COMBINATION OF ENCAPSULED PHENOTHRIN AND EMULSIFIED PRALLETHRIN

Description

Technical area

[0001] The present invention relates to a novel water-based formulation comprising two active ingredients, namely phenothrin and prallethrin. State of the art

[0002] Products currently on the market are in the form of an emulsion in water, or they are in the form of an emulsifiable concentrate intended for use in aerosols, or as a ready-to-use solution of the active ingredients.

[0003] The following product combinations are available: d-trans-tetramethrin 0.25% / d-phenothrin 0.125%; d-trans-tetramethrin 0.20% / d-phenothrin 0.1% / PBO 0.90%; d-trans-tetramethrin 0.33% / d-phenothrin 0.13%).

[0004] All these products have weaknesses, such as: Low residual effect; high toxicity; high human exposure; higher concentration of active ingredients; complete availability of the product upon application, leading to overdose; no influence on the biodegradability of the active ingredients; high concentration of aromatic / aliphatic solvents; no UV protection; sensitivity to organic substances in the environment; discoloring and not odorless. Phenothrin

[0005] (3-Phenoxyphenyl)-methyl-(1R)-cis-trans-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropanecarboxylate) belongs to type 1 synthetic pyrethroids of the first generation.

[0006] The structure is as follows:

[0007] It acts on the membrane of nerve cells upon contact or absorption, blocking the closing of the ion gates of the sodium channels during repolarization. This interrupts the transmission of nerve impulses. At low concentrations, the insect suffers from hyperactivity, while at high concentrations it becomes paralyzed and dies.

[0008] Phenothrin, first registered by the United States Environmental Protection Agency (EPA) in 1976, is available as a ready-to-use (RTU) indoor spray and carpet powder, as a pressurized concentrate, an emulsifiable concentrate, and formulated for use as a spot-on or stripe-on flea and tick treatment for pets. Formulations for pets often contain other active ingredients in addition to phenothrin. Phenothrin is also formulated for use with ultra-low volume (ULV) sprayers and indoor foggers. It is unstable to sunlight, which reduces residual efficacy and thus shortens the duration of protection. Prallethrin

[0009] (2-Methyl-4-oxo-3-prop-2-yn-1-yl-cyclopent-2-en-1-yl-2,2-dimethyl-3-(2-methylprop-1-en-1-yl)-cyclopropanecarboxylate) belongs to the type 2 pyrethroids. It is a pyrethroid that exhibits the property of rapid immediate action (knockdown effect) on household insect pests. Its structure is as follows:

[0010] The main types of formulations available are evaporator pads ("gelsenstecker") and liquid atomizers.

[0011] There are products on the brand that contain phenothrin and prallethrin. However, these do not state any residual effect, which inevitably implies that they have no residual effect, as residual effect is highly desirable. Below is a list of products containing phenothrin and prallethrin, researched in the EPA database: DUET ™< Dual-action (EPA Reg. No.: 1021-1795-8329) Raid Flying insect (EPA Reg. No. 4822-569) Raid Multi insect (EPA Reg. No. 4822-569) None of these products have any residual effect.

[0012] US 2015237861 A discloses a formulation containing tetramethrin, d-phenothrin, and piperonyl butoxide (see Table 2). However, this formulation showed insufficient residual efficacy just seven days after application, as shown in Table 4 of this document. Example 2C of this document describes a formulation containing tetramethrin and d-phenothrin, which also showed a significant decrease in efficacy within three months.

[0013] A method for producing microcapsules is described in US 8216598 by GAT Microencapsulation AG. The microcapsules can be produced by emulsion polymerization in situ, producing glycoluril polyurea microcapsules. Description of the invention

[0014] The object of the invention is to find a formulation to ensure that the two active ingredients phenothrin and prallethrin have an optimal effect.

[0015] According to the invention, the new formulation is a suspension of encapsulated phenothrin and an emulsion of prallethrin.

[0016] The formulation according to the invention can therefore be understood as an application of the above-mentioned patent in US 8216598 B to obtain a more environmentally friendly product which has better efficacy, a prolonged residual effect and an improved toxicological profile.

[0017] In this formulation, the release of phenothrin occurs in a controlled manner, so that a high consistency of effect is ensured in the control of various crawling and flying insect pests, e.g. black ants, fire ants, termites, silverfish, bedbugs, German cockroaches, American cockroaches, common houseflies, spiders, midges, gnats, mosquitoes.

[0018] Currently, there is no insect control product that combines two active ingredients, namely microencapsulated phenothrin with long residual action and emulsified prallethrin in water with immediate action, in a ZW formulation. (ZW is a mixed formulation of CS (capsule suspension) and EW (emulsion, oil in water).) The most similar products marketed to date are registered by the EPA and consist of phenothrin in free (non-microencapsulated) form and prallethrin in the form of an emulsion, but also contain PBO as an additional component. Therefore, the product according to the invention has a significant advantage: surprisingly, the product according to the invention has a residual effect of at least eight weeks, and even up to twelve weeks, which cannot be deduced from the prior art. Studies have shown that the product according to the invention causes complete mortality even after three months, tested in Musca domesticaand Blattella germanica.

[0019] The ratio (mass ratio) of phenothrin to prallethrin is preferably between 5:1 and 20:1 and in particular 10:1.

[0020] It is particularly preferred that the phenothrin be microencapsulated, with the specific particle size preferably being between 1.8 µm and 3.3 µm. The particle size is determined as a volume-weighted average by laser diffraction.

[0021] It was found that this combination has a duration of action of at least eight weeks, especially when the ratio is close to the optimal phenothrin to prallethrin ratio of 10:1. Often, the lethal effect is fully maintained for at least twelve weeks and only diminishes after sixteen weeks. Nevertheless, toxicity to humans and other warm-blooded animals is low, to which microencapsulation makes a significant contribution. Inhalation toxicity is also low due to microencapsulation.

[0022] By co-formulating with UV stabilizers, UV stability can also be ensured, ensuring long-lasting effectiveness even on sun-exposed areas. A suitable UV stabilizer is Escalo 551.

[0023] Microencapsulation allows for optimal timing of release, allowing for smaller amounts of active ingredients compared to conventional products.

[0024] Accordingly, a concentrate can contain approximately 10% phenothrin and approximately 1% prallethrin by mass. This concentrate is diluted 1:99 with water to obtain the ready-to-use product. This final product then contains approximately 0.1% phenothrin and 0.01% prallethrin by mass. This final product is ideally suited as an insecticide. As demonstrated below, the optimal application rates are approximately 25 ml / m² on non-porous surfaces and approximately 50 ml / m² on porous surfaces. The phrase "use as an insecticide" in this document is intended to exclude therapeutic applications.

[0025] The release rate is influenced by the size of the microcapsules, the proportion of monomers, pre-polymers and 3D crosslinkers, as well as by the wall thickness and wall permeability.

[0026] The storage stability is high, so that only minimal degradation of the active ingredient occurs during storage.

[0027] The active ingredients were made compatible through their release rates, which were selected with regard to their efficacy profiles to achieve a balance between efficacy, toxicity, and stability. This product allows two effects to be achieved with a single application: a rapid knockdown effect (paralysis of the insects) and a safe killing effect.

[0028] The present invention specifically addresses the efficacy of the two active ingredients and improves their inherent properties by microencapsulation and emulsification in water to enhance the immediate effect (knock-down effect) and the residual effect (delayed release). The thoroughly tested formulation contains 0.1% phenothrin and 0.01% prallethrin. This formulation is referred to as the "final product."

[0029] Prallethrin in combination with phenothrin offers superior performance in controlling household insects. Table 1 Phenothrin strengths: Prallethrin strengths: Superior efficacy profile Excellent immediate effect Non-corrosive Effective at very low levels Biodegradable Biodegradable Variety of applications Variety of applications Favorable toxicity Favorable toxicity

[0030] There are currently 198 active approvals for phenothrin products in the United States.

[0031] The concentration of phenothrin in products marketed in the US and Canada ranges from 0.096% for pet grooming sprays to 1.3% for pump-on flea control sprays. The estimated duration of effectiveness is less than two months.

[0032] The main available formulations are either oil-based or water-based aerosols. Both formulation types are often combined with synergists. In this regard, many household products containing phenothrin are sold in aerosol spray cans containing inert propellants such as propane or isobutane, which are highly flammable.

[0033] Products are available as ready-to-use indoor sprays or carpet powders, as pressurized or emulsifiable concentrates. Another form of application is flea and tick treatment with spot-on or stripe-on sprays in combination with other active ingredients. Finally, phenothrin-based products can be used with ULV sprayers and indoor fogging devices.

[0034] The application of residual insecticides to surfaces remains one of the most cost-effective and versatile methods for controlling insect pests in urban and residential areas. The surfaces to which insecticides are applied vary widely, but are usually porous. This can negatively impact the bioavailability of the insecticides. Other surfaces may also be chemically reactive and denature the active ingredient, impairing the persistence of the effect. Furthermore, insecticides applied to outdoor surfaces are subject to other adverse conditions, primarily photodegradation, which significantly reduces the persistence of the effect.

[0035] In the field of insect control, the final product is a novel combination of slow to medium release characteristics, with the release rate remaining constant until the active ingredient of the capsule is exhausted.

[0036] Once the phenothrin-containing microcapsules come into contact with an insect, the active ingredient rapidly diffuses into the insect's lipophilic cuticle. Due to this fact, the behavior and biological properties of phenothrin can be altered by microencapsulation.

[0037] The microencapsulated formulation protects the phenothrin to reduce potential degradation by sunlight. It is released periodically, resulting in a sustained-release formulation. This ensures better efficacy because the active ingredient is available at a constant and prolonged release rate.

[0038] The final product is thus a sophisticated, dual-action household insecticide. It combines the proven efficacy of microencapsulated phenothrin with the exceptionally immediate action of prallethrin. Therefore, the final product begins to work immediately.

[0039] Together, the active ingredients provide a superior control mechanism because the best effect of each active ingredient is utilized to create an insecticide that achieves unique results, increasing both insect control effectiveness and user safety.

[0040] In summary, the final product was formulated using the microencapsulation technique to create a product specifically intended for urban and domestic use, with the following profile: Highly effective active ingredients; persistence on many surfaces, including highly porous and chemically reactive surfaces; rapid, immediate action (knockdown effect) and killing.

[0041] In addition, the final product offers several significant improvements in environmental and user safety resulting from microencapsulation.

[0042] The final product may also have the following features: Sustained antioxidant formulation, UV resistance due to microencapsulation; immediate and time-controlled release lasting at least eight weeks, which is scientifically proven; slow degradation, so it only needs to be applied infrequently to maintain the lethal dose. Best way of carrying out the invention Examples of formulations according to the invention

[0043] The following explains the composition of the microcapsules and emulsion required to produce the final product. They include the following components: Table 2 component CAS number function A 1R-trans-Phenothrin TG (typically 91.5% pure) 26046-85-5 Active ingredient B Prallethrin TG (typically 93% pure) 23031-36-9 Active ingredient C BrijO20 9004-98-2 Emulsifier D Break-Thru AF5503 see SDS Defoamers E Cycat 4040 67-63-0 catalyst F Propylene glycol 57-556 Frost protection G TMXDI 2778-41-8 Wall-forming material H ONGRONAT 2100 2778-41-8 Wall-forming material I CYMEL 1170 68036-98-6 Networker J Proxel GXL 2634-33-5 Preservative K Radia 7117 61788-59-8 solvent L Synperonic PE / F 127 9003-11-6 Emulsifier M Xanthan Gum 11138-66-2 Viscosity adjuster N Zephrym PD3315 see SDS Dispersant / Crystal Growth Inhibitor O Water 7732-18-5 solvent

[0044] In the following five examples, the following proportions in wt.% of components A to O were used: Table 3 1 2 3 4 5 A 10.644 (technical) 9.74 (pure) 10.644 (technical) 9.74 (pure) 10.644 (technical) 9.74 (pure) 10.644 (technical) 9.74 (pure) 10.644 (technical) 9.74 (pure) B 1.07 (technical) 0.9951 (pure) 1.07 (technical) 0.9951 (pure) 1.07 (technical) 0.9951 (pure) 1.07 (technical) 0.9951 (pure) 1.07 (technical) 0.9951 (pure) C 0,0187 0,0187 0,0187 0,0187 0,0187 D 0,015 0,015 0,015 0,015 0,015 E 0,15 0,15 0,18 0,25 0,25 F 5,00 8,00 7,50 9,00 10,00 G 0,15 0,15 0,3 0,4 0,10 H 1,00 1,05 1,40 1,50 0,80 I 0,10 0,10 0,25 0,30 0,18 J 0,10 0,10 0,10 0,10 0,10 K 4,80 4,50 5,0 6,00 8,00 L 0,50 0,75 0,84 0,92 0,84 M 0,40 0,40 0,35 0,30 0,30 N 3,0 3,35 3,0 3,35 2,80 O 73,0523 69,7023 69,3323 66,1323 64,8823 Example 1 Preparation of the capsule suspension (CS)

[0045] For 5 kg of final product, 1670 g of CS are required. All values ​​are in wt.%. Table 4 Oil phase % by weight Water phase % by weight 1R-trans phenothrin 31,932 Synperonic PE / F 127 1,5 TMXDI 0,450 BrijO20 0,056 ONGRONAT 2100 3,000 Zephrym PD3315 3,0 Cymel 1170 0,300 Water 44,912 Radia 7117 14,400 Cycat 4040 0,45

[0046] Keep the water phase and the oil phase at 40°C in a 2-liter jacketed reactor before the emulsion process.

[0047] The water phase is added to a 2-liter jacketed reactor equipped with a Cawless mixer and a high-shear mixer at 40°C. While the Cawless mixer is running at 1600 rpm, the oil phase is added very quickly (~ 1 minute) to the water phase, initiating the emulsion polymerization process.

[0048] Once the entire oil phase is completely emulsified, the high-shear mixer is switched on at 4600 rpm. Emulsion polymerization is complete after 4 minutes.

[0049] The capsule suspension is then transferred at 60°C to the other jacketed reactor, which is only equipped with an anchor stirrer at 36 rpm.

[0050] The capsule suspension is kept at 60°C for 3 hours while stirring until the capsules are hardened and stable. Preparation of the water emulsion (EW)

[0051] For 5 kg of final product, 3330 g of protein are required. All values ​​are in wt.%. Table 5 Propylene glycol 7,5 Zephrym PD3315 3,0 Xanthan Gum 0,6 Break-Thru AF5503 0,0225 Proxel GXL 0,15 Water 87,1175 Prallethrin TG 1,61

[0052] All components of the EW formulation except xanthan gum and prallethrin are added to a 5-liter jacketed reactor equipped with a high-shear mixer.

[0053] The components are mixed with the high-shear mixer at 1200 rpm and the solution is heated to 40°C.

[0054] After the temperature has reached 40°C, xanthan gum is added at 4600 rpm until a completely transparent gel is formed.

[0055] Finally, technical prallethrin, heated to 40°C, is added while stirring at 4600 rpm for 4 minutes, obtaining a homogeneous stable emulsion in water (EW). Preparation of the final suspension of capsules mixed with the EW to form a ZW formulation:

[0056] In a 6-liter jacketed reactor, 1670 g of capsule suspension is mixed with 3330 g EW using an anchor stirrer at 36 rpm for at least 4 hours until the suspension reaches equilibrium and is stable.

[0057] The particle size of the ZW formulation is measured using a laser diffraction device and the stability of the capsule dispersion in hard water of 342 ppm at the usage ratio of 1:99. Example 2 Preparation of the capsule suspension (CS)

[0058] For 5 kg of final product, 1670 g of CS are required. All values ​​are in wt.%. Table 6 Oil phase % by weight Water phase % by weight 1R-trans phenothrin 31,932 Synperonic PE / F 127 2,25 TMXDI 0,450 BrijO20 0,056 ONGRONAT 2100 3,150 Zephrym PD3315 3,00 Cymel 1170 0,300 Water 44,912 Radia 7117 13,500 Cycat 4040 0,45

[0059] The production is carried out as in Example 1. Preparation of the water emulsion (EW)

[0060] For 5 kg of final product, 3330 g of protein are required. All values ​​are in wt.%. Table 7 Propylene glycol 12 Zephrym PD3315 3,52 Xanthan Gum 0,6 Break-Thru AF5503 0,0225 Proxel GXL 0,15 Water 82,0975 Prallethrin TG 1,61

[0061] The preparation of the water emulsion and the preparation of the final suspension are carried out as in Example 1. Example 3 Preparation of the capsule suspension (CS)

[0062] For 5 kg of final product, 1670 g of CS are required. All values ​​are in wt.%. Table 8 Oil phase % by weight Water phase % by weight 1R-trans phenothrin 31,932 Synperonic PE / F 127 2,52 TMXDI 0,900 BrijO20 0,056 ONGRONAT 2100 4,200 Zephrym PD3315 3,0 Cymel 1170 0,75 Water 41,102 Radia 7117 15,00 Cycat 4040 0,54

[0063] The production is carried out as in Example 1. Preparation of the water emulsion (EW)

[0064] For 5 kg of final product, 3330 g of protein are required. All values ​​are in wt.%. Table 9 Propylene glycol 11,25 Zephrym PD3315 3,00 Xanthan Gum 0,525 Break-Thru AF5503 0,0225 Proxel GXL 0,15 Water 83,442 Prallethrin TG 1,61

[0065] The preparation of the water emulsion and the preparation of the final suspension are carried out as in Example 1. Example 4 Preparation of the capsule suspension (CS)

[0066] For 5 kg of final product, 1670 g of CS are required. All values ​​are in wt.%. Table 10 Oil phase % by weight Water phase % by weight 1R-trans phenothrin 31,932 Synperonic PE / F 127 2,76 TMXDI 1,20 BrijO20 0,056 ONGRONAT 2100 4,50 Zephrym PD3315 3,0 Cymel 1170 0,90 Water 36,902 Radia 7117 18,00 Cycat 4040 0,75

[0067] The production is carried out as in Example 1. Preparation of the water emulsion (EW)

[0068] For 5 kg of final product, 3330 g of protein are required. All values ​​are in wt.%. Table 11 Propylene glycol 13,5 Zephrym PD3315 3,52 Xanthan Gum 0,45 Break-Thru AF5503 0,0225 Proxel GXL 0,15 Water 80,7475 Prallethrin TG 1,61

[0069] The preparation of the water emulsion and the preparation of the final suspension are carried out as in Example 1. Example 5 Preparation of the capsule suspension (CS)

[0070] For 5 kg of final product, 1670 g of CS are required. All values ​​are in wt.%. Table 12 Oil phase % by weight Water phase % by weight 1R-trans phenothrin 31,932 Synperonic PE / F 127 2,52 TMXDI 0,30 BrijO20 0,056 ONGRONAT 2100 2,40 Zephrym PD3315 3,000 Cymel 1170 0,54 Water 34,502 Radia 7117 24,00 Cycat 4040 0,75

[0071] The production is carried out as in Example 1. Preparation of the water emulsion (EW)

[0072] For 5 kg of final product, 3330 g of protein are required. All values ​​are in wt.%. Table 13 Propylene glycol 15,00 Zephrym PD3315 2,70 Xanthan Gum 0,45 Break-Thru AF5503 0,0225 Proxel GXL 0,15 Water 80,0675 Prallethrin TG 1,61

[0073] The preparation of the water emulsion and the preparation of the final suspension are carried out as in Example 1. Critical parameters for microcapsule selection

[0074] The selection of microcapsules for stability and efficacy studies is based on the desired properties for the final product.

[0075] The most important property is the release rate of the microcapsules, which is mainly controlled by: 1. Microcapsule size in µm 2. Degree of crosslinking (ratio of wall-forming material to crosslinker); 3. Wall thickness (ratio of polymer to encapsulated oil phase); 4. Mobility of the oil phase as a function of the solvent content.

[0076] Taking into account all four listed properties, the following data can be given for each example: Table 14 1 2 3 4 5 particle size medium / high medium / high low / medium low / medium medium / high Degree of networking high high medium medium low Wall thickness low low high high low Mobility of the oil phase medium medium medium medium / high high

[0077] A medium / high particle size means few particles per volume; a low / medium particle size means many particles per volume.

[0078] A high degree of cross-linking means a low release rate with a long residual effect; A medium degree of cross-linking means rapid release with medium residual efficacy; a low degree of cross-linking means rapid release with low residual efficacy.

[0079] A high wall thickness means a medium diffusion rate; a low wall thickness means a high diffusion rate.

[0080] It can be seen that in examples 1 and 2, the number of particles per volume is low; therefore, the surface area for drug delivery is too small, resulting in low efficacy. This example is therefore not suitable for further testing.

[0081] In Example 3, the number of particles per volume is high, resulting in a larger surface area for drug delivery, resulting in greater efficacy. Additionally, the particle size distribution is narrow, resulting in better dispersion stability. The extent of cross-linking results in a medium release profile with a high proportion of wall-forming material, resulting in moderate diffusion, providing sufficient residual efficacy. This example was selected for further testing.

[0082] Example 4 is similar to Example 3, but has a less narrow particle size distribution and higher mobility; this formulation is also acceptable, but not as ideal as that of Example 3.

[0083] In Example 5, the number of particles per volume is medium to high, providing a medium surface area for drug delivery, and a low residual effect due to an overly rapid release profile. Therefore, this example is not suitable for further testing.

[0084] Finally, Example 3 was selected for further testing (efficacy, toxicity). Efficacy studies on the final product ("no choice test")

[0085] The concentrate has been diluted at a ratio of 1:99 so that it can be used as a ready-to-use formulation.

[0086] To assess the residual effect of this final product in terms of knockdown and death, adult insects of different sexes were used.

[0087] After shaking the product well before use, 100 ml / m² was applied to carpet, concrete, and wood, while 50 ml / m² was applied to ceramic surfaces. The surfaces were stored under ambient conditions prior to use. The total treated surface area was 1 m² to be realistic. An untreated control (no product applied) was prepared in the same way for comparison purposes.

[0088] This was a test in which the insects were forced to remain on the respective surface ("no choice test"). The continuity of the effect was determined by repeating the same test after four and eight weeks of storage of the plates. The insects were observed for the following: Knock-down effect mortality

[0089] A complementary experiment was conducted in which the final product was sprayed directly onto the insects, measuring the immediate knockdown effect and mortality after 24 hours. In both cases, the result was 100%.

[0090] The sprayed areas showed a 100% knock-down effect on day 0 after 15 min after four weeks after 45 min after eight weeks after 60 min

[0091] Mortality was investigated on four different surfaces (concrete, wood, carpet, ceramic tiles) for the following insects: Musca domestica (housefly) Aedes aegypti (yellow fever mosquito) Culex pipiens (common mosquito) Anopheles gambiae (African malaria mosquito) Blattella germanica (German cockroach) Periplaneta americana (American cockroach) Lasius niger (black garden ant) ​​Ixodes ricinus (hard tick) Ctenocephalides felis (cat flea) Lepisma saccharina (silverfish) Cimex lectularius (bed bug) Tineola bisselliella (clothes moth) Dermatophagoides pteronyssinus (house dust mite) Tegenaria domestica (house spider) Pediculus humanus (head louse)

[0092] Mortality was 100% both on day 0 and after eight weeks.

[0093] It was thus shown that when spraying non-porous surfaces with 50 ml / m 2< and when spraying porous surfaces with 100 ml / m 2< a very good insecticidal effect with a rapid knockdown effect and complete destruction is given a residual effect which lasts for at least eight weeks after the treatment of various surfaces (ceramic tiles, carpets, wood and concrete). Efficacy studies on the final product (simulated application) - 8 weeks

[0094] Additional tests were conducted in which the insects were able to move freely, which corresponds to realistic conditions.

[0095] The test was conducted in four 15 m³ test chambers (6 m² floor area) with four replicates, in accordance with BSI 4172 Parts 1 and 2 (1993) for testing insecticides in portable pressurized cans. The test chambers were maintained at a temperature of 26°C±1°C and a relative humidity of 70%±5% throughout the test period.

[0096] The test chambers were made of washable material. The walls, ceiling, and floor were made of non-porous materials such as epoxy-coated steel and ceramic tiles.

[0097] To simulate what happens in rooms, some polystyrene blocks and cardboard boxes were placed in the test chamber to form hiding places (refuges), as well as water and food sources with: Water source (six 25 cm long water vials with cotton swabs) Food source (four spots on the ground, in the hiding places, two Petri dishes with dog biscuits)

[0098] The insects were able to reach water and food sources without coming into contact with the insecticide. They were able to hide in many places. Only half the area was treated, so the target organisms had the choice of whether or not to come into contact with the final product.

[0099] In each treatment and each replicate, insects were used as follows: 25 of each species, except for cellar spiders, which were difficult to find and of which only 5 were used, per replicate, including the corresponding untreated controls.

[0100] The comparative trials were conducted to verify the animals used in the tests and to detect unintended effects that could arise from handling or experimental conditions.

[0101] The insects were released two hours after treatment to allow enough time for the surfaces to dry.

[0102] The application was carried out using a professional GLORIA 81 sprayer with an anti-drip nozzle. The liquid was shaken vigorously between treatments.

[0103] The application dosage was 50 ml / m 2< and the treated area was half of the test chamber, e.g. 3 m 2< , i.e. 150 ml of the product was applied to each 3 m 2< area.

[0104] The routes to food and water sources were not addressed.

[0105] The following insects were tested: Musca domestica (housefly) Aedes aegypti (yellow fever mosquito) Culex pipiens (common mosquito) Anopheles gambiae (African malaria mosquito) Blattella germanica (German cockroach) Periplaneta americana (American cockroach) Lasius niger (black garden ant) ​​Solenopsis invicta (red fire ant) ​​Reticulitermes santonensis (yellow-legged ground termite) Lepisma saccharina (silverfish) Cimex lectularius (bed bug) Tegenaria domestica (house spider, cellar spider)

[0106] Mortality was 100% at both day 0 and eight weeks.

[0107] Under the conditions of this study (simulated application), the final product, applied at a rate of 50 ml / m², demonstrated complete eradication in less than one week, with 100% mortality. The residual effect remained constant over a period of eight weeks after treatment. Efficacy studies on the final product (simulated application) - 12 and 16 weeks

[0108] Additional studies were conducted to evaluate the efficacy and residual effect of the final product used to control various insect pests.

[0109] The experiment was conducted in the laboratory in a test chamber with materials simulating actual usage conditions (cardboard = hiding place / refuge + food / water source), and only half of the area was treated with the product, so that the target organisms had the choice of whether or not to come into contact with the product.

[0110] Efficacy was quantified by a percentage of population reduction after treatment and after 8 and 12 weeks.

[0111] The tested doses were 50 ml / m 2 for non-porous surfaces (ceramic tiles) and 100 ml / m 2 for porous surfaces (fibre cement).

[0112] The species selected for testing were Musca domestica (housefly) and Blattella germanica (German cockroach).

[0113] The product has proven to be very effective against both target pests, achieving complete kill (100%) up to an exposure time of 12 weeks.

[0114] A further four-week test showed that the effectiveness against Musca domestica was still present, but only slightly effective against Blattella germanica: Table 15 8 weeks 12 weeks 16 weeks Musca domestica 100% 100% 100% Blattella germanica 100% 100% 17% Toxicity studies on the final product

[0115] An oral acute toxicity test was conducted in rats to determine whether the final product could be toxic with a single oral dose. Under the study conditions, the oral acute LD 50 dose of the final product was greater than 5000 mg / kg body weight in female rats. All animals survived, gained weight, and appeared active and healthy throughout the study. Thus, the final product falls into GHS Category 5, meaning no symbols or warnings are required.

[0116] An acute inhalation toxicity test was conducted on rats to determine whether the final product could be toxic upon single exposure via inhalation (only the nose was exposed). Under the study conditions, the LC50 of the test substance was greater than 5.03 mg / L in both male and female rats. Thus, the final product also meets the requirements of Category 5.

[0117] All animals survived the exposure and gained body weight during the study. After exposure, all rats exhibited irregular breathing, but all animals recovered by day 2 and appeared active and healthy for the remainder of the two-week observation period. No gross abnormalities were observed in any of the animals when necropsied at the end of the 14-day observation period.

[0118] Acute dermal toxicity was not tested because the lethal dose in rats was already above 5000 mg / kg for the concentrate. Toxicity studies on the concentrate

[0119] Analogous studies for the concentrate (10% phenothrin and 1% prallethrin) showed that the LD 50 value in both the oral and dermal acute toxicity tests was greater than 5000 mg / kg body weight. This corresponds to Category 5 of the corresponding GHS hazard class, meaning no symbols or warnings are required.

[0120] In the acute oral toxicity study, all animals were observed at least once daily for 13 or 14 days for mortality, signs of gross envenomation, and behavioral changes. All animals survived, gained weight, and appeared active and healthy. There were no signs of gross envenomation, adverse pharmacological effects, or abnormal behavior.

[0121] In the acute dermal toxicity study, all animals were observed at least once daily for 14 days for mortality, signs of gross envenomation, and behavioral changes. All animals survived the exposure and gained body weight. No gross abnormalities were observed in any of the animals when necropsied at the end of the 14-day observation period.

[0122] In the inhalation acute toxicity study, the values ​​met the requirements for Category 4 of the corresponding GHS hazard class. All animals survived exposure to the test atmosphere. Following exposure, 8 rats showed decreased activity, and all rats also exhibited irregular breathing, abnormal gait, and tremors. However, all rats recovered by day 4 and appeared active and healthy throughout the remaining 14-day observation period. Although some animals lost or at least did not gain weight on day 1, all animals gained weight during the 14-day observation period. The observed weight loss was not considered toxicologically significant. No gross abnormalities were observed in any of the animals when necropsied after the 14-day observation period. Storage life of the final product and the concentrate

[0123] Physical and chemical properties were determined in accordance with the OECD Principles of Good Laboratory Practice and the GLP principles of the Austrian Chemicals Act 1996. The studies were conducted in 0.375 liter PET spray bottles as the final packaging material. Typical parameters such as physical state, color, odor, active ingredient content, density, pH, wet sieve residue, persistent foam, particle size, pourability, dispersion stability, and corrosion properties were determined. Four samples were analyzed: Newly manufactured product. Product after 4 freeze / thaw cycles: 18 hours each at -10±2°C and 6 hours at 20±2°C. Product after 7 days at 0±2°C. Product after 14 days at 54±2°C.

[0124] Both the final product and the concentrate were stable in these accelerated aging samples. Determination of the anaerobic biodegradation of the final product

[0125] The anaerobic biodegradation of the final product was determined according to OECD 310:2014. The samples were kept at a temperature of 20±2°C during the test period (28 days).

[0126] Since the TIC content was less than 10% at the end of the test period, it can be concluded that no abiotic degradation occurred. According to OECD 310:2014, the final product is therefore considered non-biodegradable under aerobic conditions. Determination of the effective dose on non-porous surfaces

[0127] The aim of this study was to evaluate different dosages of the final product on non-porous surfaces with regard to the control of Musca domestica (common housefly), Blattella germanica (German cockroach) and Tegenaria domestica (house spider, cellar spider)

[0128] These insects were exposed to surfaces treated with different dosages, namely 12 ml / m 2 , 25 ml / m 2 , and 35 ml / m 2 . A control experiment in which the surface was treated with water was also conducted.

[0129] Several 15 cm x 15 cm ceramic tiles were treated with the product, and the insects were exposed to them for one hour. Mortality was monitored at regular intervals.

[0130] The following results were obtained: For the tiles treated with water, mortality was below 5%, making the test valid. For the tiles treated with 12 ml / m², the following percentages of insects killed were obtained: Table 16 Time 1h 2h 3h 4h 5h 6h 7h 8h 24h 48h 72h Musca domestica 0 0 0 0 0 1 1 5 49 93 100 Blattella germanica 0 0 0 0 0 0 1 1 9 44 44 Tegenaria domestica 0 0 0 0 0 0 0 0 15 55 55

[0131] It can be seen that this dosage is insufficient because not all insects were destroyed after 24 hours.

[0132] For tiles treated with 25 ml / m 2< the following percentages were obtained: Table 17 Time 1h 2h 3h 4h 5h 6h 7h 8h 24h 48h 72h Musca domestica 0 0 0 2 5 8 13 19 100 100 100 Blattella germanica 0 0 0 2 4 13 13 16 100 100 100 Tegenaria domestica 0 0 5 5 10 19 19 20 100 100 100

[0133] Here the dosage is sufficient: after 24 hours all insects are destroyed.

[0134] For tiles treated with 35 ml / m 2< the following percentages were obtained: Table 18 Time 1h 2h 3h 4h 5h 6h 7h 8h 24h 48h 72h Musca domestica 0 1 9 17 37 55 100 100 100 100 100 Blattella germanica 0 0 3 6 11 19 24 30 100 100 100 Tegenaria domestica 0 5 10 15 20 20 25 45 100 100 100

[0135] This increase in dosage further improved the effect: the housefly was completely destroyed after just 7 hours, and the increase in dosage also brought about an improvement in the other two insect species. Determination of the effective dose on porous surfaces

[0136] The aim of this study was to evaluate different dosages of the final product on porous surfaces with regard to the control of Musca domestica (common housefly) Blattella germanica (German cockroach)

[0137] These insects were exposed to concrete treated with different dosages, namely 25 ml / m 2 , 35 ml / m 2 , and 50 ml / m 2 . A control experiment was also conducted in which concrete was treated with water.

[0138] Mortality was monitored at regular intervals.

[0139] The following results were obtained: For the concrete treated with water, mortality was below 5%, making the test valid. For the tiles treated with 25 ml / m², the following percentages were obtained: Table 19 Time 1h 2h 3h 4h 5h 6h 7h 8h 24h 48h 96h Musca domestica 0 0 0 0 0 0 0 0 100 100 100 Blattella germanica 0 0 0 0 0 0 0 0 19 36 77

[0140] It can be seen that this dosage is insufficient because not all insects were destroyed after 24 hours.

[0141] For tiles treated with 35 ml / m 2< the following percentages were obtained: Table 20 Time 1h 2h 3h 4h 5h 6h 7h 8h 24h 48h 96h Musca domestica 0 0 0 2 9 11 16 23 100 100 100 Blattella germanica 0 0 0 0 0 0 0 0 30 52 93

[0142] Here, more insects are killed after 24 hours, but not all of them. Therefore, this dosage is also insufficient.

[0143] For tiles treated with 50 ml / m 2< the following percentages were obtained: Table 21 Time 1h 2h 3h 4h 5h 6h 7h 8h 24h 48h 96h Musca domestica 0 0 3 11 16 22 28 47 100 100 100 Blattella germanica 0 0 0 0 5 8 12 17 100 100 100

[0144] Here the dosage is sufficient: after 24 hours all insects are destroyed.

Claims

1. A combination of encapsulated phenothrin and emulsified prallethrin in water.

2. The combination according to claim 1, characterised in that the mass ratio of phenothrin to prallethrin is between 5:1 and 20:1 and is preferably 10:1.

3. The combination according to claim 1 or 2, characterised in that the phenothrin is microencapsulated.

4. The combination according to claim 3, characterised in that the specific particle size of phenothrin is between 1.8 µm and 3.3 µm.

5. The combination according to any of claims 1 to 4, characterised in that it is co-formulated with a UV stabiliser.

6. The combination according to any of claims 1 to 5, characterised in that the concentration of phenothrin is 9-11 wt% and the concentration of prallethrin is 0.9-1.1 wt%.

7. The combination according to any of claims 1 to 5, characterised in that the concentration of phenothrin is 0.09-0.11 wt% and the concentration of prallethrin is 0.009-0.011 wt%.

8. A non therapeutic use of the combination according to claim 7 as an insecticide.

9. The non therapeutic use of the insecticide according to claim 8 in a concentration of 20 ml / m2 to 60 ml / m2 on non porous surfaces.

10. The non therapeutic use of the insecticide according to claim 8 in a concentration of 40 ml / m2 to 120 ml / m2 on porous surfaces.