia of Polymer Science and Engineering", vol. 7, pgs. 53-73 (1985). Minerals may be used as fillers and reinforcing agents, such as gypsum, lime, glass fibers or sand, preferably glass fibers. The amount of the additives can vary within wide limits; In general, it ranges from 1 to 80, preferably from 0.2 to 50 and especially from 0.5 to 30% by weight, based on the formulation according to the invention. The formulations according to. invention can be prepared by introducing the polymer B as a granulate or powder in a suitable kneader or "extruder where it is plasticized." Under the conditions and typical plasticizing temperatures for the polymer the active substance A can be incorporated into the molten polymer mass directly by a dosing device and The plasticization of the polymer can be carried out in mixers (Banbury, Werner &Pfleiderer) including special kneaders as well as in cutting roller extruders and in single or double shaft extruders.The cutting roller extruders are mainly used for production by loads, while with the single or double shaft extruders or the Buss-KO mixers the incorporation of the active substance is carried out continuously.Extruders or mixers suitable for the incorporation of the active substance are based on the principle of friction, the heat of friction occurs in the advance and retreat of the trees. The trees can be differentiated in the depth of passage, in the width of step, in the angle of inclination in the sense of rotation, according to each polymer mixture / active substance. The quality of the homogenization can be regulated by the kneading time and the length / diameter ratio of the extruder shafts. In order to obtain homogenous products for the thermoplastic processing to molding compositions, a dosage is recommended in the following manner: the addition of the polymer is preferably carried out in the form of granules or powders. The active substance can be added solid or liquid (as melt or solution) 'according to the required accuracy with the aid of volumetric or gravimetric dosing devices. Volumetric dosing devices include screw, cell wheel, rotary plate or vibrating gutter dozers. The gravimetric dosing devices are, for example, belt dosing scales or differential dosing scales. For good-flow polymer granules (particle size> 50 μm), vibrating gutters, helical or sheet screws and conveyor belts are advantageously used. Active substances with powder sizes between 10 and 50 μm can be treated as a liquid and dosed preferably with "chamber systems" such as cell wheel gates or double screws. The active substance can be added in the loading zone of the extruder or later downstream in one or several steps. The dosage is preferably carried out in the polymer melt, to avoid the formation of secondary agglomerates. The liquid active substances can be added, eg, to the premix (heating / cooling mixer). The waxy active substances can be first melted between 60 and 80 ° C and stored in a thermally conditioned supply vessel before being fed to the extruder. The liquid active substances can be dosed with gear pumps, helical screw pumps or single or multiple alternative pumps. The extruder is preferably fed in a place where the melt is under pressure. The pressure of the melt must be above the vapor pressure of the active substance at the respective temperature of the melt, since if steam and foam are not formed. At the injection site, the pressure must fall in the direction of the tip of the screw, that is, the pressure gradient must be negative so that the active substance fed is not "pressed" upstream. With larger amounts of active substance and large differences in viscosity between the polymer and the liquid active substance, it is advantageous to inject the liquid in several places at the same time. With thermally sensitive active substances it can be achieved in this way that the distribution of the active substance in the melt is faster. It is important that the liquid active substance is included as directly as possible in the melt and is not injected only at the edge of the inner wall of the cylinder. Film formation with low viscosity liquids in the cylinder wall can be avoided by decreasing the dosage; otherwise the transport can be impaired and in single screw extruders even be prevented. In this case injection valves that penetrate the screw channel can be used. At the site of injection the drain-off of the screw is 'then' interrupted. It absolutely must be avoided that when the dosing pump stops, penetrate the polymer melt in the injection valve and in the supply line, solidify there and block the liquid supply when the dosing pump is started again. To avoid this effect, special spring-loaded check valves can be used, in which the blockage of the return flow is directly in the discharge orifice.

The same applies to liquid active substances as for solid substances in the mixing process. But since the dosed liquids are, in the majority of cases, clearly less viscous than the polymer melt, in the case of homogenization, the problem of their disintegration arises. Essentially they only need to divide. For this, mixing rings are suitable, since they produce a distribution and extension with multiple exchange of the individual layers. Equal blends can also be achieved by installing static mixing elements installed between the transport screw and the mold. The dosage of solid or liquid active substances can also be carried out in the form of concentrates of active substance. Concentrates are intermediate products containing the active substance at a high concentration in support substances. The supporting substance for this may be polymer B or a material not miscible with polymer B (polymer, load). For its final use, it is re-diluted by mixing with another polymer granulate at the desired lower concentration. The highly concentrated active substance in such a form is intended to be a concentrate of active substance that is dosed well for different adjustable concentrations. Most of the time these "masterbatches" are presented in the form of granules.

Polymers containing active substance can be granulated in various ways. Either the extruded and fully or partially cooled bead is cut (bead granulation) or the melt is cut directly at the outlet of the nozzle before the head (eg granulation of the hydraulic ring) ). The granules containing active substance produced can be processed thermoplastically into castings or processed with another polymer to form mixtures ("masterbatch"). For the shaping, the usual procedures used for plastics can be used, such as, for example, injection-molded processing, vesicular extrusion, sheet extrusion or deep-drawing. Another method of the invention is a process for the preparation of the formulations according to the invention by mixing the components and forms of the mixture obtained. The formulations according to the invention can be used in the form of vaporization inserts in conventional vaporizing apparatuses, such as those used for the cellulose vaporization inserts. Working temperatures of 60 to 180, preferably 130 to 170 ° C, guarantee an emission to the environment of the active substance that is maintained for a long time and relatively uniform. Another object of the invention is the use of the formulations according to the invention for combating insects, such as, for example, flies and mosquitoes. The percentage data of the following Examples are referenced by weight.

E ploses Starting materials used 1. Poly-4-methyl-1-pentene from Mitsui (polymethylpentene TPX RT 18) 2. Polypropylene (Hostalen PPV 2080, PPV 2700 L, PPV 2780 L from Hoechst AG) 3. Titanium dioxide (Bayer Titan RFK-2 from Bayer AG) Example 1 Inclusion of active substances in different polymers The inclusion was made in a volumetric extruder (type of extruder 35/17 D, cooling of extruder: air, cooling input: water, 3 mm round cord nozzle, four electrically heated zones). The polymer granulate is dosed to the extruder at the corresponding temperature by means of a scale. The active substance was heated in a supply vessel heated with steam and fed by pumping with a gear pump. The step was adjusted to a total of 6 kg / h. The polymer cord that came out was cooled in a water bath and then crumbled in the granulator. The granulate was dried at approx. 50 ° C to empty water pump.

* TPXRT 18 Polymethylpentene ** PP Hostalen PPV 2080 No. 1. 9 Hostalen PPV 2700 L • E i empl o 2 Comparison with and without additives The heavy test samples were placed in the center of the planned heater and, after switching on the heating device, they were weighed accurately every 2 h. The tests were carried out until reaching the predetermined use time of 10 h Heating apparatus: Baygon Mückenfrei Heizgerát, German standard, "with fixed Resistance, 155 ° C Test sample: 34 x 22 x 2,5 mm Cycle: 2- 10 h The comparison polymethylpentene with and without addition of 20% glass fibers shows the clear increase of the vaporized amount. Example 3 Comparison with different sizing The heavy test samples were placed in the center of the intended heater and after switching on the heating device they were weighed accurately every 2 h. The tests were carried out until reaching the predetermined use time of 10 h. • Heating device: Baygon Mückenfrei Heizgerat, German standard, with fixed resistance, 155 ° C (Examples 3.1 and 3.2) Baygon Eletrico Heizer Brasilien with PTC resistance (Examples 3.3 and 3.4) Active substance: Transfluthrin (1, 3%) Cycle: 2 -10 h The addition of 20% glass fiber also led in this Example to an improvement in the behavior of vaporization. This effect is in the Brazilian format of 40 mm x 18 mm x 2.5 mm more intensely marked than in the format of 34 mm x 22 mm x 2.5 mm Example 4 Comparison with different contents of active substance The heavy test samples were placed in the center of the planned heater and after switching on the heating device they were weighed accurately every 2 h. The tests were carried out until reaching the predetermined use time of 10 h. Heating device: Baygon Mückenfrei Heizgerát, German standard, with fixed resistance, 155 ° C. Test sample: 34 x 22 x 2.5 mm Cycle: 2-10 h The increase in the concentration of active substance leads to higher emission rates and this brings with it lower residual contents. Example 5 Additives in polypropylene (version 10Q ° C) The heavy test samples were placed in the center of the planned heater and after switching on the heating device they were weighed accurately every 10 h. The tests were carried out until reaching the predetermined use time of 70-80 h. Temperature: 115 ° C DBK heating device type GD with PTC Test sample: 6.25 cm2 Cycle: 1 x 10 h / day Duration: 7 days Example 6 Fabrication of the vaporization plates The forming is done by injection molding on an Arburg machine 320 - 210 - 850, with a single shaft screw with a diameter of 35 mm, a screw filling of approx. 125 g (which "corresponds to five injections) with a reverse temperature profile of 250 ° C (nozzle) 265oC / 270 ° C / 280 ° C and a cycle time of 15 seconds.The mold temperature reaches 30 ° C, is used a cold channel mold, with 12 openings, with injection through the casting tunnel, as a previous run, ten injections of 25 g are taken, the product is dried for 15 h at 50 ° C.

Example Components Content [%] Vaporization plates for multi-day use 6.1 Polymethylpentene 92, 9 Transfluthrin 6, 6 Butylhydroxytoe 0.5 6.2 Polymethylpentene 91.2 Transfluthrin 8.3 Butylhydroxytoe 0.5 Vaporization plates for overnight use 6.3 Polymethylene 83.0 Polypropylene 14, 6 Transfluthrin 1,32 Titanium dioxide 1,0 Butylated hydroxytoe 0,06 Sudan Blau 670 0,01 0,06 Polymethylpentene 97,9 Transfluthrin 2,0 Butylhydroxytoe 0,1 Example 7 Emission of the active substance of the formulations according to the invention The emission of the active substance was determined gravimetrically. The heavy test samples were placed in the center of the cold heating apparatus (standard FALP heating device for Baygon vaporization inserts) and after the respective cycles were accurately weighed. The tests were prolonged the necessary time until the samples no longer showed weight loss. Dimension of the test sample: 34 mm x 23 mm x 2.5 mm Cycle duration: 8 h / day Example 7.1 Emission rates of the formulation of Example 6.1 over 7 cycles Example 7.2 Emission rates of the formulation of Example 6.2 over 7 cycles Example 7.3 Cumulative emission rates of the formulation of Example 6.3 over a 10-h cycle: Example 7.4 Cumulative emission rates of the formulation of Example 6.4 over a 10 h cycle: Example 8 Testing of long-lasting vaporization inserts and vaporizers with regard to the insecticidal effect against flying insects in rooms of 34 m3 MATERIAL AND METHOD The tests were carried out in rooms with the following dimensions 4.49m High: 2.66 Door Width 2.85 P Puuerta Vaporizador 1 m I 1 m Dimensions of the room: 12.8 m = 34 pv In the rooms that remain empty, the corresponding system is placed in the center on the floor. In the plug versions the systems are fixed on a tripod at a height of 30 cm. Tethers are strapped to one meter from the short sides at a height of 2 m from which wire baskets are hung with test animals. The doors close. The temperature is regulated by the heating body.

In the morning the corresponding vaporizer system is put into service and at the same time 2 wire baskets with 20 test animals (3-4 years old) are hung in the room. Hourly, until 8 hours later, other animals are hung in the room and the effect of "knock down" ("Kd") is evaluated at a rate of 15 minutes. The effect of 50% and 100% of "knock down" is determined as well as the mortality after 24 hours. The system heats up to 8 hours and then disconnects. In long-time vaporizers it is regulated by a timer so that the system works daily for 8 hours. Test animals: Mosquitoes: Aedes aegypti mw, sensitive Culex quinquefasciatus mw, resistant to DDT Example 8.1 Insecticidal effect of vaporization plates of Example 6.1 and 6.2 against susceptible mosquitoes of Aedes aeeyptv species in rooms of 34 m3 Ambient temperature: 21-27 ° C Relative air humidity: 26-38% Kd / Mortality after heating apparatus start-up Example 8.2 Insecticidal effect of vaporization plates of Example 6.1 and 6.2 against resistant mosquitoes of the Culex quinquefasciatus species in rooms of 34 m3 "Kd / Mortahda upon start-up of the heating apparatus Example 8.3 Insecticidal insecticidality of inserts of Example 6.3 against susceptible mosquitoes of the species Aßdes aeg? Pty in rooms of 34 m3 Temperature: 22-25 ° C Relative air humidity: 15-31 % (Average values of 3 trials) * 9 hours after starting the heating appliance ** 24 hours after starting the heating apparatus Example 8.4 Insecticidal activity of vaporization plates of Example 6.3 against resistant mosquitoes of the species Cule_c quinqué fasciat s in rooms of 34 m3 Temperature: 22 -25 ° C Relative air humidity: 15-31% (Average values of 3 tests) * 9 hours after start-up of the heating appliance ** 24- -hours after start-up of the heating appliance Example 8.5 Insecticidal activity of vaporisation inserts of Example 6.4 against susceptible mosquitoes of the species Aédes aegypty in rooms of 34 m3 Temperature: 22 -26 ° C Relative air humidity: 34-45% (Average values of 2 tests) Example 8.6 Insecticidal insecticide activity of Example 6.4 against resistant mosquitoes of the species Culex quinquefasciatus in rooms of 34 m3 Temperature: 22-26 ° C Relative air humidity: 34-45% (Average values of 2 tests) It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (9)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. Formulations based on A. at least one pyrethroid insecticide that is shed at high temperature, and B. at least one polymer with a softening point between 100 and 300 ° C, characterized in that they contain inorganic additive and / or because the polymer is poly -4-methylpentene.

2. Formulations according to claim 1, characterized in that as insecticidal active substance they contain d / 1-cis / trans-chrysanthemate 3-allyl-2-methyl-cyclopent-2-en-4-one-l-yl (Allethrin / Pynamin ' "), 3-allyl-2-methyl-cyclopent-2-en-4-one-l-yl d-cis / trans-chrysanthemate (Pynamin forte '"), 3-allyl-2-d-trans-chrysanthemate -methyl-cyclopent-2-en-4-one-1-yl (Bioallethrin6 '), (+) -lR-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylate of 2, 3 , 5,6-tetrafluorobenzyl (Transfluthrin, Bayothrin'-), or mixtures of these active substances.

3. Formulations according to claim 1, characterized in that they contain as an insecticide (+) -lR-trans-2,2-dimethyl-3- (2, 2-dichlorovinyl) -cyclopropanecarboxylate of 2, 3, 5, β-tetrafluorobenzyl (Transfluthrin, Bayothrin®).

4. Formulations according to claim 1, characterized in that as polymer they contain PVC (BLANDO), polystyrene, styrene / butadiene copolymer, styrene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer, poly (methyl acrylate), amorphous polycycloolefins, esters of cellulose, aromatic polycarbonates, amorphous aromatic polyamides, polyphenylene ethers, poly (ether) sulfones, polyimides, polyethylene, polypropylene, polybutylene, polymethylpentene, PVC (DURO), polyamide, polyetherramides, polyesteramides-, polyoxymethylene, poly (ethylene terephthalate), poly (butylene terephthalate), polyimide, polyether (ether) ketone and polyurethanes, mixtures of polycarbonates with poly (butylene terephthalate), mixtures of polyamide-6 and styrene / acrylonitrile copolymer, mixtures of polypropylene and polymethylpentene or mixtures of these polymers .

5. Formulations according to claim 1, characterized in that they contain polymethylpentene as a polymer.

6. Insecticidal compositions according to claim 1, characterized in that as inorganic additives they contain minerals such as, for example, gypsum, lime, glass fibers or sand.

7. Formulations according to claim 1 'characterized in that they include mixtures containing A. 0.1 to 80% by weight of transfluthrin and B. 99.9 to 20% by weight of poly-4-methyl-1-pentene, which at its it may be replaced up to half its weight by another poly-olefin, the percentage data being respectively referred to the sum of the A + B components.

8. Process for the preparation of formulations according to claims 1 to 7 by mixing the components and forms of the mixture obtained.

9. The use of formulations according to claims 1 to 7 to combat insects.