Insecticidal formulation for vector and pest control with increased contact efficacy

Abstract

To provide insecticidal formulations for vector and pest control with increased contact efficacy.SOLUTION: More specifically, the present invention relates to: insecticidal active ingredient-matrix particles; insecticidal compositions comprising the insecticidal active ingredient-matrix particles; and methods and uses of the insecticidal formulations.SELECTED DRAWING: None

Description

[Background technology]

[0001] The use of pesticides to protect fruit, vegetables and other agricultural crops from insects is well established. Following these applications, the same types of active ingredients can be used to protect humans from insect vectors such as mosquitoes (vector control) and from insects outside the agricultural environment that are referred to as sanitary pests, such as cockroaches, flies and bedbugs.

[0002] To protect humans from these insects, surfaces in and around human living and food producing environments are treated with insecticides. Contact times are often very short, necessitating a relatively fast uptake of the insecticide. In contrast to many agricultural applications, the mechanism for control of the active ingredient in these types of applications is limited to contact effects. No oral ingestion occurs, for example, when a mosquito lands and walks over the treated surface. Therefore, only a limited class of pesticides is effective for these treatments. These include, for example, pyrethroids, carbamates, organophosphates, and DDT. Obviously, the latter three are not preferred due to their toxicological profile for humans and the environment. On the other hand, pyrethroids have been widely used for vector control and specialist pest management over the past decades, resulting in the establishment of strong resistance to this mode of action.

[0003] Some other insecticidal active ingredients show efficacy against pests relevant for vector control and professional pest management, and even show the possibility of resistance breaking. However, due to their physicochemical properties, they only show limited contact efficacy. The high melting point and molecular weight of such insecticidal active ingredients require a tendency to form highly crystalline structures that are poorly soluble. As a result, the uptake in insects via contact is very limited, and insects cannot be effectively treated with known formulations, such as, for example, conventional suspension concentrate formulations in which the insecticidal active ingredients are present as crystalline entities.

[0004] On the other hand, the use of polymers and / or waxes as matrix materials is known in agricultural formulations. Many "controlled release" formulations are based on this principle and are described in the literature. For example, US Patent Application Publication No. 2006 / 0193882 discusses a formulation in which the pesticidal active ingredient is contained in a polymer matrix in order to extend the residual biological availability, but this method reduces the initial biological availability. Since the low initial biological availability is accompanied by a low contact availability, such "controlled release" formulations generally do not serve the purpose of increasing the contact efficiency of the pesticidal active ingredient when only a short contact time occurs. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] US Patent Application Publication No. 2006 / 0193882 Summary of the Invention

[0006] Description of the invention The object of the present invention was therefore to provide technical formulation means for solving the problems identified in the prior art and for taking advantage in particular of the possibility of full contact and early (fast knockdown after contact) biological effectiveness of insecticidal active ingredients with difficult physicochemical properties. A particular object was to provide technical formulation means for insecticidal active ingredients that have a high tendency to crystallize under normal conditions, but generally have a higher biological activity against pests in the amorphous state. A further object was to provide technical formulation means for pest control, in particular cockroaches, mosquitoes, flies, amphioxus, etc., with high biological contact effectiveness on various surfaces, such as flat, porous or muddy surfaces. Another object was to provide technical formulation means for pest control with resistance-destroying ability, in particular pyrethroid resistance-destroying ability.

[0007] It has now been found that this objective is addressed, as further described below, by providing insecticidal active ingredient-matrix particles in a solution.

[0008] The insecticidally active ingredient-matrix particles of the present invention relate to insecticidally active ingredient-matrix particles having a particle size d50 of 0.1 to 75 microns, said particles comprising: a) at least one insecticidal active ingredient having a melting point of 110°C or higher and a water solubility of 0.1% or less, which is distributed in the following b); b) A matrix material comprising polymerized monomer units selected from the group of C7 to C12 unsaturated aromatic hydrocarbons.

[0009] The insecticidally active ingredient-matrix particles of the present invention preferably have a particle size of 0.1 to 75 microns, more preferably 0.5 to 50 microns, and even more preferably 1 to 25 microns. The D50 value is preferably determined by laser diffraction after dispersing the insecticidally active ingredient-matrix particles of the present invention in an aqueous phase.

[0010] The insecticidally active ingredient-matrix particles of the present invention contain at least one insecticidally active ingredient having a melting point of 110°C or more, preferably 120°C or more, more preferably 130°C or more, more preferably 140°C or more, even more preferably 150°C or more, and a water solubility of 0.1% or less, preferably 0.01% or less, more preferably 0.005% or less, more preferably 0.001% or less. In another preferred embodiment of the present invention, the insecticidally active ingredient-matrix particles contain one insecticidally active ingredient having the above physicochemical properties. The melting point according to the present invention is measured under standard conditions (1 atm). The water solubility is expressed as a percentage with reference to the quotient of (g) grams of insecticidally active ingredient / 100 ml water. The water solubility is preferably measured by liquid chromatography, for example by HPLC-MS system (20°C, 1 atm and pH 7, see also Example 1 for reference).

[0011] According to a preferred embodiment of the present invention, the "at least one" insecticidal active ingredient of the present invention comprises at least one amide chemical moiety.

[0012] More preferably, at least one insecticidal active ingredient of the present invention is selected from the chemical classes of isoxazolines, meta-diamides, arylpyrazole heteroarylamides and arylpyrazoarylamides and / or is active against gamma-aminobutyric acid (GABA) receptors.

[0013] Isoxazolines are a class of compounds active against arthropods and insects relevant in the plant protection sector as well as ectoparasites on animals. They are antagonists of the gamma-aminobutyric acid (GABA) receptor. The binding site of isoxazolines is at least partially distinct from that of cyclodiene and fipronil (WL Shoopet al. Veterinary Parasitology 2014, 201, 179-189; TLMcTier et al. Veterinary Parasitology 2016, 222, 3-11; K. Nakahira et al. Pest Management Science 2015, 71, 91-95; L. Rufener et al. Parasites and Vectors). 2017, 10, 530. Prominent representatives of this class are, for example, lotilaner, sarolaner, fluralander, afoxolaner and 4-[(5S)-5-(3,5-dichloro-4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-1,2-oxazolidin-4-yl]-2-methylbenzamide (CAS 1309959-62-3).

[0014] Metadiamides are a class of compounds that act as antagonists on gamma-aminobutyric acid (GABA) receptors. A prominent representative of this class is brofuranilide. The binding site of desmethyl-brofuranilide is at least partially different from that of cyclodienes and fipronil (T. Nakao, S. Banba, Bioorganic & Medicinal Chemistry 2016, 24, 372-377).

[0015] A class of arylpyrazole heteroarylamides and arylpyrazolarylamides that can be preferably used in the context of the present invention is described in WO 2015 / 067647 and WO 2015 / 067646, which are incorporated herein by reference.Preferably, this class relates to 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide.

[0016] In this context, the term "active on the GABA receptor" preferably relates to the characteristic of a chemical molecule that modulates the biological activity of the GABA receptor.

[0017] The insecticidal active ingredient according to the present invention may be in the form of geometric isomers and / or optically active isomers or corresponding isomeric mixtures in different compositions depending on the active ingredient.These stereoisomers are, for example, enantiomers, diastereomers or geometric isomers.Therefore, the present invention encompasses the use of both pure stereoisomers and any mixtures of these isomers.

[0018] Even more preferably, the at least one insecticidal active ingredient of the present invention is selected from the following group: -2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide (CAS 1771741-86-6), - Brofuranilide: 3-[benzoyl(methyl)amino]-N-[2-bromo-4-(1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethyl)phenyl]-2-fluorobenzamide (CAS 1207727-04-5), -4-[(5S)-5-(3,5-dichloro-4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-1,2-oxazolidin-4-yl]-2-methylbenzamide (CAS 1309959-62-3), -4-[(5R)-5-(3,5-dichloro-4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl]-N-[(4S)-2-ethyl-3-oxo-1,2-oxazolidin-4-yl]-2-methylbenzamide (CAS 2061933-86-4), -4-[(5S)-5-(3,5-dichloro-4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl]-N-[(4S)-2-ethyl-3-oxo-1,2-oxazolidin-4-yl]-2-methylbenzamide (CAS 1429660-18-3), -4-[(5R)-5-(3,5-dichloro-4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-1,2-oxazolidin-4-yl]-2-methylbenzamide (CAS 1309958-03-9), -Sarolaner: 1-[6-[(5S)-5-(3,5-dichloro-4-fluorophenyl)-5-(trifluoromethyl)-4H-1,2-oxazol-3-yl]spiro[1H-2-benzofuran-3,3'-azetidin]-1'-yl]-2-methylsulfonylethanone (CAS 1398609-39-6), -Fluralaner: 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-1,2-oxazol-3-yl]-2-methyl-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]benzamide (CAS 864731-61-3 -3-Methyl-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]-5-[(5S)-5-(3,4,5-trichlorophenyl)-5-(trifluoromethyl)-4H-1,2-oxazol-3-yl]thiophene-2-carboxamide (CAS 1369852-71-0), -Afoxo-Layner: 4-[5-[3-chloro-5-(trifluoromethyl)phenyl]-5-(trifluoromethyl)-4H-1,2-oxazol-3-yl]-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]naphthalene-1-carboxamide (CAS 1093861-60-9).

[0019] Even more preferably, the "at least one" insecticidal active ingredient of the present invention is selected from the following group: -2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide (CAS 1771741-86-6), - Brofuranilide: 3-[benzoyl(methyl)amino]-N-[2-bromo-4-(1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethyl)phenyl]-2-fluorobenzamide (CAS 1207727-04-5), -4-[(5S)-5-(3,5-dichloro-4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-1,2-oxazolidin-4-yl]-2-methylbenzamide (CAS 1309959-62-3).

[0020] Most preferably, the "at least one" insecticidal active ingredient of the present invention is selected from the group of 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3-heptafluoropropan-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide (CAS 1771741-86-6) and broflanilide, and even more preferably the "at least one" insecticidal active ingredient is 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide (CAS 1771741-86-6).

[0021] In a further embodiment, the insecticidally active ingredient-matrix particles of the present invention comprise at least one of the above insecticidally active ingredients distributed, preferably uniformly distributed, in a matrix material as described herein. The distribution is preferably achieved in a heating step, in which the at least one insecticidally active ingredient and the matrix material are heated to a temperature at which the matrix material is no longer solid, preferably above the softening point of the matrix material, but below the melting point of the insecticidally active ingredient. The mixture is kept at this temperature (e.g., for 10, 15 or 20 minutes) until the above insecticidally active ingredient is uniformly distributed. The particle size of the insecticidally active ingredient-matrix particles can then be obtained by conventional grinding and / or comminuting means with conventional mixers, mills and / or grinders.

[0022] The matrix material used for the insecticidal active ingredient-matrix particles of the present invention preferably comprises polymerized monomer units selected from the group of C7-C12 unsaturated aromatic hydrocarbons having a softening point of 80°C to 130°C, more preferably having a softening point of 80°C to 115°C, and even more preferably having a softening point of 80°C to 110°C. As used herein, the term "softening point" refers to the Vicat softening temperature or Vicat hardness, which is a determination of the softening point for materials that do not have a fixed melting point, such as resins. 1mm 2The softening point is the temperature at which the specimen is penetrated to a depth of 1 mm by a flat-ended needle with a circular or square cross section of 1 mm. Preferably, the Vicat B120 test is used to measure the softening point. The Vicat B120 test is characterized by a load of 50 N and a heating rate of 120 (K / h). Standards for determining the Vicat softening point include ASTM D 1525 and ISO 306, which are roughly equivalent.

[0023] In a further preferred embodiment of the invention, the matrix material comprises polymerized monomer units selected from the group of C8-C11 and, even more preferably, from the group of C9-C10 unsaturated aromatic hydrocarbons. In this context, C7-C12, C8-C11, C9-C10 each refer to the amount of carbon atoms present in the molecule. In another particular preferred embodiment of the invention, the monomer units are selected from the group of indene, methylindene, vinyltoluene, α-methylstyrene, styrene and / or dicyclopentadiene. In a further preferred embodiment, the monomer units are selected from the group of indene and methylindene.

[0024] Particularly preferred matrix materials are products from the Novares AS, TK, TL, TN, TC, C and CA series of the Ruetgers company, with a softening point of 80-115° C. Further preferred are the matrix materials Novares Pure 85 AS (Ruetgers Group), Novares C 100 (Ruetgers Group), Novares TL 100 (Ruetgers Group), Novares TK100 (Ruetgers Group), Novares TN 100 (Ruetgers Group).

[0025] Polymerization of monomer units is described, for example, in EP1900763 A1 and is generally known to those skilled in the art. In a preferred embodiment, the polymerization is a cationic polymerization, and the weight ratio between the monomer units can be varied from matrix material to matrix material. Suitable matrix materials can also be polymerized only from one specific monomer unit, such as indene (e.g., Novares C series from Ruetgers). Furthermore, the polarity of such matrix materials can be increased by modification with phenols (e.g., Novares CA series from Ruetgers; phenol-modified indene matrix materials).

[0026] Another embodiment of the present invention refers to insecticidal active ingredient-matrix material particles of the particle size indicated above, said material particles being: a) at least one insecticidal active ingredient having a melting point of 110°C or higher and a water solubility of 0.1% or less, which is distributed in the following b); b) a matrix material having a softening point of at least 30° C. below the melting point of the at least one insecticidal active ingredient; Including, The insecticidally active ingredient-matrix material particles are characterized in that they do not exhibit a melting peak of the active ingredient when measured using differential scanning calorimetry in a second heating cycle after heating the matrix material to a temperature at least 20°C above the melting point of the at least one insecticidally active ingredient, preferably at a steady heating rate of 5-15°C / min, more preferably 10°C / min.

[0027] In this context, the "matrix material", which preferably has a softening point of at least 30°C below the melting point of the at least one insecticidal active ingredient, is preferably selected from matrix materials such as hydrocarbon resins, more preferably unsaturated aromatic hydrocarbon resins, and even more preferably C8-C12 unsaturated aromatic hydrocarbon resins. Such preferred resins comprise polymerized monomer units selected from C8-C12 unsaturated aromatic hydrocarbons. Further preferred matrix materials are described further above.

[0028] A further embodiment of the present invention relates to an insecticidally active ingredient-matrix material particle as outlined above, characterized in that the "at least one" insecticidally active ingredient and the matrix material are heated in a first heating cycle of a differential scanning calorimetry to a temperature of at least 20°C, preferably at least 20°C to 50°C, above the melting point of the at least one insecticidally active ingredient, at a constant heating rate of 5 to 15°C / min, more preferably 10°C / min.

[0029] In a preferred version of the above differential scanning calorimetry, the maximum heating temperature of the first heating cycle is held for at least 10 minutes, preferably 15 minutes, more preferably 20 minutes.

[0030] In another preferred embodiment of the present invention, the at least one insecticidal active ingredient and the matrix material are cooled to a temperature of 0°C to 40°C, preferably 15°C to 35°C, more preferably 20°C to 30°C, between the first and second heating cycles of the differential scanning calorimetry, and after the second heating cycle are cooled at a constant cooling rate of preferably 5 to 15°C / min, more preferably 10°C / min.

[0031] As used herein, the term "steady heating rate" refers to a constant temperature increase per minute that is held constant. Thus, it is preferred that the temperature increase over time is linear. Similarly, as used herein, the term "steady cooling rate" refers to a constant temperature decrease per minute that is held constant. Thus, it is preferred that the temperature decrease over time is linear.

[0032] The term "melting peak" as used herein preferably refers to an endothermic signal in a differential scanning calorimetry (DSC) thermogram. The basic principle underlying this technique is that when a sample undergoes a physical transformation, such as a phase transition, more or less heat must flow to it than a reference to keep both at the same temperature. Whether less or more heat must flow to the sample depends on whether the process is exothermic or endothermic. For example, when a solid sample melts into a liquid, more heat must flow to the sample to increase its temperature at the same rate as the reference. This is because the sample undergoes an endothermic phase transition from solid to liquid, absorbing heat.

[0033] A preferred embodiment of the present invention relates to an insecticidally active ingredient-matrix material as outlined above, characterized in that in the first heating cycle of a differential scanning calorimetry, the at least one insecticidally active ingredient and the matrix material are heated to a temperature at least 10°C above the softening point of the matrix material and at least 20°C below the melting point of the at least one insecticidally active ingredient, preferably at a constant heating rate of 5-15°C / min, more preferably 10°C / min.

[0034] The tiles used in the DSC experiments are small and do not allow for convection / agitation to be applied for proper mixing of the components (matrix material and insecticidal active ingredient), so mixing is only kinetically controlled. This can lead to false negative results when searching for a suitable matrix material. If such mixing does not occur spontaneously at a temperature at least 10°C above the softening point of the matrix material and at least 20°C below the melting point of at least one insecticidal active ingredient, then adapt the first heating cycle by waiting longer (preferably holding the maximum heating temperature of the first heating cycle for a period of at least 30 minutes, more preferably 60 minutes, even more preferably 120 minutes) or by heating to a temperature at least 20°C above the melting point of the insecticidal active ingredient to ensure uniform distribution. An effective way to determine if mixing does not occur spontaneously within the tile or if the matrix material is not suitable is to use the enthalpy of fusion of the insecticidal active ingredient. By comparing the melting enthalpy of the isolated insecticidal active ingredient with the melting enthalpy of the peak that may occur during the second heating cycle, the percentage of the insecticidal active ingredient that dissolves can be determined. If only a portion of the insecticidal active ingredient is dissolved, it is advisable to adapt the first heating cycle of the DSC to a temperature at least 20°C above the melting point of the insecticidal active ingredient to determine whether the matrix material is suitable.

[0035] Another embodiment of the present invention relates to an insecticidally active ingredient-matrix material particle as described herein, characterized in that the weight ratio between the at least one insecticidally active ingredient and the matrix material is between 1:99 and 1:1, preferably between 5:95 and 40:60.

[0036] The concentration of the insecticidal active ingredient in the matrix material particles depends on the required dosage rate of insecticidal active ingredient / m2 of treated surface. However, such products usually have a dosage of 250m 2 The formulation is applied in a 10 liter backpack sprayer capable of treating surfaces of 25 to 250 grams of the formulated product, preferably 50 to 150 grams of the formulated product, in such a 10 liter backpack sprayer.

[0037] The concentration of insecticidal active ingredient per square meter is usually 1 to 500 mg / m 2 More preferably, the range is 2 to 200 mg / m 2 The range is.

[0038] The molecular weight of the matrix material according to the present invention can vary, but is preferably between 1 and 1000 kDa.

[0039] A further embodiment of the present invention relates to an insecticidal composition, wherein the insecticidal composition comprises: a) preferably 1 to 70% by weight, more preferably 5 to 60% by weight, and even more particularly 10 to 50% by weight, of insecticidal active ingredient-matrix material particles as described herein; b) at least one surfactant, preferably at least one nonionic surfactant and / or at least one anionic surfactant, preferably the surfactant is present in an amount of 1 to 25% by weight, more preferably 2 to 25% by weight, even more preferably 2.5 to 15% by weight, c) optional further adjuvants selected from the group of antifreeze agents, antifoaming agents, preservatives, antioxidants, thickeners, colorants and binders, preferably 0-25% by weight, more preferably 0.1-20% by weight, and even more preferably 0.5-10% by weight; d) liquid phase and / or bulking agents (in each case adding up to 100% by weight of the total pesticidal composition).

[0040] Suitable anionic surfactants are all materials of this type that can normally be used in agrochemical compositions. Examples include the alkali metal salts of condensation products of fatty acid chlorides with aminosulfonic acids, the alkali metal salts of fatty alkyl and alkenyl sulfonates and sulfates (wherein fatty alkyl and alkenyl include alkyl and alkenyl groups of about 8 to 18 carbons), and alkali metal alkylbenzene sulfonates having at least 10 carbons in the alkyl group. Preferred members of this class include those having 10 to about 18 carbons in the alkyl group, ethoxylated alkylphenols having about 8 to about 15, preferably about 8 to about 10, carbons in the alkyl group, and about 4 to about 20 oxyethylene units.

[0041] More preferred anionic surfactants are selected from the group of alkali metal and alkaline earth metal salts of alkylsulfonic acids or alkylarylsulfonic acids. More preferred anionic surfactants are salts of polystyrenesulfonic acid, salts of polyvinylsulfonic acid, salts of naphthalenesulfonic acid / formaldehyde condensates, salts of naphthalenesulfonic acid, phenolsulfonic acid and formaldehyde condensates, and salts of lignosulfonic acid.

[0042] Suitable nonionic surfactants are all compounds of this type that can be commonly used in agrochemical compositions.As examples, polyethylene oxide / polypropylene oxide block copolymers, polyethylene glycol ethers of linear alcohols, reaction products of ethylene oxide and / or propylene oxide with fatty acids, as well as polyvinyl alcohol, polyvinylpyrrolidone, mixed polymers of polyvinyl alcohol and polyvinylpyrrolidone, mixed polymers of polyvinyl acetate and polyvinylpyrrolidone, and copolymers of (meth)acrylic and (meth)acrylic acid esters, as well as alkyl ethoxylates and alkylaryl ethoxylates, polyoxyamine derivatives and nonylphenol ethoxylates, which can be optionally phosphorylated and can be optionally neutralized with base.

[0043] Suitable antifreeze agents for the pesticidal components of the invention are all substances usually used for this purpose in agrochemical compositions. Preference is given to urea, glycerol, propylene glycol.

[0044] Suitable antifoaming agents for the insecticidal components of the invention are all substances usually used for this purpose in agrochemical compositions. Silicone oils and magnesium stearate are preferred.

[0045] Suitable preservatives for the pesticidal components of the invention are all substances of this type which are usually used for this purpose in pesticide compositions, for example Preventol® (Bayer AG) and Proxel (registered trademark).

[0046] Suitable antioxidants for the pesticidal components of the invention are all substances usually used for this purpose in agrochemical compositions.Butylated hydroxytoluene (2,6 di-t-butyl 4-methylphenol, BHT) is preferred.

[0047] Suitable thickeners for the pesticidal component of the thickener according to the invention are all substances of this type usually used in agrochemical compositions. Preference is given to silicates (e.g. Attagel® 50 from Engelhard) or xanthan gum (e.g. Kelzan® S from Kelko).

[0048] Suitable colorants for the pesticidal components of the invention are all the substances usually used for this purpose in agrochemical compositions, such as titanium dioxide, carbon black, zinc oxide, as well as blue pigments and permanent red FGR.

[0049] Suitable fillers are all the substances that are usually used for this purpose in agrochemical compositions.Preferably, inert fillers include inorganic particles or salts, such as carbonates, silicates and oxides, and organic substances, such as urea / formaldehyde condensates.Further examples are Ulmer White, Etiquette Violet chalk, potassium sulfate, diamonium hydrogen phosphate, kaolin, rutile, silicon dioxide, what is known as highly dispersed silica, silica gel, and natural and synthetic silicates, such as montmorillonite, bentonite and chemical modifications of these clays, as well as talc.Preferred inert fillers are carbonates, such as Ulmer White, Etiquette Violet chalk, silicates, such as kaolin, and salts, such as potassium sulfate.

[0050] Suitable binders for the pesticidal compositions according to the invention are all substances which are usually used for this purpose in pesticidal compositions, for example polyvinylpyrrolidones such as Sokalan K 30 or Sokalan K 90.

[0051] Preferred pesticide compositions are in the form of suspension concentrates (SC), water dispersible granules (WG) or water dispersible powders (WP) or spray solutions thereof.

[0052] In general, it has been surprisingly found that the insecticidal compositions according to the invention are stable even after long-term storage (2 weeks) at high (54°C) or low temperatures, and no crystal growth has been observed. By dilution with water, the SC, WG or WP can be converted into a homogeneous spray solution.

[0053] Suspension concentrate (SC) formulations, for example, require a liquid phase, which is preferably water.

[0054] For SC formulations based on the insecticidal active ingredient-matrix material particles of the invention, the insecticidal composition preferably contains one or more surfactants, preferably in an amount of 2-20% by weight, more preferably 2.5-10% by weight.

[0055] In the case of an SC formulation, the insecticide composition preferably comprises (as component (c)) an adjuvant selected from the group consisting of antifreeze agents, antifoam agents, preservatives, antioxidants and thickeners, preferably in an amount of 0.1 to 20% by weight.

[0056] The SC formulations according to the invention are prepared by mixing the components with each other in a specific desired ratio. The components can be mixed with each other in any order; if a thickening agent is present, it is preferably added after the grinding step. The solid components are also used in a finely ground state. However, it is also possible that the suspension formed after mixing the components is first subjected to a coarse grinding and then fine grinding to achieve a particle size d50 of the insecticidal active ingredient-matrix material particles and the same d50 for the other components. Thus, the SC formulation has a particle size d50 of all components between 0.1 and 75 microns, more preferably between 0.5 and 50 microns, even more preferably between 1 and 25 microns. Suitable for carrying out the preparation of the SC are the usual mixers, mills and grinders used in the manufacture of agrochemical formulations.

[0057] During the preparation of the SC formulation, the temperature may vary within a certain range. Generally, the process is carried out at 10-60°C, preferably 15-45°C, under normal pressure.

[0058] Wettable powder (WP) formulations require a bulking agent.

[0059] For WP formulations, the insecticidal composition desirably contains one or more surfactants (as component (b)), preferably in an amount of from 2 to 25% by weight, more preferably from 2.5 to 15% by weight.

[0060] In the WP formulation, the insecticidal composition preferably contains an adjuvant (as component (c)) selected from the group of antifoaming agents, preservatives, antioxidants, preferably in an amount of 0.5-10% by weight. The WP formulation according to the invention is prepared by mixing the components with each other in a specific desired ratio. The components can be mixed with each other in any order. Also, the solid components are used in a finely ground state. However, it is also possible to subject the suspension formed after mixing the components to first a coarse grinding and then a fine grinding to achieve a particle size d50 of all components between 0.1 and 75 microns, preferably between 0.5 and 50 microns, more preferably between 1 and 25 microns.

[0061] Suitable for carrying out the process according to the invention are dry grinding equipment such as conventional mixers and air jet mills, which are employed for producing agrochemical formulations.

[0062] The water-dispersible granule (WG) formulation according to the present invention can be prepared, for example, as extrusion granule, fluidized bed granule or spray-dried granule according to the standard method applicable in the agrochemical industry.Generally, the basis of extrusion granule is WP type premix (TK), and the basis of other techniques is suspension concentrate (slurry).In addition to the composition described, these TK and slurry can have filler and / or binder as further components described herein.

[0063] For WG formulations, the insecticidal composition preferably comprises one or more surfactants (constituent (b)), preferably in an amount of 2 to 25% by weight, more preferably 2.5 to 15% by weight.

[0064] In the case of a WG formulation, the insecticidal composition preferably comprises (as component (c)) an adjuvant selected from the group of antifoaming agents, preservatives, antioxidants, binders, preferably in an amount of 0.5 to 10% by weight.

[0065] In the case of a WG formulation, the insecticidal composition preferably comprises (as component (d)) a filler, which in any case is added up to 100% by weight relative to the total WG formulation.

[0066] Another embodiment of the present invention relates to the use of the insecticidal active ingredient-matrix material particles described herein or the insecticidal composition described herein for controlling certain insects and / or arachnids (preferably of the subclass Acarina), and in particular mosquitoes, flies, mites, lice, ants, termites, termites and cockroaches.

[0067] The pest is preferably controlled through contact of the pest with the pesticidal active ingredient-matrix material particles described herein or the pesticidal composition described herein. Preferably, ingestion is not required. The term "control" of a pest refers to the possibility of knocking down, killing, and / or repelling the pest.

[0068] The insecticidal active ingredient-matrix material particles described herein or the insecticidal compositions described herein are preferably used outside the agricultural environment, especially for vector control and specialised pest management applications.

[0069] For the purposes of the present invention, a vector is an arthropod, in particular an insect or arachnid, capable of transmitting pathogens, such as viruses, nematodes, single-cell organisms and bacteria, from a reservoir (plant, animal, human, etc.) to a host. The pathogens are either transmitted to the host mechanically (e.g. trachoma by non-biting flies) or injected into the host (e.g. malaria parasites by mosquitoes).

[0070] Examples of diseases or pathogens that they transmit are: 1) Mosquitoes: Anopheles: malaria, filariasis; Crex: Japanese encephalitis, other viral diseases, filariasis, other insect infections; Aedes: yellow fever, dengue fever, other viral diseases, filariasis; - Black flies (Simuliidae): transmission of insects, especially Onchocerca volvulus; Diptera (Psychodidae): Transmission of leishmaniasis, 2) Lice: skin infection, epidemic typhus; 3) Fleas: plague, endemic typhus, tapeworms; 4) Flies: Sleeping sickness (trypanosomiasis); cholera and other bacterial diseases; 5) Ticks: tick disease, epidemic typhus, rickettsialpox, tularemia, St. Louis encephalitis, tick-borne encephalitis (TBE), Crimean-Congo hemorrhagic fever, borreliosis; 6) Ticks: For example, Borrelia afzelii (Borrelia burgdorferi sensu lato.), Borrelia duttoni (relapsing fever), tick-borne encephalitis, Coxiella burnetii, Babesiosis (Babesia canis canis), and ehrlichiosis.

[0071] In the sense of the present invention, examples of vectors are insects capable of transmitting plant viruses to plants, such as aphids, flies, leafhoppers or thrips. Other vectors capable of transmitting plant viruses are spider mites, lice, beetles and nematodes.

[0072] Further preferred examples of vectors in the sense of the present invention are insects and arachnids such as mosquitoes, in particular those of the genera Aedes, Anopheles, such as A. gambiae, A. arabiensis, A. funestus, A. dirus (malaria) and Culex, flies of the family Psychodidae, such as Phlebotomus, Lutzomyia, lice, fleas, flies and mites, which are capable of transmitting pathogens to animals and / or humans.

[0073] The insecticidal active ingredient-matrix material particles described herein or the insecticidal composition described herein are suitable for use in the prevention of diseases and / or pathogens transmitted by vectors.Therefore, a further aspect of the present invention is the use of the active compound combination according to the present invention for vector control, for example in agricultural, horticultural, garden and leisure facilities, and in the protection of materials and stored products.

[0074] Furthermore, the insecticidal active ingredient-matrix material particles described herein, or the insecticidal compositions described herein, are suitable for professional pest management applications against common pests occurring in domestic situations and public / commercial establishments, such as cockroaches, mosquitoes, ants, mites, flies, stored product pests, occasional pests, termites, etc.

[0075] Professional pest management is undertaken to reduce pest numbers to acceptable levels by using a variety of strategies.

[0076] Examples of common types of pests found in and around homes and public / commercial buildings include: 1) Cockroaches: American cockroach (Periplaneta americana), German cockroach (Blattella germanica), Brown banded cockroach (Supella longipalpa), Oriental cockroach (Blatta orientalis) 2) Mosquitoes (see Vector Control) 3) Ants: Black house ants, foul-smelling garden ants, fire ants / red imported fire ants, ghost ants, pharaoh ants, white-footed ants 4) Mites: Dust mites, dirt mites, 5) Flies: Filth flies or houseflies and related species (Muscidae); Sarcophagidae; Bottle flies and blowflies (Calliphoridae); Black flies (Dactylidae); Horseflies and deer flies (Tachypodidae), Fruit flies (Drosophilidae) 6) Stored product pests: Primary cotyledonous (beetle) pests include grain weevils (S. granarius, S. zeamais, S. oryzae), small grain borer (Rhizopertha dominica), and sawtooth grain beetle (Oryzaephilus surinamensis). Secondary beetle pests include the flour beetle (Tribolium castaneum and Tribolium confusum), and the major lepidopteran pests (moths) are secondary; these are common in domestic kitchens and pantries as they feed regularly on processed foods. 7) Occasional pests: Silverfish, millipedes, booklice / pig lice, clothing moths, gypsum bag worms, flea flies, dog ticks, fleas, carpet beetles, black carpet beetles, 8) Termites: Odontotermes spp., Microcerotermes spp., Coptotermes spp., Heterotermes spp., Reticulitermes spp., Zootermopsis spp., Cryptotermes spp., Incisitermes spp., Marginitermes spp., and the like.

[0077] Another embodiment of the present invention relates to a method of controlling pests with the pesticidal active ingredient-matrix material particles described herein, or the pesticidal compositions described herein.

[0078] Another embodiment of the present invention relates to a method for identifying useful matrix materials for pesticidal compositions by differential scanning calorimetry, the method comprising: a) heating an insecticidal active ingredient having a melting point of 110°C or more and a water solubility of 0.1% or less and a matrix material to be tested to a temperature at least 20°C (preferably at least 20°C but not more than 50°C) higher than the melting point of at least one insecticidal active ingredient in a first heating cycle of a differential scanning calorimetry measurement, preferably at a constant heating rate of 5°C to 15°C / min, more preferably 10°C / min; b) holding the maximum heating temperature of the first heating cycle for at least 10 minutes, preferably at least 15 minutes, and more preferably at least 20 minutes; c) Then, the temperature is cooled to a temperature between 0 and 40°C (preferably 15 and 35°C, more preferably 20 and 30°C), d) In the second heating cycle step, the temperature is increased to a temperature at least 20° C. higher than the melting point of at least one insecticidal active ingredient at a constant heating rate of preferably 5 to 15° C. / min, more preferably 10° C. / min; e) A useful matrix material is identified if the insecticidal active ingredient-matrix material combination does not exhibit a melting peak when measured in the second heating cycle of a differential scanning calorimetry.

[0079] Particularly preferred matrix materials are identified by DSC as indicated above, when the first step a) is carried out as follows.

[0080] Step a): In a first heating cycle of differential scanning calorimetry, an insecticidal active ingredient with a melting point of 110°C or more and a water solubility of 0.1% or less and a matrix material to be tested (preferably with a softening point of at least 30°C below the melting point of the insecticidal active ingredient) are heated at a constant heating rate to a temperature at least 20°C lower than the melting point of at least one insecticidal active ingredient (preferably at least 10°C higher than the softening point of the matrix material). However, as mentioned above, such a procedure may give rise to false negative results when searching for a suitable matrix material. Therefore, it is also necessary to adapt step e) of the above-mentioned method, preferably as shown below:

[0081] Step e): If the insecticidally active ingredient-matrix material combination does not exhibit a melting peak when measured in the second heating cycle of the differential scanning calorimetry, or if it exhibits a melting peak of the insecticidally active ingredient, compare only the melting enthalpy of the insecticidally active ingredient measured by DSC (under the same heating conditions) with the melting enthalpy of the insecticidally active ingredient observed during the second heating cycle of the insecticidally active ingredient-matrix material combination in the DSC.

[0082] By comparing the difference in enthalpy of fusion, the fraction of the insecticidal active ingredient that dissolves in the matrix material can be determined and therefore the suitability of the matrix can also be assessed.

[0083] Another embodiment of the present invention relates to a method of increasing the contact efficacy of an insecticidally active ingredient having a melting point of 110° C. or higher and a water solubility of 0.1% or less with an insecticidally active ingredient-matrix material particle as described herein or an insecticidal composition as described herein, as compared to a conventional suspension concentrate formulation having the same insecticidally active ingredient.

[0084] Conventional suspension concentrate (SC) formulations refer to those dispersed in water. Such conventional SC formulations are known to be useful for active ingredients that have high melting points and are insoluble in water. Conventional suspension concentrates are usually produced by mixing the active ingredient powder with an aqueous solution of wetting agents and dispersing agents, followed by a wet milling process in a bead mill to obtain a particle size distribution in the range of 1 to 10 microns. Other materials, such as thickeners, can then be added to modify the rheological properties of the system to reduce elongation of particle separation and settling on storage. Typical wetting / dispersing agents used in conventional SC formulations are sodium lignosulfonate, sodium naphthalene sulfonate-formaldehyde condensates, fatty alcohol ethoxylates, tristrylphenol ethoxylate phosphate esters, EO / PO block copolymers, and graft copolymers. Urea, glycerol, or propylene glycol are used as antifreeze agents. Thus, conventional SC formulations contain insecticidal active ingredients (5-60% by weight), wetting and dispersing agents (2.5-15% by weight), antifreeze agents (4-13% by weight), other additives such as thickeners (0.2-2% by weight), and water (in each case up to 100% by weight of the total conventional SC formulation).

[0085] The present invention will be illustrated in more detail with reference to the following examples, but is not limited to the use forms described in the examples.

[0086] Working Example: 1. Representative physicochemical parameters of the insecticidal active ingredients used according to the invention

[0087] [Table 1]

[0088] The reported melting points, given in Table 1, were determined by differential thermal analysis using a Mettler Toledo 822 or 823 DSC instrument for technical grade active ingredients under normal conditions (1 atm). Samples were heated in perforated aluminum crucibles from 25°C to 300°C at a heating rate of 3 K / min. The melting point is first determined by defining a baseline for the temperature range to be evaluated. A tangent line is then drawn to the turning point on the endothermic side of the peak, and the intersection with the baseline is taken as the melting point of the substance under consideration.

[0089] The reported aqueous solubilities, shown in Table 1, are measured as follows: Preparation of calibration standards: At least three calibration points are obtained by preparing a 1000 ppm solution of the analyte in acetonitrile and diluting, if necessary, to 0.01 mg / L with acetonitrile. Sample preparation: Fill each of the two cavities of the well with approximately 0.6 mg of homogenized sample and add 500 μL of pH 7 phosphate buffer. Add a glass pearl to each cavity and seal and shake the deep well at 1600 rpm at 23°C for at least 24 hours. After the shaking operation, filter the solution. An aliquot of the filtrate is analyzed by AD and MS detection via a DHPLC-MS system. The peak areas of all selected single DAD and ion traces are taken for calculation. The calculation is performed by external calibration (linear regression) against the areas of the standards. The average of all calculated values ​​gives the aqueous solubility of the active ingredient.

[0090] 2. Determining the suitability of matrix materials for the insecticidal active ingredient under investigation by differential scanning calorimetry (DSC) Using differential scanning calorimetry (Mettler Toledo DSC 822e or 823 DSC), a few mg of matrix material and the insecticidal active ingredient under study were loaded into the tiles and closed.

[0091] The weight ratios of matrix material to insecticidal active ingredient were as follows:

[0092] [Table 2] JPEG2024155923000003.jpg111150

[0093] As a reference an empty closed tile was used. After equilibration in the machine, both tiles are heated according to the following program: Heat to 25-130℃ at a heating rate of 10℃ / min. 20 minute wait -Cool down to 25℃ at a rate of 10℃ / min -Heating rate 10℃ / min from 25℃ to 200℃ -Cool down to 25℃ at a rate of 10℃ / min.

[0094] If the weight ratio between the matrix material and the insecticidal active ingredient is not optimal, e.g. if there is too much insecticidal active ingredient and it cannot be evenly distributed in the matrix material within the given time using the above program, the content of insecticidal active ingredient can be reduced and the program run again or the maximum heating temperature is maintained for a longer period or alternatively the following program can be applied: Heat from 25°C to 200°C at a heating rate of 10°C / min (the upper limit temperature can be changed depending on the melting point of the insecticidal active ingredient being considered, and must be 20°C above this melting point), 20 minute wait - Heats at a rate of 10℃ / min and cools to 25℃ Heat from 25°C to 200°C at a heating rate of 10°C / min (the upper limit temperature can be changed depending on the melting point of the insecticidal active ingredient being considered, and must be 20°C above this melting point). Heat up at a rate of 10°C / min and cool down to 25°C.

[0095] Results: For samples 1-3, the melting peak of the insecticidal active ingredient during the second heating cycle was not observed by DSC, indicating that the matrix material is suitable for the insecticidal active ingredient studied. For sample 4, the melting peak of the insecticidal active ingredient during the second heating cycle was observed by DSC, indicating that the matrix material is not suitable for the insecticidal active ingredient studied.

[0096] Using the same procedure and program as above, other matrix material-pesticidally active ingredient combinations have been investigated using the insecticidal active ingredient and matrix material that did not show a melting peak of the insecticidal active ingredient during the second heating cycle in the DSC, as follows:

[0097] Insecticidal active ingredient: 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide in combination with one of the following matrix materials: Novares Pure 85 AS (Ruetgers Group), Novares C 100 (Ruetgers Group), Novares TL 100 (Ruetgers Group), Novares TK 100 (Ruetgers Group), Novares TN 100 (Ruetgers Group).

[0098] 3. Preparation of Insecticidal Active Ingredient-Matrix Particles 40.0 grams of 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide was added to 60.0 grams of Novares CA 100 (Ruetgers Group). The mixture was stirred and heated to 130° C. The temperature was maintained with stirring until the active ingredient was evenly distributed. The mixture was then cooled to room temperature.

[0099] The obtained matrix active ingredient composition was ground using a mixer equipped with a cutting device (food processor Braun-Couchen Mastin 3210).

[0100] In a similar manner, the same (or other) insecticidal active ingredient-matrix particles (also at other concentrations) can be made.

[0101] 4. Preparation of Water-Dispersible Granule (WP) Formulations Based on the Insecticidal Active Ingredient-Matrix Particles Prepared in Example 3 For the preparation of WP 10, 25 g of insecticidal active ingredient-matrix particles according to Example 3 were added to a mixer with a cutting device and stirred with 5% by weight of Oparyl MT 804 (Giovanni Bozzetto SpA), 10% by weight of Baykanol SL (Lanxess) and 60% by weight of Kaolin Tec (Ziegler & Co. GmbH). The mixture was then milled by air jet milling to obtain a WP containing 10% insecticidal active ingredient with the required physicochemical properties.

[0102] For the preparation of WP 20, 50 g of insecticidal active ingredient-matrix particles according to Example 3 were added to a mixer with a cutting device and stirred with 5% by weight of Oparyl MT 804 (Giovanni Bozzetto SpA), 10% by weight of Baykanol SL (Lanxess) and 35% by weight of Kaolin Tec (Ziegler&Co.GmbH). The mixture was then milled by air jet milling to obtain a WP containing 20% ​​by weight of insecticidal active ingredient with the required physicochemical properties.

[0103] For the preparation of WP 5, 50 g of insecticidal active ingredient-matrix particles according to Example 3 (based on 10 g of broflanilide and 90 g of Novares CA 100 matrix material) were added to a mixer equipped with a cutting device and stirred with 2% by weight of Oparyl MT 804 (Giovanni Bozzetto SpA), 5% by weight of Baykanol SL (Lanxess), 2% by weight of Ultrasil VN 3 (Evonik) and 38% by weight of Kaolin Tec (Ziegler&Co. GmbH). The mixture was then milled by air jet milling to obtain a WP containing 5% by weight of insecticidal active ingredient with the required physicochemical properties.

[0104] 5. Preparation of Suspension Concentrate (SC) Formulations Based on the Insecticidal Active Ingredient-Matrix Particles Prepared in Example 3 For the preparation of SC 100, 25 g of insecticidal active ingredient-matrix particles according to Example 3 are mixed with 3.0 g Atlox 4913 (Croda), 10 g propylene glycol, 0.12 g Proxel GXL 20 (Lonza), 0.1 g Silcolap 426 R (Solvay), 1 g Synperonic PE / F 127 (Croda), and 1 g Lucramul PS 16 (Levaco) until a homogeneous suspension is formed. The homogeneous suspension is first coarsely ground and then finely ground, resulting in a suspension in which 90% of the solid particles have a particle size smaller than 10 μm. Then, 0.4 grams of Kelzan (CP Kelco) and 59.38 grams of demineralized water are added at room temperature while stirring. This results in a homogeneous suspension concentrate.

[0105] 6. Preparation of Conventional SC Formulations To compare the properties of conventional SC formulations and formulations according to the invention, the following conventional SC formulations were prepared: SC formulation with deltamethrin (SC200) (SC25, SC100), SC formulation with 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide (SC25, SC100), and SC wax formulation with deltamethrin (SC2.5%).

[0106] A SC formulation with deltamethrin and 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide was prepared as follows: The liquid ingredients shown in Table 3 were mixed, then the solids were added, and the mixture was stirred until a uniform suspension was formed. The uniform suspension was first coarsely ground and then finely ground. The result is a suspension in which 90% of the solid particles have a particle size of 10 μm or less. Kelzan and water are then added at room temperature with stirring. This results in a uniform suspension concentrate.

[0107] [Table 3] JPEG2024155923000005.jpg120150

[0108] An SC wax formulation with deltamethrin (SC 2.5%) was prepared according to Example 1 according to WO2016 / 001285A1.

[0109] 7. Comparison of biological contact effects against cockroaches using the WP formulation of the present invention and the conventional SC formulation Dilute spray solutions were prepared by dissolving a specified amount of the formulation in tap water.

[0110] A WP 20 formulation prepared according to Example 4 containing 20 g of active ingredient per 100 g formulation was used. 143 mg of the WP 20 formulation was dissolved in 50 ml of tap water and applied to an area of ​​1 square meter in a volume of 35 ml (corresponding to 20 mg, each 4 mg active ingredient / m 2 (ai / m 2 The mixture was transferred to a spraying robot that could spray evenly. The active ingredient was 4 mg / m 2 A 1:5 dilution of the stock solution was made for surface concentrations of 1. The surface was a glazed tile.

[0111] Also, 0.3 ml of the conventional SC 100 formulation prepared according to Example 6 (100 g active ingredient per liter) was added to 49.7 ml of tap water. 35 ml of this solution was sprayed onto 1 square meter with a spray robot, resulting in 20 mg, 4 mg active ingredient per m 2 The active ingredient was deposited at 4 mg / m 2 For surface concentrations of 1:5, a 1:5 dilution of the stock solution was made. The surface was a vitrified tile.

[0112] Control: As a negative control, 50 ml of pure tap water was transferred to the spray robot. 35 ml of tap water was sprayed over an area of ​​1 square meter. The surface sprayed was a vitrified tile.

[0113] Adult Periplaneta americana (American cockroach) insects were then placed on the dry surface of the vitrified tile for 30 minutes after a 24-hour drying period. The test insects were then removed from the surface and transferred to a clean container for further observation. The read-out times of the insects were 24 hours, 48 ​​hours and 72 hours after contact with the treated surface. Mortality was measured in percentage (%). In the examples, 100% mortality means that all test insects were killed, while 0% means that no mortality was observed. The results are shown in Table 4.

[0114] [Table 4]

[0115] 8. Comparison of biological contact effects against bedbugs using the WP formulation of the present invention and a conventional SC formulation A similar test as described in Example 7 was carried out using Cimex lectularius (bedbugs) instead of the American cockroach and the following formulation: WP 20 as described in Example 7.

[0116] Also, 0.3 ml of a conventional SC 100 formulation (100 g active ingredient / liter) prepared according to Example 6 was added to 49.7 ml of tap water. 35 ml of the solution was sprayed over 1 square meter with a spray robot, resulting in 20 mg, 4 mg active ingredient / m 2 The surface concentration was 4 mg active ingredient / m 2 Therefore, a 1:5 dilution of the original solution was made. The surface was a vitrified tile.

[0117] The control was the same as in Example 7. The results are shown in Table 5.

[0118] [Table 5]

[0119] 9. Comparison of the biological contact efficacy against mosquitoes with the WP formulation of the present invention and a conventional SC formulation A similar test as described in Example 7 was carried out using Anopheles funestus (malaria mosquito) instead of the American cockroach. The insect read-out time was 24 hours after contact with the treated surface. The following formulations were used: WP 20 as described in Example 7.

[0120] The WP 10 formulation having 10 g of active ingredient per 100 g formulation prepared in Example 4 was used. 285 mg of the WP 10 formulation was dissolved in 50 ml of tap water and applied in a volume of 35 ml (equivalent to 20 mg, 4 mg active ingredient / m2) per square meter area. 2 The robot was then moved to a spraying robot that could spray the area evenly over the entire surface, achieving a surface concentration of 4 mg active ingredient / m 2 Therefore, a 1:5 dilution of the stock solution was made. The surface was a vitrified tile.

[0121] Additionally, 1.15 ml of a conventional SC 25 formulation (25 g active ingredient per liter) prepared according to Example 6 was added to 48.85 ml of tap water. 35 ml of this solution was sprayed by a spray robot onto 1 square meter, resulting in 20 mg, 4 mg active ingredient / m 2 The active ingredient was deposited at 4 mg / m 2 For surface concentrations, a 1:5 dilution of the stock solution was made. The surface was a vitrified tile.

[0122] The control was the same as in Example 7. The results are shown in Table 6.

[0123] [Table 6]

[0124] 10. Comparison of biological contact effects against mosquitoes between the WP formulation of the present invention and the SC formulation of the present invention A similar test as described in Example 9 was carried out with Anopheles funestus (malaria mosquito). However, the formulation was sprayed onto the vitrified tiles via a glass nozzle and a compressed air pressure of 0.2 bar. The spray radius was adjusted so that 1 ml completely covered the test surface, which corresponds to 20 mg active ingredient / m2. 2 Equivalent to 4 mg active ingredient / m 2 or 0.8 mg active ingredient / m 2 For surface concentrations, 1:5 or 1:10 dilutions of the stock solution were made.

[0125] The following formulations were used: - WP10 as described in Example 9 and Example 4, respectively. - SC 100 as described in Example 7 and Example 5, respectively. The control was the same as in Example 7. The results are shown in Table 7.

[0126] [Table 7]

[0127] Taken together, Examples 7 to 9 show the improved contact biological efficacy of the formulations according to the invention compared to conventional formulations having the same active ingredient.

[0128] 11. Long-term efficacy against mosquitoes by the WP formulation of the present invention Vitrified and non-vitrified tiles were treated with the WP 10 and WP 20 formulations described in Example 9, and with the WP 5 based on broflanilide described in Example 4, and then stored at ambient conditions. An additional set of treated tiles was stored in a climate chamber at conditions of 27°C and 80% air humidity. Monthly contact bioassays showed that the insecticidal effect of the treated surfaces remained stable after a period of 28 weeks, regardless of storage conditions. Contact bioassays were performed as outlined in Example 9.

[0129] The results are shown in Table 8 (control was the same as in Example 7).

[0130] [Table 8]

[0131] 12. Long-term efficacy of the WP formulation of the present invention against mosquitoes Vitrified tiles were treated with the WP 10 formulation described in Example 9, based on 4-[(5S)-5-(3,5-dichloro-4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-1,2-oxazolidin-4-yl]-2-methylbenzamide described in Example 4, and then stored at ambient conditions. Contact bioassays showed that the insecticidal efficacy of the treated surfaces was stable after a period of 8 weeks. Contact bioassays were performed as outlined in Example 9.

[0132] The results are shown in Table 9 (as a control, the active ingredient was dissolved in acetone and sprayed onto the tiles, resulting in the formation of a crystalline residue as seen for SC).

[0133] [Table 9]

[0134] 13. Biological performance of known SC formulations of deltamethrin and “controlled release” formulations of deltamethrin in contact bioassays against mosquitoes As outlined in Example 9, a contact bioassay was conducted using the "controlled release" deltamethrin SC 2.5 wax formulation and the conventional SC 200 formulation (both prepared as described in Example 6).

[0135] The results are shown in Table 10 (control was the same as in Example 7).

[0136] [Table 10]

[0137] The results in Table 10 indicate that "controlled release" formulations are generally not suitable for obtaining optimal results in terms of contact and initial biological availability.

Claims

1. Insecticidal active ingredient-matrix material particles having a particle size d50 of 0.1 to 75 microns, wherein: a) At least one insecticidal active ingredient selected from the group consisting of isoxazoline, metadiamide, arylpyrazole heteroarylamide, and arylpyrazole arylamide, distributed in b) below, b) A matrix material comprising polymerized monomer units selected from the group of C7 to C12 unsaturated aromatic hydrocarbons, wherein the monomer units are selected from the group consisting of indene, methyl indene, phenol-modified indene, vinyltoluene, α-methylstyrene, styrene, dicyclopentadiene, and any combination thereof. Includes, The at least one insecticidal active ingredient has a melting point of 110°C or higher and a water solubility of 0.1% (w / v) or lower. The matrix material has a softening point at least 30°C lower than the melting point of the at least one insecticidal active ingredient. Insecticidal active ingredient-matrix material particles characterized by not showing a melting peak of the active ingredient when measured in a second heating cycle after being heated to a temperature at least 20°C higher than the melting point of at least one insecticidal active ingredient at a steady heating rate using differential scanning calorimetry.

2. The insecticidal active ingredient-matrix material particle according to claim 1, characterized in that, in a first heating cycle of differential scanning calorimetry, the at least one insecticidal active ingredient and the matrix material are heated at a steady heating rate to a temperature at least 20°C above the melting point of the at least one insecticidal active ingredient.

3. The insecticidal active ingredient-matrix material particle according to claim 2, further characterized in that the maximum heating temperature of the first heating cycle is maintained for at least 10 minutes.

4. The insecticidal active ingredient-matrix material particle according to claim 2 or 3, further characterized in that at least one insecticidal active ingredient and matrix material are cooled at a steady cooling rate to a temperature of 0°C to 40°C between a first heating cycle and a second heating cycle.

5. The insecticidal active ingredient-matrix material particle according to any one of claims 1 to 4, characterized in that the weight ratio between the at least one insecticidal active ingredient and the matrix material is 1:99 to 1:

1.

6. The insecticidal active ingredient-matrix material particle according to any one of claims 1 to 5, characterized in that the at least one insecticidal active ingredient is selected from the group consisting of 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl]-1H-pyrazole-4-yl}-N-methylnicotinamide, brofranilide, and 4-[(5S)-5-(3,5-dichloro-4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazole-3-yl]-N-[(4R)-2-ethyl-3-oxo-1,2-oxazolidine-4-yl]-2-methylbenzamide.

7. The insecticidal active ingredient-matrix material particle according to any one of claims 1 to 6, characterized in that the molecular weight of the matrix material is 1 to 1000 kDa.

8. The following: a) Insecticidal active ingredient - matrix material particles according to any one of claims 1 to 7, b) One or more surfactants, c) Any further adjuvants selected from the group consisting of antifreeze, defoaming agents, preservatives, antioxidants, thickeners, colorants and binders, d) Liquid phase and / or filler A composition containing the following:

9. the below described: a) Insecticidal active ingredient according to any one of claims 1 to 7 - matrix material particles 1 to 70% by weight, b) 1-25% of one or more surfactants, c) 0 to 25% by weight of an adjuvant selected from the group consisting of antifreeze, defoaming agents, preservatives, antioxidants, thickeners, colorants, and binders. d) In all cases, liquid phase and / or filler added up to 100% by weight of the total composition. The composition according to claim 8, comprising:

10. The composition according to claim 8 or 9, in the form of a suspension concentrate (SC), water-dispersible granules (WG), or hydrated powder (WP), or a spray solution thereof.

11. Use of the insecticidal active ingredient-matrix material particles according to any one of claims 1 to 7 or the composition according to any one of claims 8 to 10 for knocking down, killing, or repelling pests, or any combination thereof (except in methods for treating humans).

12. A method for knocking down, killing, or repelling pests using the insecticidal active ingredient-matrix material particles described in any one of claims 1 to 7 or the composition described in any one of claims 8 to 10, or any combination thereof (excluding methods for treating humans).

13. The following method for identifying matrix materials for composition preparation by differential scanning calorimetry: a) At least one insecticidal active ingredient selected from the group consisting of isoxazoline, metadiamide, arylpyrazole heteroarylamide, and arylpyrazoarylamide, and the matrix material to be tested are heated at a steady heating rate to a temperature at least 20°C higher than the melting point of the at least one insecticidal active ingredient in the first heating cycle of the differential scanning calorimetry. b) Maintain the maximum heating temperature of the first heating cycle for at least 10 minutes. c) Next, lower the temperature to a temperature between 0°C and 40°C. d) In the second heating cycle step, the temperature is raised at a steady heating rate to a temperature at least 20°C higher than the melting point of the at least one insecticidal active ingredient. e) When measured in the second heating cycle of the differential scanning calorimetry method, if the combination of the insecticidal active ingredient and the matrix material does not show a melting peak, a useful matrix material is identified.

14. A method for increasing the contact efficacy of an insecticidal active ingredient selected from the group consisting of isoxazoline, metadiamide, arylpyrazole heteroarylamide, and arylpyrazoarylamide by using insecticidal active ingredient-matrix material particles according to any one of claims 1 to 7 or a composition according to any one of claims 8 to 10.