Insecticidal formulations with improved contact efficacy for vector control and pest control

Abstract

The present invention relates to an insecticidal formulation for the control of vectors and pests with improved contact efficacy, more specifically to an insecticidal active ingredient-matrix granule and to an insecticidal composition comprising such an insecticidal active ingredient-matrix granule, and to a method and the use of said insecticidal formulation.

Description

Background of the Invention

[0002] The use of pesticides to protect fruits, vegetables, and other crops from insects is widely recognized. In addition to these applications, the same types of active ingredients can also be used to protect people from disease-carrying insects such as mosquitoes (vector control) and insects known as sanitary pests outside the agricultural environment, such as cockroaches, flies, and bed bugs.

[0003] To protect people from these insects, pesticides are used to treat surfaces inside and around people's living and food processing environments. Because the contact time is typically short, relatively rapid ingestion of the pesticide is required. Compared to many agricultural applications, the control mechanism of the active ingredient in these types of applications is limited to contact efficacy. For example, oral ingestion does not occur when mosquitoes land and walk on treated surfaces. Therefore, only a limited number of pesticide types are effective for these treatments. Examples include pyrethroids, carbamates, organophosphates, and DDT. Clearly, the latter three are not preferred due to their toxicological properties to humans and the environment. On the other hand, pyrethroids have been used very extensively in vector control and specialized pest management over the past few decades, resulting in the development of strong resistance to this mode of action.

[0004] Some other insecticidal active ingredients have shown efficacy, and even resistance-breaking potential, in vector control and specialized pest management of related pests. However, due to their physicochemical properties, they exhibit only limited contact efficacy. The high melting point and molecular weight of these insecticidal active ingredients tend to form insoluble, highly crystalline structures. Therefore, insect uptake through contact is very limited, and known formulations such as conventional suspension concentrates—in which the insecticidal active ingredient exists in crystalline form—cannot effectively treat these insects.

[0005] On the other hand, the use of polymers and / or waxes as matrix materials in agricultural formulations is known. Many “controlled-release” formulations are based on this principle and have been documented in the literature. For example, US20060193882A discusses a formulation in which the agrochemical active ingredient is included in a polymer matrix to prolong residual bioefficacy. However, this approach reduces initial bioefficacy. Low initial bioefficacy is accompanied by low contact efficacy; therefore, such “controlled-release” formulations are generally not suitable for enhancing the contact efficacy of pesticide active ingredients when only a short contact time occurs. Detailed Implementation

[0006] Therefore, the object of the present invention is to provide technical formulation means to address problems identified in the prior art, particularly to develop the potential for complete contact and initial (rapid knockdown after contact) bioavailability of insecticidal active ingredients with challenging physicochemical properties. One specific object is to provide technical formulation means for insecticidal active ingredients that exhibit a high tendency to crystallize under normal conditions but generally have higher bioavailability against pests in an amorphous state. Another object is to provide technical formulation means for pest control, particularly cockroaches, mosquitoes, flies, bed bugs, etc., which exhibit high biocontact efficacy on various surfaces, such as flat, porous, or muddy surfaces. Yet another object is to provide technical formulation means for pest control that possesses resistance breakthrough potential, particularly pyrethroid resistance breakthrough potential.

[0007] It has now been found that this objective has been achieved, and a solution having an insecticidal active ingredient—matrix particles—is provided, as further described below.

[0008] The insecticidal active ingredient-matrix particles of the present invention relate to insecticidal active ingredient-matrix particles with a particle size d50 of 0.1 to 75 micrometers, which contain

[0009] a) at least one insecticidal active ingredient having a melting point equal to or higher than 110°C and a water solubility equal to or lower than 0.1%, and wherein at least one insecticidal active ingredient is distributed in b).

[0010] b) A matrix material containing wax.

[0011] The particle size of the insecticidal active ingredient-matrix particles of the present invention is preferably 0.1 to 75 micrometers, more preferably 0.5 to 50 micrometers, and even more preferably 1 to 25 micrometers. Preferably, the D50 value is determined by laser diffraction after the insecticidal active ingredient-matrix particles of the present invention are dispersed in an aqueous phase.

[0012] The insecticidal active ingredient-matrix particles of the present invention comprise at least one insecticidal active ingredient having a melting point equal to or higher than 110°C, preferably equal to or higher than 120°C, more preferably equal to or higher than 130°C, even more preferably equal to or higher than 140°C, and even more preferably equal to or higher than 150°C; and a water solubility equal to or lower than 0.1%, preferably equal to or lower than 0.01%, more preferably equal to or lower than 0.005%, and even more preferably equal to or lower than 0.001%. In another preferred embodiment of the present invention, the insecticidal active ingredient-matrix particles comprise an insecticidal active ingredient having the above-described physicochemical properties. The melting point of the present invention is measured under standard conditions (1 atm). Water solubility is expressed as a percentage, referring to the quotient of (g) grams of insecticidal active ingredient / 100 ml of water. Water solubility is preferably measured using liquid chromatography, for example using an HPLC-MS system (at 20°C, 1 atm and pH 7, see also Example 1 for reference).

[0013] 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 group.

[0014] More preferably, the at least one insecticidal active ingredient of the present invention is selected from isoxazoline, m-diamide, arylpyrazolium arylamide and arylpyrazolium arylamide, and / or has activity against γ-aminobutyric acid (GABA) receptors.

[0015] Isoxazolines are a class of compounds active against arthropods, insects, and ectoparasites in plant protection. They are antagonists of the γ-aminobutyric acid (GABA) receptor. The binding sites of isoxazolines are at least partially different from those of cyclopentadiene and fipronil (WLShoop et 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 & Vectors 2017, 10, 530). Prominent examples of this class include, for example, lotilana, saralaner, 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-oxazolidine-4-yl]-2-methylbenzamide (CAS 1309959-62-3).

[0016] m-Diamides are a class of compounds used as γ-aminobutyric acid (GABA) receptor antagonists. A prominent example of this class is broflanilide. The binding site of desmethyl-broflanilide is at least partially different from that of cyclopentadiene and fipronil (T. Nakao, S. Banba Bioorganic & Medicinal Chemistry 2016, 24, 372–377).

[0017] Arylpyrazol-heteroarylamides and arylpyrazol-arylamides that may preferably be used in conjunction with the present invention are described, for example, in WO 2015 / 067647A1 and WO 2015 / 067646A1, which are incorporated herein by reference. Preferably, this class relates to 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,3,3,3-heptafluoroprop-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide.

[0018] In this context, the term "active against GABA receptors" preferably refers to the properties of chemical molecules that regulate the physiological activity of GABA receptors.

[0019] Depending on the active ingredient, the insecticidal active ingredient of the present invention may be in the form of a geometric and / or optically active isomer or a mixture of corresponding isomers with different compositions. These stereoisomers are, for example, enantiomers, diastereomers, or geometric isomers. Therefore, the present invention covers the use of pure stereoisomers and any mixtures of these isomers.

[0020] Even more preferably, the at least one insecticidal active ingredient of the present invention is selected from:

[0021] -2-Chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide (CAS 1771741-86-6),

[0022] - Brombutamide: 3-[benzoyl(methyl)amino]-N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-(trifluoromethyl)phenyl]-2-fluorobenzamide (CAS 1207727-04-5),

[0023] -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-oxazolidine-4-yl]-2-methylbenzamide (CAS 1309959-62-3),

[0024] -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-oxazolidine-4-yl]-2-methylbenzamide (CAS 2061933-86-4),

[0025] -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-oxazolidine-4-yl]-2-methylbenzamide (CAS 1429660-18-3),

[0026] -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-oxazolidine-4-yl]-2-methylbenzamide (CAS 1309958-03-9),

[0027] -sarolaner: 1-[6-[(5S)-5-(3,5-dichloro-4-fluorophenyl)-5-(trifluoromethyl)-4H-1,2-oxazol-3-yl]spiro[1H-2-benzofuran-3,3'-azacyclobutane]-1'-yl]-2-methylsulfonyl ethyl ketone (CAS 1398609-39-6),

[0028] -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),

[0029] -Lotilaner: 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 (CAS1369852-71-0),

[0030] - Afoxolaner: 4-[5-[3-chloro-5-(trifluoromethyl)phenyl]-5-(trifluoromethyl)-4H-1,2-oxazol-3-yl]-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]naphthyl-1-carboxamide (CAS 1093861-60-9).

[0031] Even more preferably, the "at least one" insecticidal active ingredient of the present invention is selected from:

[0032] -2-Chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide (CAS 1771741-86-6),

[0033] - Brombutamide: 3-[benzoyl(methyl)amino]-N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-(trifluoromethyl)phenyl]-2-fluorobenzamide (CAS 1207727-04-5),

[0034] -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-oxazolidine-4-yl]-2-methylbenzamide (CAS 1309959-62-3).

[0035] Most preferably, the "at least one" insecticidal active ingredient of the present invention is selected from 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide (CAS 1771741-86-6) and bromuconazole, 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-heptafluoroprop-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide (CAS 1771741-86-6).

[0036] In another embodiment, the insecticidal active ingredient-matrix particles of the present invention comprise at least one of the aforementioned insecticidal active ingredients, which are distributed in a matrix material as described herein, and preferably uniformly distributed in the matrix material as described herein. This distribution is preferably achieved by a heating step, wherein at least one insecticidal active ingredient and the matrix material are heated at 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 insecticidal active ingredient. The mixture is maintained at this temperature (e.g., for 10, 15, or 20 minutes) until the insecticidal active ingredient is uniformly distributed. The particle size of the insecticidal active ingredient-matrix particles can then be obtained using conventional grinding and / or milling methods using conventional mixers, mills, and / or grinders.

[0037] According to the present invention, the “matrix material” to be used is wax, which has a softening point under standard conditions preferably of 50 to 160°C, more preferably of 60 to 140°C, more preferably of 70 to 120°C, and even more preferably of 70 to 110°C.

[0038] As used in this article, the term "softening point" refers to the Vicat softening temperature or Vicat hardness, and is the determination of the softening point for materials without a definite melting point, such as waxes. A sample with a 1mm... 2 The temperature at which a flat-tipped needle with a circular or square cross-section penetrates the specimen to a depth of 1 mm is defined as the temperature. 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 largely equivalent.

[0039] Useful waxes preferably include plant waxes, such as cotton wax, carnauba wax, candelilla wax, jasmine wax, and sugarcane wax; animal waxes, such as beeswax, lanolin wax, and shellac wax; and mineral waxes, such as pure ceresin, ceresin wax, and lignite wax. Furthermore, according to the invention, chemically modified waxes, such as hydrogenated jojoba wax, lignite wax, and / or fully synthetic waxes, such as polyalkylene waxes, polyethylene glycol waxes, amide waxes, Fischer-Tropsch paraffin wax, and / or fluorocarbon waxes, can be used.

[0040] Other suitable waxes according to the invention are hydrogenated and non-hydrogenated fats such as triglycerides, or fatty acids such as stearin, coconut oil, or hydrogenated oils such as hydrogenated palm oil or hydrogenated castor oil.

[0041] According to the present invention, the wax can be used in coarse crystalline, microcrystalline or amorphous form.

[0042] According to the present invention, carnauba wax and lignite wax are particularly preferred as matrix materials. Carnauba wax is especially preferred.

[0043] Examples of particularly preferred waxes are carnauba wax (from Mosselmann), Licowax S, or Licowax KSL (from Clariant).

[0044] Another embodiment of the present invention relates to insecticidal active ingredient-matrix material particles having the above-mentioned particle size, comprising

[0045] a) at least one insecticidal active ingredient having a melting point equal to or higher than 110°C and a water solubility equal to or lower than 0.1%, and wherein at least one insecticidal active ingredient is distributed in b).

[0046] b) A matrix material, preferably wherein the softening point of the matrix material is at least 30°C lower than the melting point of the at least one insecticidal active ingredient.

[0047] The characteristic feature is that, in the second heating cycle measurement, after heating to a temperature at least 20°C higher than the melting point of the at least one insecticidal active ingredient using differential scanning calorimetry at a stable heating rate of preferably 5 to 15°C / min and more preferably 10°C / min, the insecticidal active ingredient-matrix material particles do not exhibit a melting peak of the active ingredient.

[0048] In this regard, the "matrix material" is preferably wax. Preferred wax matrix materials have been further described above.

[0049] Another embodiment of the present invention relates to insecticidal active ingredient-matrix material particles as described above, characterized in that, in the first heating cycle of scanning calorimetry, the "at least one" insecticidal active ingredient and the matrix material are heated to a temperature at least 20°C, preferably at least 20°C but not more than 50°C, higher than the melting point of the at least one insecticidal active ingredient at a stable heating rate of preferably 5°C to 15°C / min and more preferably 10°C / min.

[0050] In a preferred version of differential scanning calorimetry as described above, the maximum heating temperature of the first heating cycle is maintained for at least 10 minutes, preferably 15 minutes, and more preferably 20 minutes.

[0051] In another preferred embodiment of the invention, between the first and second heating cycles of differential scanning calorimetry and preferably after the second heating cycle, the at least one insecticidal active ingredient and the matrix material are each cooled to a temperature of 0°C to 40°C, preferably 15°C to 35°C, and more preferably 20°C to 30°C at a stable cooling rate of 5°C to 15°C / min and more preferably 10°C / min.

[0052] As used herein, the term "steady heating rate" refers to a constant increase in temperature per minute. Therefore, the increase in temperature over time is preferably linear.

[0053] Similarly, as used herein, the term "steady cooling rate" refers to a constant temperature decrease per minute. Therefore, the temperature decrease over time is preferably linear.

[0054] As used herein, the term "melting peak" preferably refers to an endothermic signal in a differential scanning calorimetry (DSC) thermogram. The basic principle of this technique is that when a sample undergoes a physical transformation, such as a phase transition, more or less heat is required to flow to it than to a reference to maintain 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, as a solid sample melts into a liquid, more heat is required to flow to the sample to raise its temperature at the same rate as the reference. This is because the sample absorbs heat during the endothermic phase transition from solid to liquid.

[0055] A preferred embodiment of the present invention relates to insecticidal active ingredient-matrix material particles as described above, characterized in that, in the first heating cycle of scanning calorimetry, the at least one insecticidal active ingredient and the matrix material are heated to a temperature at least 10°C higher than the softening point of the matrix material and at least 20°C lower than the melting point of the at least one insecticidal active ingredient at a stable heating rate preferably 5°C to 15°C / min and more preferably 10°C / min.

[0056] Because the refractory tiles used in DSC experiments are very small and convection / stirring cannot be applied to fully mix the components (matrix material and insecticidal active ingredient), mixing is only kinetically controlled. This can lead to false negative results when searching for compatible matrix materials. If such mixing does not occur spontaneously at a temperature at least 10°C higher than the softening point of the matrix material and at least 20°C lower than the melting point of the at least one insecticidal active ingredient, a longer waiting time should be applied (preferably maintaining the maximum heating temperature of the first heating cycle for at least 30 minutes, more preferably 60 minutes, or even more preferably 120 minutes), or the first heating cycle should be conditioned by heating to a temperature at least 20°C higher than the melting point of the insecticidal active ingredient to ensure uniform distribution. An effective method to determine whether mixing in the refractory tile will occur spontaneously or whether the matrix material is suitable is the enthalpy of melting of the insecticidal active ingredient. The fraction of dissolved insecticidal active ingredient can be determined by comparing the enthalpy of melting of the separated insecticidal active ingredient with the enthalpy of melting of the possible peak that appears during the second heating cycle. If only part of the insecticidal active ingredient dissolves, it is preferable to adjust the first heating cycle of the DSC by heating to a temperature at least 20°C higher than the melting point of the insecticidal active ingredient in order to determine whether the matrix material is suitable.

[0057] Another embodiment of the present invention relates to insecticidal active ingredient-matrix material particles as described herein, characterized in that the weight ratio of the at least one insecticidal active ingredient to the matrix material is 1:99 to 1:1, preferably 5:95 to 40:60.

[0058] The concentration of the insecticidal active ingredient in the resulting insecticidal composition—specifically in the matrix material particles—depends on the required dose rate of the insecticidal active ingredient per square meter of treated surface. However, such products are typically sprayed using a 10-liter backpack sprayer, which can treat 250 square meters. 2 The surface. For this 10-liter backpack spray solution, use 25 to 250 grams of the product, preferably 50 to 150 grams.

[0059] The concentration of the insecticidal active ingredient per square meter is typically 1 to 500 mg / m². 2 And more preferably 2 to 200 mg / m 2 .

[0060] Another embodiment of the present invention relates to an insecticidal composition, wherein the insecticidal composition comprises:

[0061] a) Insecticidal active ingredient-matrix material particles as described herein, preferably 1 to 70% by weight, more preferably 5 to 60% by weight, and even more preferably 10 to 50% by weight.

[0062] b) At least one surfactant, preferably said surfactant is present in 1 to 25% by weight, more preferably 2 to 25% by weight, and even more preferably 2.5 to 15% by weight.

[0063] c) Optional other additives selected from antifreeze agents, defoamers, preservatives, antioxidants, thickeners, and colorants, preferably 0 to 25% by weight, more preferably 0.1 to 20% by weight, and even more preferably 0.5 to 10% by weight.

[0064] d) Liquid phase (which in any case totals 100% by weight of the total insecticidal composition).

[0065] Suitable surfactants are all such substances that are commonly used in agrochemical compositions. Conventional emulsifiers, especially wax emulsifiers, are suitable for this purpose. Nonionic wax emulsifier 4106 (from Clariant) – a mixture of alkyl ethoxylates – is particularly preferred.

[0066] Other surfactants that can be used according to the invention are nonionic surfactants, particularly selected from the following: polyethylene oxide-polypropylene oxide block copolymers, polyethylene glycol ethers of linear alcohols, reaction products of fatty acids with ethylene oxide and / or propylene oxide, and polyvinyl alcohol, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinylpyrrolidone, copolymers of polyvinyl acetate and polyvinylpyrrolidone, copolymers of (meth)acrylic acid and (meth)acrylate, additional alkyl ethoxylates and alkyl aryl ethoxylates that may be optionally phosphorylated and optionally neutralized with a base, polyoxyamine derivatives, and nonylphenol ethoxylates. Nonionic surfactants selected from the following are particularly preferred: polyethylene glycol ethers of linear alcohols and reaction products of fatty acids with ethylene oxide or propylene oxide.

[0067] Other surfactants that can be used according to the invention are anionic surfactants, particularly alkali metal salts and alkaline earth metal salts selected from alkyl sulfonic acids or alkyl aryl sulfonic acids. Particularly preferred anionic surfactants are salts of polystyrene sulfonic acid, salts of polyethylene sulfonic acid, salts of naphthalene sulfonic acid-formaldehyde condensation products, salts of condensation products of naphthalene sulfonic acid, phenol sulfonic acid and formaldehyde, and salts of lignin sulfonic acid.

[0068] The antifreeze agents suitable for use in the insecticidal compositions of the present invention are all those substances commonly used for this purpose in agricultural chemical compositions. Urea, glycerol, and propylene glycol are preferred.

[0069] The defoamers suitable for use in the insecticidal compositions of the present invention are all those substances commonly used for this purpose in agricultural chemical compositions. Silicone oil and magnesium stearate are preferred.

[0070] Preservatives suitable for use in the insecticidal compositions of the present invention are all those substances commonly used for this purpose in agricultural chemical compositions. Examples include... (from Bayer AG) and

[0071] The antioxidants suitable for use in the insecticidal compositions of the present invention are all those substances commonly used for this purpose in agrochemical compositions. Butylated hydroxytoluene (2,6-di-tert-butyl-4-methylphenol, BHT) is preferred.

[0072] Thickeners suitable for use in the insecticidal compositions of the present invention are all those substances commonly used for this purpose in agricultural chemical compositions. Preferred are silicates (e.g., from Engelhard). 50) or xanthan gum (e.g., from Kelko) ).

[0073] Colorants suitable for use in the insecticidal compositions of the present invention are all those substances commonly used for this purpose in agricultural chemical compositions. Examples include titanium dioxide, carbon black, zinc oxide, and blue pigments and permanent red FGR.

[0074] The preferred insecticidal composition is in the form of a suspension concentrate (SC) or a spray solution thereof.

[0075] Typically, surprisingly, the insecticidal compositions of the present invention remain stable even after prolonged storage (2 weeks) at high temperatures (54°C) or under cold conditions, and no crystal growth is observed. The SC formulation can be converted into a uniform spray solution by dilution with water.

[0076] For suspension concentrate (SC) formulations, a liquid phase is necessary, and water is preferred.

[0077] For SC formulations based on the insecticidal active ingredient-matrix material particles of the present invention, the insecticidal composition preferably contains one or more surfactants, preferably 2 to 20% by weight, more preferably 2.5 to 10% by weight.

[0078] For SC formulations, the insecticidal composition preferably contains (as characteristic (c)) an adjuvant selected from antifreeze agents, defoamers, preservatives, antioxidants and thickeners, preferably 0.1 to 20% by weight.

[0079] The SC formulation of the present invention is prepared by mixing the components with each other in a specific desired proportion. The components can be mixed in any order; if a thickener is present, it is preferably added after the grinding process. Conveniently, the solid components are used in a finely ground state. However, the suspension formed after mixing the components can also be coarsely ground first, and then finely ground to achieve the same d50 for the insecticidal active ingredient-matrix material particles as for the other components. Therefore, the particle size d50 of all components in the SC formulation is 0.1 to 75 micrometers, more preferably 0.5 to 50 micrometers, and even more preferably 1 to 25 micrometers. Conventional mixers, mills, and grinders used for preparing agricultural chemical formulations are suitable for preparing SC.

[0080] When preparing SC formulations, the temperature can vary within a certain range. Typically, the process is carried out at a temperature of 10°C to 60°C, preferably 15°C to 45°C, and at normal pressure.

[0081] Another embodiment of the invention relates to the use of insecticidal active ingredient-matrix material particles or insecticidal compositions as described herein for the control of pests, particularly insects and / or arachnids (preferably Acari), and especially mosquitoes, flies, mites, ticks, lice, ants, termites and cockroaches.

[0082] The pests are preferably controlled by contacting them with insecticidal active ingredient-matrix material particles as described herein or insecticidal compositions as described herein. Oral ingestion is preferably not required. The term "pest control" refers to the possibility of knocking down, killing, and / or repelling pests.

[0083] The insecticidal active ingredients-matrix material particles or insecticidal compositions described herein are preferably used outside of agricultural environments, particularly for vector control and specialized pest management applications.

[0084] For the purposes of this invention, a vector is an arthropod, particularly an insect or arachnid, capable of transmitting pathogens (e.g., viruses, worms, single-celled organisms, and bacteria) from a reservoir (plant, animal, human, etc.) to a host. Pathogens can be mechanically transmitted to the host (e.g., trachoma transmitted by a non-stinging fly) or transmitted to the host after injection (e.g., Plasmodium transmitted by mosquitoes).

[0085] Examples of the vectors, diseases, or pathogens they transmit include:

[0086] 1) Mosquitoes: Anopheles mosquitoes: malaria, filariasis; Culex mosquitoes: Japanese encephalitis, other viral diseases, filariasis, transmission of other worms; Aedes mosquitoes: yellow fever, dengue fever, other viral diseases, filariasis;

[0087] - Simuliidae: transmission of worms, especially Onchocerca volvulus; Psychodidae: transmission of leishmaniasis;

[0088] 2) Lice: skin infections, epidemic typhus;

[0089] 3) Fleas: plague, endemic typhus, tapeworms;

[0090] 4) Flies: Sleeping sickness (trypanosomiasis); cholera, other bacterial diseases;

[0091] 5) Mites: Mite infestation, epidemic typhus, rickettsial pox, tularemia, St. Louis encephalitis, tick-borne encephalitis (TBE), Crimean-Congo hemorrhagic fever, borreliosis;

[0092] 6) Ticks: Borellioses such as Borrelia bungdorferi sensu lato., Borrelia duttoni, tick-borne encephalitis, Q fever (Coxiella burnetii), babesiosis (Babesia canis subspecies), ehrlichiosis.

[0093] Examples of disease vectors in this invention are insects capable of transmitting plant viruses to plants, such as aphids, flies, leafhoppers, or thrips. Other disease vectors capable of transmitting plant viruses include spider mites, lice, beetles, and nematodes.

[0094] Other preferred examples of vectors in the sense of this invention are insects and arachnids capable of transmitting pathogens to animals and / or humans, such as mosquitoes, especially those of the genera *Aedes*, *Anopheles*, such as *Anopheles gambiae*, *Anopheles arabiensis*, *Anopheles funestus*, *Anopheles dirus* (malaria), and *Culex*; midges of the family *Psychodidae* such as *Phlebotomus* and *Lutzomyia*; lice; fleas; flies; mites and ticks.

[0095] The insecticidal active ingredient-matrix material particles or the insecticidal composition described herein are suitable for the prevention of vector-borne diseases and / or pathogens. Therefore, another aspect of the invention is the use of the active compound complexes of the invention for vector control, for example in agriculture, horticulture, gardens and recreational facilities, and in the protection of materials and stored products.

[0096] In addition, the insecticidal active ingredient-matrix material particles as described herein or the insecticidal composition as described herein are suitable for professional pest management applications targeting common pests found in home environments and public / commercial locations, such as cockroaches, mosquitoes, ants, mites, flies, stored product pests, occasional pests, termites, etc.

[0097] Various strategies are used for professional pest management to reduce pest numbers to acceptable levels.

[0098] Examples of common pest types found in or around homes and public / commercial premises include:

[0099] 1) Cockroaches: American cockroach (Periplaneta americana), German cockroach (Blatella Germanica), brown-banded cockroach (Supella longipalpa), and oriental cockroach (Blatta orientalis);

[0100] 2) Mosquitoes (see Vector Control);

[0101] 3) Ants: Black house ants, scented garden ants, fire ants / invasive red imported fire ants, ghost ants, pharaoh ants, white-legged ants;

[0102] 4) Mites: dust mites, dirt mites;

[0103] 5) Flies: filth flies or houseflies and their close relatives (Muscidae), flesh flies (Sarcophagidae), bottle flies and green bottle flies (Calliphoridae), black flies (Simuliidae), horseflies and deer flies (Tabanidae), fruit flies (Drosophilidae);

[0104] 6) Pests of stored products: Primary coleopteran (beetle) pests include grain weevils (Sitophilus granarius, S. zeamais, S. oryzae), grain borers (Rhyzoperthadominica), and saw beetles (Oryzaephilus surinamensis). Secondary beetle pests include face weevils (Tribolium castaneum and T. confusaum). Major lepidopteran pests (moths) are minor; they regularly feed on processed foods and are therefore more common in home kitchens and pantries.

[0105] 7) Occasional pests: wood-boring insects, millipedes, booklice, clothes moths, gypsum beetles, flea flies, dog ticks, fleas, carpet beetles, black carpet beetles;

[0106] 8) Termites: Genus *Odontotermes* spp., *Microcerotermes* spp., *Coptotermes* spp., *Heterotermes* spp., *Reticulitermes* spp., *Zootermopsis* spp., *Cryptotermes* spp., *Incisitermes* spp., *Marginitermes*, etc.;

[0107] Another embodiment of the invention relates to a method for controlling pests using insecticidal active ingredient-matrix material particles as described herein or insecticidal compositions as described herein.

[0108] Another embodiment of the present invention relates to a method for identifying useful matrix materials for insecticidal compositions using differential scanning calorimetry:

[0109] a) In the first heating cycle of differential scanning calorimetry, the insecticidal active ingredient with a melting point equal to or higher than 110°C and a water solubility equal to or lower than 0.1% and the matrix material to be tested are heated to a temperature at least 20°C (preferably at least 20°C but not exceeding 50°C) higher than the melting point of the at least one insecticidal active ingredient, at a stable heating rate preferably 5°C to 15°C / min and more preferably 10°C / min.

[0110] b) Maintain 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.

[0111] c) Then cool the temperature to a temperature of 0°C to 40°C (preferably 15°C to 35°C, more preferably 20°C to 30°C).

[0112] d) In the second heating cycle step, the temperature is raised to a temperature at least 20°C higher than the melting point of the at least one insecticidal active ingredient at a stable heating rate preferably from 5°C to 15°C / min and more preferably from 10°C / min.

[0113] e) If the insecticidal active ingredient matrix material complex does not show a melting peak when measured in the second heating cycle of differential scanning calorimetry, it is identified as a useful matrix material.

[0114] When the first step a) is performed as follows, the particularly preferred matrix material is identified using DSC as described above:

[0115] Step a): In the first heating cycle of differential scanning calorimetry, the insecticidal active ingredient with a melting point equal to or higher than 110°C and a water solubility equal to or lower than 0.1% and the matrix material to be tested (preferably with a softening point at least 30°C lower than the melting point of the insecticidal active ingredient) are heated at a stable heating rate to a temperature at least 20°C lower than the melting point of the at least one insecticidal active ingredient (preferably at least 10°C higher than the softening point of the matrix material). However, as mentioned above, this procedure may lead to false negative results when searching for compatible matrix materials. Therefore, step e) of the above method needs to be adjusted, preferably as follows:

[0116] Step e): If the insecticidal active ingredient matrix material complex does not exhibit a melting peak when measured in the second heating cycle of differential scanning calorimetry, or if it does exhibit a melting peak of the insecticidal active ingredient, the useful matrix material is identified by comparing the enthalpy of melting of the insecticidal active ingredient measured alone in DSC (under the same heating conditions) with the enthalpy of melting of the insecticidal active ingredient observed in the second heating cycle of DSC for the insecticidal active ingredient matrix material complex.

[0117] By comparing the differences in melting enthalpy, the fraction of insecticidal active ingredients dissolved in the matrix material can be determined, thus allowing for the assessment of the matrix's suitability.

[0118] Another embodiment of the invention relates to a method that, compared with the contact efficacy of conventional suspension concentrate formulations with the same insecticidal active ingredient, improves the contact efficacy of an insecticidal active ingredient with a melting point equal to or higher than 110°C and a water solubility equal to or lower than 0.1% with insecticidal active ingredient-matrix material particles as described herein or insecticidal compositions as described herein.

[0119] Conventional suspension concentrates (SCs) are dispersions in water. These conventional SCs are known to be suitable for active ingredients with high melting points and insolubility in water. Conventional suspension concentrates are typically prepared by premixing the active ingredient powder in an aqueous solution of a wetting agent and a dispersant, followed by wet milling in a bead mill to obtain a particle size distribution of 1 to 10 micrometers. Other materials, such as thickeners, can then be added to modify the rheological properties of the system, reducing particle separation and sedimentation during storage. Typical wetting agents / dispersants used in conventional SCs include sodium lignosulfonate, sodium naphthalenesulfonate-formaldehyde condensate, aliphatic alcohol ethoxylates, tristyrylphenol ethoxylate phosphates, EO / PO block copolymers, and graft copolymers. Antifreeze agents such as urea, glycerol, or propylene glycol are used. Therefore, 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 (which in any case total 100% by weight of the total conventional SC formulation).

[0120] The invention will be described in more detail with reference to the following embodiments, but is not in any way limited to the forms of use described in the embodiments.

[0121] Example:

[0122] 1. Representative physicochemical properties of the insecticidal active ingredient used according to the present invention

[0123] Table 1:

[0124]

[0125]

[0126] As shown in Table 1, the recorded melting points were determined using industrial-grade active ingredients under normal conditions (1 atm) using differential scanning calorimetry (DSC) with a Mettler Toledo 822 or 823 DSC instrument. Samples were heated from 25°C to a maximum of 300°C in a perforated aluminum crucible at a heating rate of 3 K / min. Melting points were determined by first specifying a baseline for the temperature range to be evaluated. A tangent line was then drawn at the inflection point on the endothermic side of the peak, and the intersection of this line and the baseline was represented as the melting point of the substance under study.

[0127] As shown in Table 1, the recorded water solubility determinations were performed as follows: Preparation of calibration standards: A 1000 ppm solution of the analyte in acetonitrile was prepared, and at least three calibration points were obtained by diluting the solution to 0.01 mg / L with acetonitrile if necessary. Sample preparation: Approximately 0.6 mg of homogenized sample was filled into each of the two cavities of the deep well, and 500 μL of pH 7 phosphate buffer was added. Glass beads were added to each cavity, the deep well was sealed, and the solution was shaken at 1600 rpm at 23 °C for at least 24 hours. After the shaking process, the solution was filtered. Aliquots of the filtrate were analyzed using an HPLC-MS system equipped with DAD and MS detectors. The peak areas of all selected individual DADs and ion trajectories were used for calculations. The calculations were performed by external calibration (linear regression) of the standard sample areas. The average of all calculated values ​​gives the water solubility of the active ingredient.

[0128] 2. The suitability of the matrix material for the studied insecticidal active ingredient was determined using differential scanning calorimetry (DSC).

[0129] Using a differential scanning calorimeter (Mettler Toledo DSC 822e or 823DSC), a few milligrams of matrix material and the insecticidal active ingredient under study were placed in a refractory plate and sealed.

[0130] The weight ratios of the matrix material and the insecticidal active ingredient are as follows:

[0131] Table 2:

[0132]

[0133]

[0134] Use an empty, sealed refractory board as a reference. After balancing in the machine, heat the two refractory boards according to the following procedure:

[0135] • Heating from 25°C to 130°C at a heating rate of 10°C / minute.

[0136] Wait 20 minutes.

[0137] • Cool to 25°C at a cooling rate of 10°C / minute.

[0138] • Heating from 25°C to 200°C at a heating rate of 10°C / minute.

[0139] • Cool to 25°C at a cooling rate of 10°C / minute.

[0140] If the weight ratio between the matrix material and the insecticidal active ingredient is not optimal, and for example, there is an excessive amount of insecticidal active ingredient, it cannot be uniformly distributed in the matrix material within a given time using the above procedure. The content of the insecticidal active ingredient can be reduced, and the procedure can be run again, or the maximum heating temperature can be maintained for a longer period, or the following procedure can be applied:

[0141] • Heat from 25°C to 200°C at a heating rate of 10°C / min (the upper limit temperature may vary depending on the melting point of the insecticidal active ingredient being studied, and should be 20°C higher than that melting point).

[0142] Wait 20 minutes.

[0143] • Cool to 25°C at a cooling rate of 10°C / minute.

[0144] • Heat from 25°C to 200°C at a heating rate of 10°C / min (the upper limit temperature may vary depending on the melting point of the insecticidal active ingredient being studied, and should be 20°C higher than that melting point).

[0145] • Cool to 25°C at a cooling rate of 10°C / minute.

[0146] result: For samples 1 to 3, no melting peak of the insecticidal active ingredient was detected during the second heating cycle of DSC, indicating that the matrix material is suitable for the insecticidal active ingredient under study. For sample 4, a melting peak of the insecticidal active ingredient was detected during the second heating cycle of DSC, indicating that the matrix material is not suitable for the insecticidal active ingredient under study.

[0147] Similar to the processes and procedures described above, other matrix material-insecticide conjugates have been studied using the insecticidal active ingredient, and matrix materials that do not exhibit melting peaks of the insecticidal active ingredient during the second heating cycle of DSC have been identified, as follows:

[0148] Insecticidal active ingredient: 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide combined with one of the following matrix materials: Licowax S or Licowax KSL (from Clariant).

[0149] 3. Preparation of insecticidal active ingredient-matrix particles

[0150] 30.0 g of 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide was added to 70.0 g of palm wax (Mosselmann). The mixture was stirred and heated to 130°C. This temperature was maintained while stirring until the active ingredient was uniformly distributed. The mixture was then cooled to room temperature.

[0151] The matrix active ingredient composition was obtained by grinding using a mixer (Braun Kuechenmaschine 3210 food processor) equipped with a cutting device.

[0152] Similar to this method, the same (or other) insecticidal active ingredients can be prepared. - Matrix particles (and those with other concentrations).

[0153] 4. Based on the insecticidal active ingredient prepared as in Example 3 - Preparation of Suspension Concentrate (SC) Formulations of Matrix Particles

[0154] For the preparation of SC 90, 300 grams of the insecticidal active ingredient according to Example 3 were used. - The matrix particles were mixed with 30.0 g of wax emulsifier 4106 (from Clariant), 5 g of aerosil 200 (Evonik), 0.4 g of Proxel GXL 20 (Lonza), and 1 g of Silcolapse 426R (Solvay), and the mixture was stirred until a homogeneous suspension was formed. The homogeneous suspension was first coarsely ground, then finely ground to form a suspension in which 90% of the solid particles had a particle size of less than 10 μm. Subsequently, 4 g of Kelzan (CP Kelco) and 659.6 g of softened water were added at room temperature with stirring. A homogeneous suspension concentrate was obtained.

[0155] 5. Preparation of conventional SC formulations

[0156] To compare the characteristics of the formulations of the present invention with those of conventional formulations, the following conventional SC formulations were prepared: an SC formulation containing deltamethrin (SC200), an SC formulation containing 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide (SC25, SC100), and an SC wax formulation containing deltamethrin (SC 2.5%).

[0157] The preparation of SC formulations containing deltamethrin and SC formulations containing 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide was as follows: The liquid components as shown in Table 3 were mixed, then the solids were added, and the mixture was stirred until a homogeneous suspension was formed. The homogeneous suspension was first coarsely ground, then finely ground to form a suspension in which 90% of the solid particles had a particle size of less than 10 μm. Subsequently, Kelzan and water were added at room temperature with stirring. A homogeneous suspension concentrate was obtained.

[0158] Table 3:

[0159]

[0160]

[0161] According to WO2016 / 001285A1, an SC wax formulation (SC 2.5%) containing deltamethrin was prepared according to Example 1.

[0162] 6. Comparing the bio-contact efficacy of the SC formulation of this invention with conventional SC formulations against mosquitoes. A diluted spray solution is prepared by dissolving a specific amount of the formulation in tap water.

[0163] The SC 90 formulation containing 9g active ingredient / 100g formulation, prepared according to Example 4, was used. An appropriate amount of the SC 90 formulation was dissolved in an appropriate amount of tap water and transferred to a spraying robot capable of uniformly spraying a 35ml volume onto an area of ​​1 square meter. The target is active ingredient / m 2 (abbreviated as ai / m) 2 The surface concentration was 4 mg, and this target was achieved. The sprayed surface was glazed tile.

[0164] In addition, an appropriate amount of the conventional SC 25 formulation (25g active ingredient / L) prepared according to Example 5 was added to an appropriate amount of tap water.

[0165] Using a spray robot, 35 ml of the solution was sprayed onto 1 square meter to obtain 4 mg of active ingredient / m². 2 The surface is glazed tile.

[0166] Control: 50 ml of pure tap water was transferred to the spray robot as a negative control. 35 ml of tap water was sprayed over an area of ​​1 square meter. The sprayed surface was glazed tile.

[0167] Then, after a 24-hour drying period, Anopheles bauhinia (malaria mosquito) insects were placed on the dry surface of the glazed tile for 30 minutes. Afterward, the test insects were removed from the surface and transferred to a clean container for further observation. The insect readout time was 24 hours after contact with the treated surface. Mortality was measured as a percentage (%). In this example, 100% mortality meant that all test insects had died, while 0% meant that no mortality was observed. The results are shown in Table 4.

[0168] Table 4:

[0169]

[0170] Compared to conventional SC formulations (SC 25) with the same surface concentration of the same active ingredient, the SC formulation (SC 90) of the present invention exhibits better bio-contact efficacy against mosquitoes.

[0171] 7. In contact bioassays for mosquito resistance, known SC formulations containing deltamethrin and formulations containing deltamethrin... Biological properties of controlled-release formulations .

[0172] Similar to that described in Example 6, contact bioassays were performed using controlled-release deltamethrin SC 2.5 wax formulation and conventional SC 200 formulation, both prepared as described in Example 5. The results are shown in Table 5 (the controls are the same as in Example 6).

[0173] Table 5:

[0174]

[0175] The results in Table 5 indicate that controlled-release formulations are generally not suitable for achieving optimal results in terms of contact efficacy and initial biological efficacy.

Claims

1. An insecticidal active ingredient-matrix material particle having a particle size d50 of 0.1 to 75 micrometers, comprising... a) at least one insecticidal active ingredient selected from 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylnicotinamide, brofenoxamidine, 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-oxazolidine-4-yl]-2-methylbenzamide, wherein the at least one insecticidal active ingredient is distributed in b). b) A wax-containing matrix material, wherein the softening point of the matrix material is at least 30°C lower than the melting point of the at least one insecticidal active ingredient, and wherein, In the second heating cycle measurement, after heating to a temperature at least 20°C higher than the melting point of the at least one insecticidal active ingredient at a stable heating rate using differential scanning calorimetry, the insecticidal active ingredient-matrix material particles did not show a melting peak of the active ingredient.

2. The insecticidal active ingredient-matrix material particles according to claim 1, characterized in that, The weight ratio of the at least one insecticidal active ingredient to the matrix material is 1:99 to 1:

1.

3. An insecticidal composition comprising the insecticidal active ingredient-matrix material particles according to claim 1 or 2, wherein the insecticidal composition contains... a) Insecticidal active ingredient-matrix material particles according to claim 1 or 2, b) One or more surfactants, c) Other additives optionally selected from antifreeze, defoamers, preservatives, antioxidants, thickeners and colorants. d) Liquid phase.

4. The insecticidal composition according to claim 3, wherein the insecticidal composition comprises a) 1 to 70% by weight of the insecticidal active ingredient-matrix material particles according to claim 1 or 2, b) 1 to 25% by weight of one or more surfactants, c) 0 to 25% by weight of additives selected from antifreeze, defoamers, preservatives, antioxidants, thickeners and colorants. d) Liquid phase, which, in any case, is made up to 100% by weight of the total insecticidal composition.

5. The insecticidal composition according to any one of claims 3 to 4, wherein the insecticidal composition is in the form of a suspension concentrate (SC) or a spray solution thereof.

6. Use of the insecticidal active ingredient-matrix material particles according to claim 1 or 2, or the insecticidal composition according to any one of claims 3 to 5, for the control of pests.

7. A method for controlling pests, wherein the insecticidal active ingredient-matrix material particles according to claim 1 or 2 or the insecticidal composition according to any one of claims 3 to 5 are used.

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