Storage stability aqueous suspension concentrate
A pesticide composition combining SDHI and DMI fungicides with crystal growth inhibitors stabilizes formulations against Ostwald ripening, maintaining stability and flowability for extended periods, addressing the challenges of low-melting-point azole fungicides in aqueous suspension concentrates.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- BAYER AG
- Filing Date
- 2021-12-13
- Publication Date
- 2026-06-08
AI Technical Summary
Existing pesticide formulations face challenges with crystal growth due to Ostwald ripening, leading to undesirable properties such as reduced efficacy, increased dosage requirements, and clogging of application equipment, particularly in compositions containing low-melting-point azole fungicides like difenoconazole and fluopyram, which are difficult to stabilize in aqueous suspension concentrates.
A pesticide composition comprising succinate dehydrogenase inhibitors (SDHI) like fluopyram or isoflucipram, demethylation inhibitors (DMI) like difenoconazole, and crystal growth inhibitors, without using hydroxypropyl methylcellulose, to stabilize the formulation and prevent crystal growth, ensuring free-flowing stability for extended periods.
The composition effectively prevents crystal growth, maintaining stability and flowability for up to several years, enhancing storage life and preventing nozzle clogging while ensuring effective pest control.
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Abstract
Description
Technical Field
[0001] The present invention provides an aqueous suspension concentrate composition of a pesticide containing a bactericidal active ingredient suspended in water.
Background Art
[0002] background There is a continuing need to develop effective pest control formulations such as herbicides, fungicides, insecticides, herbicides, and nematicide formulations that exhibit desired properties including improved storage stability and storage life.
[0003] The storage stability of pesticide compositions can be adversely affected by many chemical and physical phenomena that cause crystal growth known as, for example, Ostwald ripening.
[0004] In pesticide compositions, crystal growth of compounds including agricultural active compounds in, for example, pest control compositions can result in undesirable properties. For example, lack of efficacy of the pest control agent, the need for increased dosage of the pest control agent, sub-optimal concentration of the active substance in the formulation, reduction in the storage life of the formulation, and / or blockage in the filters and nozzles used for application when the formulation is applied.
[0005] Crystal growth can occur by either of two mechanisms: (1) slow diffusion and / or (2) slow attachment. The rate of crystal / particle growth is determined by the slower process.
[0006] Furthermore, Ostwald ripening can be accelerated by temperature cycling.
[0007] There is a need to provide formulations of agricultural active ingredients suspended in water that do not undergo Ostwald ripening or that reduce or delay the occurrence of this phenomenon. There is also a continuing need to extend the storage life of agricultural formulations. Furthermore, there is always a need to increase the bioavailability of the active ingredient in the formulation, for example, by increased penetrability.
[0008] WO2017 / 121695 describes a combination of herbicide and carrier to prevent aggregation and improve redispersibility. US Prov.62 / 676518 describes the use of fluopyram and isoflucipram in combination with hydroxypropyl methylcellulose ether (HPMC) in aqueous suspension concentrates.
[0009] WO2015 / 124330 describes the use of hydroxypropyl methylcellulose ether (HPMC) in combination with xanthan gum or other polysaccharides, providing a storage-stable aqueous sterilized suspension concentrate. [Prior art documents] [Patent Documents]
[0010] [Patent Document 1] International Publication No. 2017 / 121695 [Patent Document 2] U.S. Provisional Application 62 / 676518 [Patent Document 3] International Publication No. 2015 / 124330 [Overview of the Initiative] [Problems that the invention aims to solve]
[0011] However, none of these studies describe the combination of azole fungicides such as difenoconazole with a penetration enhancer, or succinate dehydrogenase inhibitors ("SDHI") such as fluopyram or isoflucypram. Furthermore, such mixtures of fungicides lower the melting point of the corresponding active ingredients.
[0012] In particular, difenoconazole and fluopyram, as well as mixtures of difenoconazole and isoflucipram, have a melting point of only 65°C, which makes it extremely difficult to obtain crystal growth-stable aqueous suspension concentrates, as the tendency for crystal growth increases as the melting points of the active ingredients and their respective mixtures decrease. The melting points were measured using a Mettler DTA (open, nitrogen purged on aluminum, height 160 μL) with a nitrogen stream of 80 mL / min at a heating cycle of 3 K / min, 30–450°C. The weight ratios were 1:1 for difenoconazole:isoflucipram and 1:2 for difenoconazole:fluopyram.
[0013] Another object of the present invention was to include penetration enhancers in the formulation. These enhancers provide faster uptake of the active ingredient at higher concentrations with or without minimal loss of the active ingredient from the plant surface due to physical washing or splashing effects, but these penetration enhancers not only swell the waxy layer of the plant leaves but also solubilize the active ingredient in the formulation, so as the solubilization of the active ingredient occurs, the crystal growth behavior is further increased.
[0014] A further object of the present invention was to provide a formulation in which crystal growth of DMI and SDHI in the mixed formulation is prevented or significantly reduced.
[0015] DMI (demethylation inhibitors) or sterol biosynthesis inhibitors (SBIs) fungicides belong to FRAC code 3, which includes triazoles and imidazoles. DMIs act by inhibiting the biosynthesis of ergosterol, a major component of the plasma membrane of certain fungi and necessary for fungal growth. Fungal resistance to DMI fungicides is characterized and is generally known to be controlled by several independent mutations in the fungi, or by the accumulation of what is known as "sequential selection" or "shift."
[0016] Therefore, in preferred embodiments, DMI and SDHI (succinate dehydrogenase inhibitor) are used in combination as an aqueous suspension concentrate. None of the above-mentioned literature describes the use of DMI and SDHI aqueous formulations that reduce crystal growth with a combination of low-melting-point active ingredients, particularly without using hydroxypropyl methylcellulose, and preferably with a penetration enhancer in the formulation.
[0017] In one embodiment, a penetration enhancer is essential.
[0018] In one embodiment of the present invention, the pesticide composition comprises, as an active ingredient, at least one DMI and at least one succinate dehydrogenase inhibitor ("SDHI" / FRAC class C2). Succinate dehydrogenase ("SDH") is an enzyme complex found in the inner mitochondrial membrane of eukaryotes and in many bacterial cells. SDH is involved in both the citric acid cycle and the electron transport chain. In the citric acid cycle, SDH catalyzes the oxidation of succinates to fumarates by coupling with the reduction of ubiquinone to ubiquinol. This catalytic action occurs in the inner mitochondrial membrane.
[0019] In pest control compositions such as suspensions and other agricultural chemical compositions, crystal growth of the active ingredient can result in a thicker, more viscous composition. In fluopyram suspension concentrates, for example, long, needle-shaped crystals are observed, leading to solidification of the suspension concentrate during storage. Furthermore, the needle-shaped particles or precipitates tend to clog nozzles and pipes, which presents problems during application.
[0020] In difenoconazole formulations and other DMI-based fungicides, rather flat crystals that grow over time are observed. Furthermore, these growing crystals tend to aggregate with the grown needle-shaped crystals of SDHI. Therefore, finding a non-aggregating recipe is a challenge.
[0021] The present invention solves the above-mentioned problems. [Means for solving the problem]
[0022] In particular, in one embodiment of the present invention, the combination of low melting point DMI and SDHI suspended in water can be stabilized with respect to crystal growth, and in one embodiment, said stabilization is achieved without using hydroxypropyl methylcellulose (HPMC) as a crystal growth inhibitor (which is also a crystal growth inhibition carrier).
[0023] In another aspect of the present invention, the present invention relates to a composition comprising at least one succinate dehydrogenase inhibitor, one DMI, one penetration enhancer and at least one crystal growth inhibitor.
[0024] In yet another aspect of the present invention, the present invention relates to a composition comprising at least one succinate dehydrogenase inhibitor, one DMI, one penetration enhancer, at least one binder and at least one crystal growth inhibitor.
[0025] The present invention further relates to a method for controlling or reducing pests including nematodes, insects, and fungal spores in plants or crops, which comprises applying a composition comprising the above recipe to a plant or its habitat.
[0026] Further objects, features and advantages of the present invention will become apparent from the following detailed description.
Embodiments for Carrying Out the Invention
[0027] Detailed explanation The present applicants have found that the pesticidal composition of the present invention exhibits reduced crystal growth, thereby increasing the storage life of the composition, while effectively controlling plant pests such as insects, nematodes, and fungi and fungal spores, and at the same time, the composition exhibits enhanced penetration / uptake properties.
[0028] "Controlling" means a preventive, therapeutic, or curative reduction of damage compared to untreated plants, more preferably the infestation is essentially avoided, and most preferably fungal, insect, and / or nematode infestation is completely suppressed. The composition may be applied preventively before fungal, insect, or nematode infestation and / or after infestation to cure or control the infestation.
[0029] The term "fungus" should be understood to mean all species of fungi, as well as all fungal-like organisms, including oomycetes.
[0030] The term "fungal spores" should be understood to refer to all spores produced by all species of fungi and fungal-like organisms (including oomycetes).
[0031] "Crystal growth" should be understood as an increase in crystals or particle size in a fungicide or other pesticide composition, resulting from Ostwald ripening or other phenomena.
[0032] In one embodiment, the disclosure provides a composition in which crystal growth is inhibited such that the composition does not gel and remains free-flowing for at least 7 days, or at least 14 days, or at least 21 days, or at least 28 days after manufacture and storage at high temperatures (i.e., 40°C and / or 45°C). In another embodiment, the formulation should be stable and maintain free flow for at least 6 months, or at least 1 year, or at least 2 years after manufacture under ambient storage conditions or at room temperature, where room temperature in this application is 20°C unless otherwise specified.
[0033] In one embodiment, the disclosure provides a composition that can extend its shelf life beyond two years, or beyond three years, or beyond five years, and maintain free flow without exhibiting significant crystal growth or deposit accumulation.
[0034] In another embodiment, the disclosure provides a method for preventing, reducing, or eliminating crystal growth in a composition, such as a composition comprising one or more SDHIs as active ingredients, where at least one crystal growth inhibitor is added to the composition, one DMI, and one penetration enhancer.
[0035] Therefore, the object of the present invention is a pesticide composition comprising the following: a) At least one SDHI fungicide, b) At least one DMI fungicide, c) at least one crystal growth inhibitor c1) and optionally at least one further crystal growth inhibitor c2 and / or c3), d) At least one ionic dispersant selected from lignin and / or naphthalene-based sulfonates and polymer condensates, e)d) at least one additional emulsifier and / or dispersant, different from the above, f) At least one penetration enhancer, g) Optionally, further additives such as colorants, thickeners, defoamers, and antifreezes. h) Optionally, additional pest control agents different from (a) and (b), and i) Up to 100% water. In one embodiment, at least one crystal growth inhibitory support c1) and at least one crystal growth inhibitory support c2 are present in the composition. In one embodiment, at least one crystal growth inhibitory support c1), at least one crystal growth inhibitory support c2), and at least one crystal growth inhibitory support c3) are present in the composition. In one embodiment, components g) and / or i) are essential and not optional. In a preferred embodiment, at least one component g) is a binder. In a preferred embodiment, the composition does not contain HPMC as CGI c). SDHI is most preferably selected from the group consisting of fluopyram and isoflucipram. DMI is most preferably difenoconazole. In one embodiment, the combined melting point of compounds a) and b) is 50 to 120°C, preferably 50 to 90°C, more preferably 55 to 80°C, even more preferably 58 to 70°C, and most preferably 59 to 68°C. In another preferred embodiment, the composition does not contain further pest control agents. Percentages (unless otherwise specified) should be considered weight percentages, and the weight percentages of the composition should total 100. The following proportions of individual components are based on the total weight of the composition, and when these proportions are added together, they represent 100% of the entire composition, which is composed of component i) (solvent). The proportion of SDHI bactericide a) in the composition according to the present invention is, Preferably 2 to 80% by weight, More preferably 5 to 50% by weight, More preferably, 8-35% by weight, and Most preferably, it is 10 to 30% by weight. The proportion of DMI bactericide b) in the composition according to the present invention is, Preferably 2 to 50% by weight, More preferably 3 to 35% by weight, Comfortably 5-25% by weight, Most preferably, it is 8-20% by weight. Furthermore, the total of a) and b) and any further pest control agents is preferably 15-80% by weight, more preferably 20-70% by weight, and most preferably 30-50% by weight. The proportion of crystal-inhibiting carrier c1) in the composition according to the present invention is, Preferably 0.1 to 10% by weight, More preferably 0.2 to 8% by weight, More preferably 0.3 to 3% by weight, and Most preferably, it is 0.4 to 1.5% by weight. The proportion of crystal-inhibiting support c2) in the composition according to the present invention is, Preferably 0-10% by weight, More preferably 0.1 to 8% by weight, More preferably 0.3 to 3% by weight, and Most preferably, it is 0.4 to 1.5% by weight. The proportion of crystal-inhibiting support c3) in the composition according to the present invention is, Preferably 0-10% by weight, More preferably 0.05 to 3% by weight, Comfortably 0.1 to 1% by weight, Most preferably, it is 0.1 to 1.0% by weight. The proportion of dispersant d) in the composition according to the present invention is, Preferably 0.2 to 5% by weight, More preferably 0.3 to 2.5% by weight, More preferably 0.7 to 2.0% by weight, and The most preferred amount is 0.8–2.0% by weight. The proportion of one additional emulsifier and / or dispersant e) in the composition, different from d), Preferably 0.5 to 10% by weight, More preferably 0.7 to 8% by weight, Comfortably 1.5-5% by weight, and Most preferably, it is 2-4% by weight. The proportion of the penetration enhancer f) (component g) -if present- in the composition according to the present invention is, Preferably 3 to 25% by weight, More preferably 4-15% by weight, Comfortably 5-12% by weight, Most preferably, it is 7-11% by weight. The proportion of further additives g) in the composition according to the present invention (if present) is, Preferably 0-12% by weight, More preferably 0.1 to 10% by weight, More preferably 0.5 to 8% by weight, and Most preferably, it is 1 to 6% by weight. The proportion of further pest control agents h) -if present-in the composition according to the present invention is, Preferably 0-20% by weight, More preferably 5-15% by weight, A more preferable percentage is 5-15% by weight. A preferred embodiment of the present invention is a component a) 2~80% by weight b) 2~50% by weight c1) 0.1~10% by weight c2) 0.1~8wt% d) 0.2~5% by weight e) 0.5~10% by weight f) 3~25% by weight g) 0~12% by weight h) 0~20% by weight i) Up to 100 It is a composition containing [the specified ingredient]. A more preferred embodiment of the present invention is a component a) 2~80% by weight b) 2~50% by weight c1) 0.1~10% by weight c2) 0.1~8wt% d) 0.2~5% by weight e) 0.5~10% by weight f) 3~25% by weight g) 0.1~10% by weight h) 0~15% by weight i) Up to 100 It is a composition containing [the specified ingredient]. A more preferred embodiment of the present invention is a component a) 2~80% by weight b) 2~50% by weight c1) 0.1~10% by weight c2) 0.1~8wt% c3) 0.05~3wt% d) 0.2~5% by weight e) 0.5~10% by weight f) 3~25% by weight g) 0.5~8% by weight h) 0~15% by weight i) Up to 100 It is a composition containing [the specified ingredient]. A more preferred embodiment of the present invention is a component a) 10~30% by weight b) 8~20% by weight c1) 0.4~1.5wt% c2) 0.4~1.5wt% d) 0.8~2wt% e) 2~4% by weight f) 7~11% by weight g) 1~6% by weight h) 0~15% by weight i) Up to 100 It is a composition containing [the specified ingredient]. A more preferred embodiment of the present invention is a component a) 10~30% by weight b) 8~20% by weight c1) 0.4~1.5wt% c2) 0.4~1.5wt% c3) 0.1~1wt% d) 0.8~2wt% e) 2~4% by weight f) 7~11% by weight g) 1~6% by weight h) 0~15% by weight i) Up to 100 It is a composition containing [the specified ingredient]. In this specification, within the preferred range described in the present invention, different preferred levels should be understood to be able to be combined with each other in permutations, but in any case, the same preferred levels, in particular the most preferred embodiment / preferred level, should be combined with each other in each case and are actually disclosed as such combinations. Particularly preferred is always the narrowest range combination. Compositions consisting only of essential components (not optional components), such as those described in this application, should also be considered disclosed.
[0036] SDHI inhibits succinate dehydrogenase in fungal mitochondrial chains, thereby inhibiting electron transport. SDHI can be classified into two classes: (1) inhibitors that bind in the succinate pocket and thereby prevent oxidation, and (2) inhibitors that bind in the ubiquinone pocket and thereby prevent reduction. Fluopyram belongs to the ubiquinone-type inhibitor class.
[0037] Bactericidal compounds classified under SDHI (FRAC code 7) include benzamides, pyrazole-4-carboxamides, phenyl-benzamides, phenyl-oxo-ethylthiopreneamides, furan-carboxamides, oxatiin-carboxamides, thiazole-carboxamides, N-methoxy-(phenyl-ethyl)-pyrazole-carboxamides, pyridine-carboxamides, and pyrazine-carboxamides.
[0038] In particular, SDHI includes (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxyne, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapiroxad, (2.008) furametpyr, (2.009) isofetamide, (2.010) isopyrazam (anti-epimerized enantiomer 1R, 4S, 9S), (2.011) isopyrazam (anti-epimerized enantiomer 1S, 4R, 9R), (2.012) isopyrazam (anti-epimerized racemate 1RS, 4SR, 9SR), (2.013) isopyrazam (syn-epimerized racemate) 1RS, 4SR, 9RS and anti-epimerated racemic mixture (1RS, 4SR, 9SR mixture), (2.014) Isopyrazam (syn-epimerated enantiomer 1R, 4S, 9R), (2.015) Isopyrazam (syn-epimerated enantiomer 1S, 4R, 9S), (2.016) Isopyrazam (syn-epimerated racemic mixture) (1RS, 4SR, 9RS), (2.017) Penflufen, (2.018) Penthiopyrad, (2.019) Pidiflumetofen, (2.020) Pyraziflumid, (2.021) Sedaxane, (2.022) 1,3-Dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.023) 1,3-Dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide Boxamide, (2.024)1,3-dimethyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.025)1-methyl-3-(trifluoromethyl)-N-[2'-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.026)2-fluoro-6-(trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)benzamide, (2.027)3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.028)Imprufluxam, (2.029)3-(difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.030)fluindapyr, (2.031)3-(difluoromethyl)-N-[(3R) -7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.032)3-(difluoromethyl)-N-[(3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.033)5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridine-2-yl]oxy}phenyl)ethyl]quinazoline- 4-amine, (2.034)N-(2-cyclopentyl-5-fluorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.035)N-(2-tert-butyl-5-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.036)N-(2-tert-butylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl Tyl-1H-pyrazole-4-carboxamide, (2.037)N-(5-chloro-2-ethylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.038)isoflucypram, (2.039)N-[(1R,4S)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalene-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.040)N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalene-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.041)N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.042)N-[2-chloro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5- Fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.043)N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.044)N-[5-chloro-2-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.045)N-cyclopropyl-3-(difluoro Methyl)-5-fluoro-1-methyl-N-[5-methyl-2-(trifluoromethyl)benzyl]-1H-pyrazole-4-carboxamide, (2.046)N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-fluoro-6-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.047)N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.048 )N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carbothioamide, (2.049)N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.050)N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(5-fluoro-2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.051) N-Cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-4,5-dimethylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.052) N-Cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-fluorobenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.053) N-Cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.054) N-Cyclopropyl-N-(2-Cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide Thamide, (2.055)N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.056)N-cyclopropyl-N-(2-cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.057)pyrapropoyne, (2.058)N-[rac-(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)nicotinamide, (2.059)N-[(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)nicotinam, and. (3.001) Ametoctrazine, (3.002) Amisulbrom, (3.003) Azoxystrobin, (3.004) Coumethoxystrobin, (3.005) Coumoxystrobin, (3.006) Cyazofamide, (3.007) Dimoxystrobin, (3.008) Enoxastrobin, (3.009) Famoxadone, (3.010) Fenamidon, (3.011) Fluphenoxy 3.012) fluoxastrobin, 3.013) kresoximmethyl, 3.014) metminostrobin, 3.015) orysastrobin, 3.016) picoxystrobin, 3.017) pyraclostrobin, 3.018) pyrametostrobin, 3.019) pyraoxystrobin, 3.020) trifloxystrobin, 3.021) (2E)-2-{2-[({[(1E) -1-(3-{[(E)-1-fluoro-2-phenylvinyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylacetamide, (3.022)(2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazole-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpenta-3-enamide, (3.023)(2R)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.024)( 2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.025) fenpicoxamide, (3.026) mandestrobin, (3.027) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-formamide-2-hydroxybenzamide, (3.028)(2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazole-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpenta-3-enamide, (3.(029) Selected from the group including methyl{5-[3-(2,4-dimethylphenyl)-1H-pyrazole-1-yl]-2-methylbenzyl}carbamate, (3.030) methyltetraprole, and (3.031) floryl picoxamide.
[0039] In one embodiment, the pesticide composition of the present invention comprises at least one benzamide compound. In a more preferred embodiment, the pesticide composition of the present invention comprises fluopyram.
[0040] The International Union of Pure and Applied Chemistry (IUPAC) name for fluopyram is N-[2-[3-chloro-5-(trifluoromethyl)pyridine-2-yl]ethyl]-2-(trifluoromethyl)benzamide. Fluopyram is chemically C 16 H 11 It is written as Cl F6N2O. [ka]
[0041] Fluopyram is a fungicidal and nematodic benzamide compound characterized as a succinate dehydrogenase inhibitor ("SDHI") and belongs to the Fungicide Resistance Action Committee ("FRAC") mechanism of action group C, FRAC code 7 (see www.frac.info / docs / default-source / publications / frac-code-list / frac-code-list-2017-final.pdf). Specifically, fluopyram is pyridinyl-ethyl-benzamide.
[0042] Further bactericidal benzamide compounds include benzohydroxamic acid, fluopicolide, fluopimamide, thioxamide, triclamide, zarilamid, and zoxamide.
[0043] In another embodiment, the pesticide composition of the present invention comprises at least one pyrazole-4-carboxamide. In another preferred embodiment, the pesticide composition of the present invention comprises isoflucipram.
[0044] The compound isoflucipram is a fungicide from Bayer CropScience AG, whose name was approved in March 2017 by the International Organization for Standardization ("ISO") Technical Committee ISO / TC 81 for the general name of pesticides and other agricultural chemicals.
[0045] The International Union of Pure and Applied Chemistry (IUPAC) name for isoflucipram is N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide. Isoflucipram is chemically C 19 H 21 It is written as ClF3N3O. [ka]
[0046] Isoflucipram is a pyrazole compound, specifically pyrazole-4-carboxamide. Therefore, isoflucipram is characterized as an SDHI belonging to FRAC mechanism of action group C, FRAC code 7.
[0047] Further pest control pyrazole compounds include oxathiapiproline, ravenzazole, fenpyrazamine, methyltetrapole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, benzovindiflupyr, bixafen, fluindapyr, fluxapyroxad, flametopyr, impilfluxam, isopyrazam, penflufen, penthiopyrad, pidflumetofen, and sedaxane.
[0048] In another preferred embodiment, the pesticide composition of the present invention comprises fluopyram and / or isoflucipram.
[0049] Ergosterol biosynthesis inhibitors, e.g., (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxyconazole, (1.004) fenhexamide, (1.005) fenpropidine, (1.006) fenpropimorph, (1.007) fenprapramin, (1.008) fluquinconazole, (1.009) flutriafol, (1.010) imazalil, (1.011) imazalil sulfate, (1.012) ipconazole, (1.013) metco Nazole, (1.014) Mycrobutanil, (1.015) Paclobutrazol, (1.016) Prochloraz, (1.017) Propiconazole, (1.018) Prothioconazole, (1.019) Pyrisoxazole, (1.020) Spiroxamine, (1.021) Tebuconazole, (1.022) Tetraconazole, (1.023) Triadimenol, (1.024) Tridemorph, (1.0 25) Triticonazole, (1.026)(1R,2S,5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazole-1-ylmethyl)cyclopentanol, (1.027)(1S,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazole-1-ylmethyl)cyclopentanol, (1.028)(2R)-2-(1-chlorocyclopropyl)-4-[ (1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazole-1-yl)butan-2-ol, (1.029)(2R)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazole-1-yl)butan-2-ol, (1.030)(2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazole-1-yl)propan-2-ol, (1.031)(2S)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazole-1-yl)butan-2-ol, (1.032)(2S)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazole-1-yl)butan-2-ol, (1.033)(2S)-2-[4-( 4-Chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazole-1-yl)propan-2-ol, (1.034)(R)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridine-3-yl)methanol, (1.035)(S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-di [Fluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.036)[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.037)1-({(2R,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl (1.038)1-({(2S,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4-triazole, (1.039)1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole-5-yl Thiocyanate, (1.040)1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole-5-yl Thiocyanate, (1.041)1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole-5-yl Thiocyanate, (1.(042)2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.043)2-[(2R,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.044)2-[(2R,4S,5R)-1-(2,4-dichlorophenyl)-5-hydro [Xy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thion, (1.045)2-[(2R,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thion, (1.046)2-[(2S,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2, 4-Triazole-3-thione, (1.047)2-[(2S,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.048)2-[(2S,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.049)2-[(2S,4S,5S)-1-(2 ,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thion, (1.050)2-[1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thion, (1.051)2-[2-chloro-4-(2,4-dichlorophenoxy)phenyl]-1-(1H-1,2,4-triazole-1-yl)propan-2-ol, (1.052)2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1H-1,2,4-triazole-1-yl)butan-2-ol, (1.053)2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazole-1-yl)butan-2-ol, (1.054)2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazole-1-yl)pentan-2-ol, (1.05 5) Mefentrifluconazole, (1.056) 2-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thion, (1.057) 2-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thion, (1.0 58) 2-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.059) 5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazole-1-ylmethyl)cyclopentanol, (1.060) 5-(allylsulfanil)-1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl [lan-2-yl]methyl}-1H-1,2,4-triazole, (1.061)5-(allylsulfanil)-1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.062)5-(allylsulfanil)-1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.(063)N'-(2,5-dimethyl-4-{[3-(1,1,2,2-tetrafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.064)N'-(2,5-dimethyl-4-{[3-(2,2,2-trifluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.065)N'-(2,5-dimethyl-4-{[3-(2,2,3,3-tetrafluoropropoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N -Methylimidoformamide, (1.066)N'-(2,5-dimethyl-4-{[3-(pentafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.067)N'-(2,5-dimethyl-4-{3-[(1,1,2,2-tetrafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.068)N'-(2,5-dimethyl-4-{3-[(2,2,2-trifluoroethyl)sulfanyl]phenoxy}phenyl) -N-ethyl-N-methylimidoformamide, (1.069)N'-(2,5-dimethyl-4-{3-[(2,2,3,3-tetrafluoropropyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.070)N'-(2,5-dimethyl-4-{3-[(pentafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.071)N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide (1.072)N'-(4-{[3-(difluoromethoxy)phenyl]sulfanyl}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.073)N'-(4-{3-[(difluoromethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.074)N'-[5-bromo-6-(2,3-dihydro-1H-inden-2-yloxy)-2-methylpyridine-3-yl]-N-ethyl-N-methylimidoformamide, (1.(075)N'-{4-[(4,5-dichloro-1,3-thiazole-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide, (1.076)N'-{5-bromo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridine-3-yl}-N-ethyl-N-methylimidoformamide, (1.077)N'-{5-bromo-6-[(1S)-1-(3,5-difluoro [Lofenyl)ethoxy]-2-methylpyridine-3-yl}-N-ethyl-N-methylimidoformamide, (1.078)N'-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridine-3-yl}-N-ethyl-N-methylimidoformamide, (1.079)N'-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridine-3-yl}-. N-ethyl-N-methylimidoformamide, (1.080)N'-{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridine-3-yl}-N-ethyl-N-methylimidoformamide, (1.081)ipfentrifluconazole, (1.082)2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2 ,4-triazole-1-yl)propan-2-ol, (1.083)2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazole-1-yl)propan-2-ol, (1.084)2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazole-1-yl)propan-2-ol, (1.085)3-[2-(1 -Chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile, (1.086)4-[[6-[rac-(2R)-2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazole-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, (1.087)N-isopropyl-N' -[5-Methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenylethyl)phenyl]-N-methylimidoformamide, (1.088)N'-{5-bromo-2-methyl-6-[(1-propoxypropan-2-yl)oxy]pyridine-3-yl}-N-ethyl-N-methylimidoformamide, (1.089)hexaconazole, (1.090)penconazole, (1.091)fenbuconazole. Difenoconazole is preferred, and the combination of difenoconazole and SDHI fluopyram is particularly preferred. In preferred embodiments, compounds a) and b) are present in a ratio of 4:1 to 1:2, preferably 3:1 to 1:1, more preferably 2:1 to 1:1, and most preferably 2:1.
[0050] The crystal-inhibiting carrier c1) is selected from the group consisting of clays, minerals, and synthetic silicas. Clays are based on carbonates, sulfates, phosphates, and silicates, and are obtained from earth alkalis and alkali metals. Typical examples include kaolin, silicates, silicates, Agsorb® LVM®-GA (Attapulgit), Harborlite® 300 (Perlit), Collys® HV, Omya® (Calcium Carbonate), Kaolin® Tec 1 (Kaolin, Aluminum Hydrosilicat), Steamic® OOS (Talc, Magnesium Silicone), Steamic® OOS (Talc, Magnesium Silicone), Bentonite, Hectorite, Attapulgite, Montmorillonite, Smectotite, and other silicate materials such as Benton (Elementis), Attagel® (Engelhard), Agsorb® (Oil-Dri Corporation), or Hectorite® (Akzo Nobel), or Van Gel-Reihe (RTVanderbilt). Particularly preferred are highly dispersed silica acids (exothermic and precipitated), such as Sipernat and Aerosil types from Evonik.
[0051] The crystal growth inhibitor c2) is a polymer crystal growth inhibitor selected from the group of polymer surfactants or a combination of polymer surfactants. Suitable polymer surfactants include, for example, polycarboxylates, acrylic copolymers, fatty alcohol ethoxylates, castor oil-based ethoxylates, fatty acid ethoxylates, EO-PO block copolymers (i.e., poloxamers), sorbitan(ol) ester ethoxylates, lanolin alcohol ethoxylates, polyol esters, lanolin alcohols, oleic / oleic fatty acids, vegetable and animal fat fatty acids, and lanolin fatty acids. Examples of polymer surfactants also include homopolymers or copolymers of vinylpyrrolidone, vinyl alcohol, or vinyl acetate. Preferably, c2) is selected from the group of polycarboxylate dispersants.
[0052] As the crystal growth inhibitor carrier c3), known cellulose ethers can be used as the crystal growth inhibitors of the present invention. Cellulose ethers are generally known compounds that are commercially available, for example, as Methocel® from Dow Chemical Company or as Culminal® from Hercules. They can be prepared by etherification of polysaccharide cellulose. The production process may be carried out in any one of several steps. The reactions that usually occur are alkalization and alkylation. These reactions can be carried out in or without a solvent. Pure cellulose has a large crystalline region due to hydrogen-bonded hydroxyl groups and is therefore insoluble in water and most organic solvents. In the first step of cellulose ether production, cellulose can be activated with sodium hydroxide to form alkali cellulose. In some processes, alkali cellulose is oxidatively decomposed much more rapidly than cellulose. A controlled decrease in the degree of polymerization allows for adjustment of the solution viscosity of the final product. The type of cellulose ether is determined by the selection of substituents. Mixed ethers can be produced using a mixture of reactants or by stepwise addition of substituents. This reaction step can be carried out under pressure and at high temperature. Alkylation can be carried out using alkyl halides. In epoxides, this process is called alkoxylation. As with all polymer reactions, this reaction may not occur uniformly along the polymer chain.
[0053] The cellulose ether may be methylhydroxyethylcellulose or hydroxypropylmethylcellulose. In one embodiment, the cellulose ether is hydroxypropylmethylcellulose. The cellulose ether may have a solubility in water of at least 3 g / l, preferably at least 10 g / l, and especially at least 20 g / l at 20°C. The molecular weight of the cellulose ether is usually determined by its kinematic viscosity or dynamic viscosity. Lower viscosity typically means a cellulose ether with a lower molecular weight. In a particular embodiment, the cellulose ether is Methocel® K200M Premium Hydroxypropyl Methylcellulose from Dow Chemical Company. In another embodiment, the cellulose ether is Methocel E15 Premium from Dow Chemical Company. Dispersant d) is selected from the group of sulfonates based on naphthalene and / or lignin. Examples include Galoryl® MT 800 (sodium dibutylnaphthalene sulfonate), Morwet® IP (diisopropylnaphthalene sulfonate), Nekal® BX (alkylnaphthalene sulfonate), salts of alkylnaphthalene sulfonic acid, salts of alkylnaphthalene sulfonic acid-formaldehyde condensation products, salts of naphthalene sulfonic acid, phenol sulfonic acid and formaldehyde condensation products. Anionic surfactants d) from the group of condensation products of formaldehyde and Naphthalene-formamide condensates, respectively: Naphthalinsulfonates Galoryl® DT 201 (naphthalene sulfate, hydroxypolymer formaldehyde, and sodium methylphenol salt), Galoryl® DT 250 (condensation product of phenol and naphthalene), Reserve® C (condensation product of phenol and naphthalene), Morwet® D-425 (Akzo-Nobel), and Terperse® D-2020 (Huntsman). Unsubstituted naphthalene sulf is preferred on formaldehyde dehydrogenation condensates containing product Morwet® D-425. Examples of lignin include, for example, available calcium, potassium, ammonium, or sodium ligninsulfonates such as Reax® 88, Kraftsperse® 25S (Westvaco), and type Borresperse® (Borregard).
[0054] E) is an emulsifier and dispersant different from d) and f). Suitable ones include sulfonates, sulfates, phosphates, carboxylates and alkali salts, earth alkali salts or ammonium salts of mixtures, as well as alkyl sulfonates and alkyl phosphates and alkylaryl sulfonates or alkylaryl phosphates and diphenyl sulfonates, α-olefin sulfonates, lignin sulfonates, sulfonates from fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of dodecyl and tridecylbenzene, sulfosuccinates or sulfosuccinates (sulfosuccinamates). Examples of sulfates and sulfonates are fatty acids and oils, ethoxylated alkylphenols, alcohols, ethoxylated alcohols or sulfates of fatty acid esters. An example of a phosphate is a phosphate ester. Examples of carboxylates are alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates. Anionic emulsifiers of alkali metal salts, alkaline earth metal salts and ammonium salts of polystyrene sulfonic acid, and salts of polyvinyl sulfonic acid are also preferred. Examples include calcium dodecylbenzenesulfonate such as Rhodocal® 70 / B (Solvay), phenyl sulfonate CA100 (Clariant), or isopropylammonium dodecylbenzenesulfonate such as Atlox® 3300B (Croda). Other representative examples include phenylsulfonic acid CA (Ca-dodecylbenzenesulfonate), Soprophor® type (any esterified derivative of tristryl phenoxyethoxylate), Emulsogen® 3510 (alkylated EO / PO copolymer), Emulsogen® EL 400 (ethoxylated castor oil), Tween® grade (sorbitan ethoxylate), and Calsogen® AR 100 (calcium dodecylbenzenesulfonate).Further typical surfactants e) include Soprophor® 3D33, Soprophor® 4D384, Soprophor® BSU, Soprophor® CY / 8 (Solvay), and Hoe® S3474, and Sapogenat® T 100 in the form of Sapogenat® T products (Clariant). Suitable nonionic dispersants e), such as emulsifiers, wetting agents, surfactants, and dispersants, are common surfactants present in formulations of pesticide active compounds. Examples that can be cited include ethoxylated nonylphenols, reaction products of linear or branched alcohols with ethylene oxide and / or propylene oxide, ethylene oxide-propylene oxide block copolymers, end-capped and non-end-capped alkoxylated linear and branched, saturated and unsaturated alcohols (e.g., butoxypolyethylenepropylene glycol), reaction products of alkylphenols with ethylene oxide and / or propylene oxide, ethylene oxide-propylene oxide block copolymers, polyethylene glycol and polypropylene glycol, as well as fatty acid esters, fatty acid polyglycol ether esters, alkyl sulfonates, alkyl sulfates, aryl sulfates, ethoxylated arylalkylphenols, such as tristrylphenol ethoxylate having an average of 16 ethylene oxide units per molecule, as well as ethoxylated and propoxylated arylalkylphenols and sulfated or phosphorylated arylalkylphenol ethoxylates or ethoxylated and propoxylates. Particularly preferred are tristrylphenol alkoxylates and fatty acid polyglycol ether esters. Tristrylphenol ethoxylate, tristrylphenol ethoxypropoxylate, and castor oil polyglycol ether esters are particularly preferred, either individually or in mixtures.A suitable nonionic dispersant e) may also be selected from the group including polyvinylpyrrolidone (PVP), polyvinyl alcohol, copolymers of PVP and dimethylaminoethyl methacrylate, butylated PVP, copolymers of vinyl chloride and vinyl acetate, and partially hydrolyzed vinyl acetate, phenolic resins, Luviskol® (polyvinylpyrrolidone), Mowiol® (polyvinyl alcohol), or modified cellulose types such as modified cellulose. Polyvinylpyrrolidone types are preferred, and low molecular weight types such as Luviskol® K30 or Sokalan® K30 are particularly preferred. Other preferred nonionic emulsifiers e) are selected from the group of di- and tri-block copolymers of alkylene oxides. Suitable compounds based on ethylene oxide and propylene oxide, having an average molecular weight of 200 to 10,000, preferably 1,000 to 4,000 g / mol, and with a mass fraction of polyethoxylated blocks varying between 10 and 80%, such as Synperonic® PE series (Uniqema), Pluronic® PE series (BASF), VOP® 32, or Genapol® PF series (Clariant).
[0055] Definition f) Further additives f) included in the formulation according to the present invention are penetration enhancers, and all substances that can be commonly used in pesticides for this purpose are suitable. The following are preferred as additive f), for example, Oils that function as penetration enhancers, suitable oils are all substances of this type that can be conventionally used in pesticides. Preferably, they are oils of plant, mineral, and animal origin, as well as alkyl esters of these oils. Examples: - Sunflower oil, rapeseed oil, corn oil, soybean oil, rice bran oil, olive oil; - Ethylhexyl oleate, ethylhexyl palmitate, ethylhexyl myristate / ethylhexyl laurate, ethylhexyl laurate, ethylhexyl caprylate / caprate, isopropyl myristate, isopropyl palmitate, methyl oleate, methyl palmitate, ethyl oleate, rapeseed oil methyl ester, soybean oil methyl ester, rice bran oil methyl ester, - Mineral oils, such as Exxsol® D100, Solvesso® 200ND, and white oils. - Tris-alkyl-phosphate ester, preferably tris(2-ethylhexyl)phosphate, such as Disflamoll® TOF. The uptake enhancer can also be selected from the following group of compounds: i. Ethoxylated branched alcohols having 2 to 20 EO units (e.g., Genapol® X-type); ii. Methyl-end capped ethoxylated branched alcohols containing 2 to 20 EO units (e.g., Genapol® XM-type); iii. Ethoxylated coconut alcohol containing 2 to 20 EO units (e.g., Genapol® C-type); iv. Ethoxylated C12 / 15 alcohols containing 2 to 20 EO units (e.g., Synperonic® A-type); v. Propoxyethoxylated alcohols, branched or linear, e.g., Antarox® B / 848, Atlas® G5000, Lucramul® HOT 5902; vi. Propoxy-ethoxylated fatty acids, Me end caps, e.g., Leofat® OC0503M; vii. Alkyl ether citrate surfactants (e.g., Adsee® CE range, Akzo Nobel); viii. Ethoxylated monoesters or diesters of glycerol containing fatty acids having 8 to 18 carbon atoms and an average of 10 to 40 EO units (e.g., Crovol® range); ix. Castor oil ethoxylates are 5-40 EO units (e.g., Berol® range, Emulsogen® EL range); x. Ethoxylated oleic acid containing 2 to 20 EO units (e.g., Alkamuls® A and AP); xi. Ethoxylated sorbitan fatty acid esters containing fatty acids having 8 to 18 carbon atoms and an average of 10 to 50 EO units (e.g., Arlatone® T, Tween range). Also, methyl-terminated propoxy-ethoxylated fatty acids, such as Leofat® OC0503M; Organically modified polysiloxanes, e.g., BreakThru® OE444, BreakThru® S240, Silwett® L77, Silwett® 408; Monoesters and diesters of sodium sulfosuccinate salts having branched or linear alcohols with 1 to 10 carbon atoms; Ethoxylated diacetylenediol (e.g., Surfynol®). Table: Illustrative trade names and CAS numbers of preferred compound f) [Table 1] Further optional additives g), such as rainproofing additives, adhesives, surfactants, solvents, wetting agents, emulsifiers, biocides, microcides, dispersants, thickeners, stabilizers, carriers, adjuvants, diluents, micronutrient or macronutrient fertilizers, feeding inhibitors, insect molting inhibitors, insect mating inhibitors, insect maturation inhibitors, nutrient or horticultural supplements, or any combination thereof may be used: Other than the thickeners in c) to g), the organic thickeners are preferred, and these may be natural or biotechnically modified thickeners or organic synthetic thickeners. Typical synthetic thickeners include Rheostrux® (Croda), Thixin®, or the Thixatrol® series (Elementis). These are typically acrylate-based. Typical organic thickeners are based on xanthan gum or cellulose (such as hydroxyethyl or carboxymethylcellulose) or a combination thereof. It is preferable to use naturally modified thickeners based on xanthan gum. Typical representative examples include, for example, Rhodopol® (Solvay), Kelzan® (Kelco Corp), and Satiaxane® (Cargill). Further additives and auxiliary agents g) include wetting agents, pH adjusters, defoamers, biocides, disintegrants, adhesion promoters, antifreeze agents, preservatives, dyes or fertilizers, and surfactants different from components d, e and f) and c), and various fillers, antifreeze agents, defoamers and biocides are preferably added. Suitable rainproofing additives are acrylic-based emulsion polymers or polymer dispersions and styrene-based emulsion polymers or polymer dispersions, where b) is an aqueous polymer dispersion having a Tg in the range of -100°C to 30°C, preferably -60°C to 20°C, more preferably -50°C to 10°C, and most preferably -45°C to 5°C, such as Acronal V215, Acronal 3612, Licomer ADH 205, and Atplus FA. Particularly preferred are Licomer ADH 205 and Atplus FA. Preferably, the polymer is selected from the group consisting of acrylic polymers, styrene polymers, vinyl polymers and their derivatives, polyolefins, polyurethanes and natural polymers and their derivatives. More preferably, the polymer is selected from the group consisting of acrylic polymers, styrene-butadiene copolymers, styrene-maleic anhydride copolymers, polyvinyl alcohol, polyvinyl acetate, partially hydrolyzed polyvinyl acetate, methyl vinyl ether-maleic anhydride copolymers, carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, and silicon-modified polyvinyl alcohol, isopropylene-maleic anhydride copolymers, polyurethanes, cellulose, gelatin, casein, oxidized starch, starch-vinyl acetate graft copolymers, hydroxyethylcellulose, methylcellulose, ethylcellulose, carboxymethylcellulose, and acetylcellulose. Most preferably, the polymer is selected from copolymers of acrylate and styrene. The acrylate is selected from a list including 2-ethylhexyl acrylate, butyl acrylate, sec-butyl acrylate, ethyl acrylate, methyl acrylate, acrylic acid, acrylamide, isobutyl acrylate, methyl methacrylate, or combinations thereof. The styrene is selected from a list including styrene, tert-butylstyrene, para-methylstyrene, or combinations thereof. In a preferred embodiment, the polymer has a molecular weight of 40,000 or less, preferably 10,000 or less. In a preferred embodiment, polymer D is an emulsion polymer as described in WO2017 / 202684. The glass transition temperature (Tg) is known for many polymers and, if not defined in this invention, is determined according to ASTM E1356-08 (2014) "Standard Test Method for Assignment of Glass Transition Temperatures by Differential Scanning Calorimetry". Samples are dried at 110°C for 1 hour prior to DSC to eliminate the influence of water and / or solvents. DSC sample size is 10-15 mg, measured under N2 at 20°C / min from -100°C to 100°C. Tg is defined as the midpoint of the transition region. Suitable defoaming agents include silicone-based or silane-based surfactant compounds, such as Tegopren® products (Goldschmidt), SE® products (Wacker), and Bevaloid® (Kemira), Rhodorsil® (Solvay), and Silcolapse® products (Blustar Silicones), preferably SE® (Wacker), Rhodorsil®, and Silcolapse® products, and particularly preferably products such as Silcolapse® 5020. Suitable antifreezes are from the group consisting of ureas, diols, and polyols, such as ethylene glycol and propylene glycol, glycerol, preferably propylene glycol or glycerol. Suitable biocides include, for example, Acticide® MBS (Biocide, Thor Chemie), CIT, MIT, or BIT, such as Proxel® GXL (BIT) and Acticide® SPX (MIT, CIT). Suitable adhesion promoters include polyvinylpyrrolidone (PVP), polyvinyl alcohol, copolymers of PVP and dimethylaminoethyl methacrylate, butylated PVP, copolymers of vinyl chloride and vinyl acetate, sodium salts of copolymers of propensulanic acid and partially hydrolyzed vinyl acetate, sodium caseinate, phenolic resins, modified cellulose types such as Luviskol® (polyvinylpyrrolidone), Mowiol® (polyvinyl alcohol), and modified cellulose. The polyvinylpyrrolidone type is preferred, and the low molecular weight type such as Luviskol® K30 is particularly preferred.
[0056] Suitable disintegrants are selected from the group of modified carbohydrates, such as microcrystalline cellulose and cross-linked polyvinylpyrrolidone, e.g., Avicel® PH 101 (microcrystalline cellulose), Agrimer® XLF (cross-linked polyvinylpyrrolidone), and Disintex® 200 (cross-linked polyvinylpyrrolidone). Cross-linked polyvinylpyrrolidone such as Agrimer® XLF is preferred. Suitable defoamers can be selected from the group of phosphate esters having lower alcohols, C6-C10 alcohols, silicone surfactants (suspend emulsification of hydrophobized silica particles in aqueous emulsion concentrates based on liquid silicone surfactants), e.g., polydimethylsiloxane, and adsorbents thereof on solid support materials such as Rhodorsil® 432 (silicone surfactant), butyl phosphate, isobutyl phosphate, n-octanol, Wacker ASP15 (polydimethylsiloxane, absorbed onto a solid support), and Defoamer® SE (polydimethylsiloxane). Suspension emulsions of hydrophobic silica particles in aqueous emulsion concentrates based on liquid silicone surfactants, such as the defoamer SE (polydimethylsiloxane), and solid defoamers, such as Wacker ASP 15 (polydimethylsiloxane), are preferred. Tackifiers, such as carboxymethylcellulose, and natural and synthetic polymers in the form of powders, granules, or latex, such as gum arabic, polyvinyl alcohol, and polyvinyl acetate, as well as natural phospholipids, such as cephalin and lecithin, and synthetic phospholipids, can be used in the formulation. Other possible additives are mineral oil and vegetable oil.
[0057] Colorants, inorganic pigments such as iron oxide, titanium dioxide, and Prussian blue, as well as organic dyes such as alizarin dyes, azo dyes, and metal phthalocyanine dyes, and micronutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum, and zinc may also be used. In addition, one or more of biocides, antifreezes, defoamers, and other inertants or excipients may be included in the final formulation. In one embodiment, the compositions disclosed herein may contain one or more biocides and / or microbiotides present at a total w / w concentration of 0.001% to 10%, or 0.01% to 1%, or 0.05% to 0.5%.
[0058] In one embodiment, the compositions disclosed herein may contain one or more thickeners or stabilizers present at a total w / w concentration of 0.001% to 10%, or 0.05% to 5%, or 0.01% to 1%. Additionally, an antifoaming agent such as (SAG30, Antifoam 8830) may be used in a desired amount, for example, 0.001% to 1% by weight of the final composition. Furthermore, an antifreeze such as propylene glycol or glycerin may be used, for example, at 0% to 20% by weight.
[0059] In one embodiment, the compositions disclosed herein may comprise one or more additional pest control agents h) such as herbicides, insecticides, fungicides, bactericidal agents, acaricides, nematicides or pheromones, or other biologically active compounds. The mixture thus obtained has a broad activity spectrum.
[0060] In another embodiment, the composition of the present invention comprises one or more Gram-negative bacteria and / or one or more members of the genus Bacillus.
[0061] Preferred species include Bacillus agri, Bacillus aizawai, Bacillus albolactis, Bacillus amyloliquefaciens, Bacillus firmus, Bacillus coagulans, Bacillus endoparasiticus, Bacillus endorhythmos, Bacillus firmus, Bacillus kurstaki, Bacillus lacticola, Bacillus lactimorbus, and Bacillus lactis. Bacillus lactis), Bacillus laterosporus, Bacillus lentimorbus, Bacillus licheniformis, Bacillus megaterium, Bacillus medusa, Bacillus metiens, Bacillus natto, Bacillus nigrificans, Bacillus popillae, Bacillus pumilus, Bacillus siamensis, Bacillus sphaerix (Bacillus Bacillus species (Bacillus sphaericus), Bacillus subtilis, Bacillus thuringiensis, Bacillus uniflagellatus, Bacillus cereus, and "Bergey's Manual of Systematic Bacteriology,These are Bacillus species selected individually or in combination from the group consisting of those listed in the category of the genus Bacillus in the first edition (1986).
[0062] In one embodiment of the present invention, the Bacillus species is one of B. firmus, B. amyloliquefaciens, B. subtilis, or B. thuringiensis.
[0063] In another embodiment, the compositions disclosed herein may be applied to plants, plant parts, or their habitats in combination with one or more compositions comprising further known herbicides, insecticides, fungicides, bactericidal agents, acaricides, nematicides, or pheromones, or other biologically active compounds. In some examples, synergistic effects can be obtained, i.e., the activity of the mixture exceeds the activity of the individual components. Such additional active substances can be used in any desired ratio with the succinate dehydrogenase inhibitor of the composition, for example, with a weight ratio of SDHI to the additional component of 1:100 to 100:1, or 50:1 to 1:50, or 25:1 to 1:25, or 1:10 to 10:1, or 5:1 to 1:5.
[0064] These additional compounds and / or compositions can be determined by systematic field trials, which are within the capabilities of those skilled in the art.
[0065] Suitable additional fungicides that can be used in combination with the compositions disclosed herein include, for example, the following known fungicides: (1) Inhibitors of nucleic acid synthesis, e.g., venalaxyl, venalaxyl-M, bupirimate, clodilacon, dimethyrimol, etyrimol, flaraxyl, himexazole, metalaxyl, metalaxyl-M, offrace, oxadixyl and oxolinic acid. (2) Inhibitors of mitosis and cell division, such as benomyl, carbendazim, chlorphenazole, diethofencarb, etaboxam, fuberidazole, pencyclon, thiabendazole, thiophanate, thiophanate-methyl and zoxamide. (3) Respiratory inhibitors, e.g., diflumetrim as a CI respiratory inhibitor; bixafen, boscalid, carboxyne, fenflam, flutolanil, fluopyram, flametopyr, flumesirox, isopyrazam (9R component), isopyrazam (9S component), mepronil, oxycarboxyne, penthiopyrad, tifluzamide as CIII respiratory inhibitors; amisulbrom, azoxystrobin, cyazofamide, dimoxystrobin, enestrobrin, famoxadone, fenamidon, fluoxastrobin, kresoxim-methyl, metminostrobin, oryzastrobin, picoxystrobin, pyraclostrobin, pyribencarb, trifloxystrobin. (4) Compounds that can act as uncoupling agents, for example, binapacril, dinocap, fluazinam, and meptyldinocap. (5) Inhibitors of ATP production, such as fentin acetate, fentin chloride, fentin hydroxide, and silthiofams. (6) Inhibitors of amino acid and / or protein biosynthesis, e.g., andprim, blastosidine-S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim, and pyrimethanil. (7) Inhibitors of signal transduction, such as fenpiclonil, fludioxonil, and quinoxyfen. (8) Inhibitors of lipids and membrane synthesis, such as biphenyl, clozolinate, edifenphos, etridiazole, iodocarb, ipropenphos, iprodione, isoprothiolane, procymidone, propamocarb, propamocarb hydrochloride, pyrazophos, tolclophosmethyl and vinclozoline. (9) Inhibitors of ergosterol biosynthesis, e.g., aldimorph, azaconazole, vitertanol, bromconazole, cyproconazole, diclobutrazol, difenoconazole, diniconazole, diniconazole-M, dodemorph, dodemorph acetate, epoxyconazole, etaconazole, phenalimol, fenbuconazole, fenhexamide, fenpropidine, fenpropimorph, fluquinconazole, flurprimidol, flusilazole, flutriafole, fluconazole, fluconazole-cis, hexa Conazole, imazalil, imazalil sulfate, imibenconazole, ipconazole, metconazole, mycrobutanil, naphthifine, nualimol, oxpoconazole, paclobutrazol, pefurazoate, penconazole, piperalin, prochloraz, propiconazole, prothioconazole, pyributicarb, pyrifenox, quinconazole, simeconazole, spiroxamine, tebuconazole, terbinafine, tetraconazole, triadimefon, triadimenol, tridemorph, triflumizole, triforine, triticonazole, uniconazole, viconazole, and voriconazole. (10) Inhibitors of cell wall synthesis, e.g., benciavalicarb, dimethomorph, flumorph, iprovalicarb, mandipropamide, polyoxin, polyoxolim, prothiocarb, validamycin A, and valifenal. (11) Inhibitors of melanin biosynthesis, such as carpropamide, diclocimet, phenoxanil, phthalide, pyroquilon, and tricyclazole. (12) Compounds that can induce host defense, such as acibenzoral-S-methyl, probenazole, and thiadinyl. (13) Compounds capable of multi-site action, such as Bordeaux mixture, captahole, captan, chlorothalonyl, copper naphthenate, copper oxide, copper oxychloride, copper hydroxide and other copper preparations, copper sulfate, diclofluanide, dithianone, dozin, dozin free base, ferbam, fluoroholpet, holpet, guazatin, guazatin acetate, iminoctadine, iminoctadine albesylate, iminoctadine triacetate, mancopper, manzeb, maneb, methylam, methylam zinc, oxin-copper, propamidine, propineb, sulfur and sulfur preparations (calcium polysulfide, thyram, tolylfluanid, zineb and zillam). (14) Further compounds, e.g., 2,3-dibutyl-6-chlorothieno[2,3-d]pyrimidine-4(3H)-one, ethyl(2Z)-3-amino-2-cyano-3-phenylpropane-2-enoate, N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide, N-{2-[1,1'-bi(cyclopropyl)-2-yl]phenyl}-3-(di Fluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-1-methyl-N-(3',4',5'-trifluorobiphenyl-2-yl)-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-1-methyl-1H-pyrazole-4-carboxamide, (2E) -2-(2-{[6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidine-4-yl]oxy}phenyl)-2-(methoxyimino)-N-methylethaneamide, (2E)-2-{2-[({[(2E,3E)-4-(2,6-dichlorophenyl)buta-3-en-2-ylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethaneamide, 2-chloro-N-(1,1 ,3-trimethyl-2,3-dihydro-1H-inden-4-yl)pyridine-3-carboxamide, N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamide, 5-methoxy-2-methyl-4-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)-2,4-dihydro-3H-1,2,4-Triazole-3-one, (2E)-2-(methoxyimino)-N-methyl-2-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)ethanamide, (2E)-2-(methoxyimino)-N-methyl-2-{2-[(E)-({1-[3-(trifluoromethyl)phenyl]ethoxy}-imino)methyl]phenyl}ethanamide, (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenyl-eth [Nyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methyl-ethaneamide, 1-(4-chlorophenyl)-2-(1H-1,2,4-triazole-1-yl)cycloheptanol, methyl 1-(2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)-1H-imidazole-5-carboxylate, N-ethyl-N-methyl-N'-{2-methyl-5-(trifluoromethyl)-4-[3-(trimethylsilyl)propoxy]phenyl} Imidoformamide, N'-{5-(difluoromethyl)-2-methyl-4-[3-(trimethylsilyl)propoxy]phenyl}-N-ethyl-N-methylimidoformamide, O-{1-[(4-methoxyphenoxy)methyl]-2,2-dimethylpropyl}1H-imidazole-1-carbothioate, N-[2-(4-{[3-(4-chlorophenyl)propa-2-in-1-yl]oxy}-3-methoxyphenyl)ethyl]-N2-(methylsulfonyl)valineamide, 5-chloro-7-(4-methyl Lupiperidine-1-yl)-6-(2,4,6-trifluorophenyl)[1,2,4]triazolo[1,5-a]pyrimidine, 5-amino-1,3,4-thiadiazole-2-thiol, propamocarb-fosetyl, 1-[(4-methoxyphenoxy)methyl]-2,2-dimethylpropyl 1H-imidazole-1-carboxylate, 1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide, 2,3,5,6-Tetrachloro-4-(methylsulfonyl)pyridine, 2-butoxy-6-iodo-3-propyl-4H-chromen-4-one, 2-phenylphenol and salts, 3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide, 3,4,5-trichloropyridine-2,6-dicarbonitrile, 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidine-3- Il]pyridine, 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, quinoline-8-ol, quinoline-8-ol sulfate (2:1) (salt), 5-methyl-6-octyl-3,7-dihydro[1,2,4]triazolo[1,5-a]pyrimidine-7-amine, 5-ethyl-6-octyl-3,7-dihydro[ [1,2,4]Triazolo[1,5-a]pyrimidine-7-amine, bentazole, bethoxazine, capsimycin, carvone, quinomethionate, chloreneb, cufraneb, cyflufenaamide, cymoxanil, cyprosulfamide, dazomet, debacarb, dichlorophene, diclomazine, dichlorane, diphenzocort, diphenzocort methyl sulfate, diphenylamine, ecomate, felimzone, flumethol, fluopicolide, fluolimide, Fursulfamide, fluthianil, fosetyl-aluminum, fosetyl-calcium, fosetyl-sodium, hexachlorobenzene, irumamycin, isothianil, metasulfocarb, methyl(2E)-2-{2-[({cyclopropyl[(4-methoxyphenyl)imino]methyl}thio)methyl]phenyl}-3-methoxyacrylate, methylisothiocyanate, metraphenone, (5-bromo-2-methoxy-4-methylpyridine-3-yl)(2,3,4-Trimethoxy-6-methylphenyl)methanone, Mildiomycin, Torniphanide, N-(4-chlorobenzyl)-3-[3-methoxy-4-(propa-2-in-1-yloxy)phenyl]propanamide, N-[(4-chlorophenyl)(cyano)-methyl]-3-[3-methoxy-4-(propa-2-in-1-yloxy)phenyl]propanamide, N-[(5-bromo-3-chloropyridine-2-yl)methyl]-2,4-di Chloropyridine-3-carboxamide, N-[1-(5-bromo-3-chloropyridine-2-yl)ethyl]-2,4-dichloropyridine-3-carboxamide, N-[1-(5-bromo-3-chloropyridine-2-yl)-ethyl]-2-fluoro-4-iodopyridine-3-carboxamide, N-{(Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide N-{(E)-[(cyclopropyl-methoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide, natamycin, nickel dimethyldithiocarbamate, nitrotar-isopropyl, octylinone, oxamocarb, oxyphentin, pentachlorophenol and salts, phenazine-1-carboxylic acid, phenothrin, phosphite and its salts, propamocarb focetilate, propanosyl Examples include 1-sodium, proquinazide, pyrrolenitrin, quintozen, S-propa-2-en-1-yl5-amino-2-(1-methylethyl)-4-(2-methylphenyl)-3-oxo-2,3-dihydro-1H-pyrazole-1-carbothioate, tecrophthalam, technazen, triazoxide, triclamide, 5-chloro-N'-phenyl-N'-propa-2-in-1-ylthiophene-2-sulfonohydrazide, and zaryramide.
[0066] Any desired useful plant or crop can be treated with the composition of the present invention to promote plant health.
[0067] In one embodiment, the composition of the present invention is cotton, flax, grapes, fruits or plant crops, for example, species of the genus Vitis (e.g., grapes and wine grapes), species of the genus Citrullus (e.g., watermelon), species of Pistacia (e.g., pistachios), species of Prunus (e.g., cherries), species of the family Rosaceae (e.g., fruits such as apples and pears, as well as drupes such as apricots, almonds and peaches), species of the genus Ribesioidae (e.g., Juglandaceae (e.g., walnuts), species of the genus Betulaceae (e.g., birch), species of the family Anacardiaceae (e.g., beech), species of the family Fagaceae (e.g., mulberry), species of the family Oleaceae (e.g., olive). sp.), Actinidaceae sp., Lauraceae sp., Musaceae sp. (e.g., banana trees and plantins), Rubiaceae sp., Theaceae sp., Sterculiceae sp., Rutaceae sp. (lemons, oranges, grapefruits, etc.), Solanaceae sp. (e.g., tomatoes), Liliaceae sp., Asteraceae sp. (e.g., lettuce), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp., Papilionaceae sp.) (e.g., peas), Rosaceae sp. (e.g., strawberries); major crops, e.g., Graminae sp. (e.g., maize, grass, or grains, e.g., wheat, rice, barley, and rye), Asteraceae sp. (e.g., sunflowers), Cruciferae sp. (e.g., rapeseed), Fabaceae sp.(e.g., peanuts), legumes (Papilionaceae sp.) (e.g., soybeans), nightshade species (Solanaceae sp.) (e.g., potatoes), amaranth species (Chenopodiaceae sp.) (e.g., beetroot), horticultural crops and forest crops; and can be used to process genetically modified homologs of these crops.
[0068] In this context, "plant" is understood to mean all plants and plant populations, such as desired wild plants or crop plants (including naturally occurring crop plants). Crop plants or crops may be obtained by conventional breeding and optimization methods, or by biotechnology and genetic engineering methods, or a combination thereof, and may include transgenic plants and plant varieties that may or may not be protected by the rights of plant breeders.
[0069] The compositions described herein can be applied to soil, plants, crops, seeds, leaves, or plant parts thereof in a single application step. In another embodiment, the compositions described herein are applied to plants, crops, seeds, leaves, or plant parts thereof in multiple application steps, for example, two, three, four, five or more application steps. In another embodiment, the second, third, fourth, or fifth or later application steps may use the same or different compositions. The methods described herein also provide embodiments in which multiple application steps are omitted.
[0070] The compositions described herein can be applied to soil, plants, crops, seeds, or parts of the plants thereof at one or more application intervals of about 30 minutes, about 1 hour, about 2 hours, about 6 hours, about 8 hours, about 12 hours, about 1 day, about 5 days, about 7 days, about 10 days, about 12 days, about 14 days, about 21 days, about 28 days, about 35 days, about 45 days, about 50 days, or about 56 days.
[0071] The compositions described herein may be applied to plants, crops, seeds, or parts thereof once or multiple times during the growth, planting, or harvesting period. In another embodiment, the compounds or compositions described herein are applied to plants, crops, seeds, or parts thereof one, two, three, four, or five or more times during the growth, planting, or harvesting period. In yet another embodiment, the compounds or compositions described herein are applied to plants, crops, seeds, or parts thereof only once, two or fewer times, or three or fewer times during the growth, planting, or harvesting period. In yet another embodiment, the compounds or compositions are applied to seeds in a single step. In yet another embodiment, the seeds described herein are planted in a one-pass application step.
[0072] In another embodiment, the disclosure provides pre-planting, pre-germination, post-germination, application steps, or combinations thereof. In yet another embodiment, the compounds or compositions described herein are first applied in a pre-planting step, followed by one or more pre-germination or post-germination steps. In yet another embodiment, the disclosure provides only pre-planting steps.
[0073] The methods described herein can be used to treat genetically modified organisms (GMOs), such as plants or seeds. A genetically modified plant (or transgenic plant) is a plant in which heterologous genes are stably incorporated into its genome. The term “heterologous gene” essentially means a gene that, when provided or assembled outside the plant and introduced into the nuclear, chloroplast, or mitochondrial genome, gives a new or improved agrochemical or other characteristic of the transformed plant by expressing a protein or polypeptide of interest, or by downregulating or silencing other genes present in the plant (e.g., using antisense techniques, cosuppression techniques, or RNA interference-RNAi techniques). Heterologous genes located in the genome are also called transgenes. A transgene defined by its specific location in the plant genome is called a transformation or transgenic event.
[0074] In one embodiment, the plants may be obtained by traditional breeding and optimization methods, or by biotechnological and recombinant methods, or a combination thereof, and may include transgenic plants and plant varieties that may or may not be protected by the rights of plant breeders.
[0075] In another embodiment, plant species and varieties found in the wild or obtained by conventional biological breeding methods, such as hybridization or protoplast fusion, as well as portions of these species and varieties, are processed. In yet another embodiment, transgenic plants and varieties obtained by recombinant methods are processed, where appropriate, in combination with conventional methods (genetically modified organisms) and portions thereof.
[0076] "Plant parts" should be understood to mean all of the above-mentioned above-ground and underground parts and organs of a plant, such as shoots, leaves, flowers, roots, needles, stems, fruiting bodies, fruits and seeds, tubers and rhizomes, etc. Plant parts also include harvested crops, as well as vegetative and reproductive materials, such as cuttings, tubers, rhizomes, twigs and seeds.
[0077] Seeds, plant parts, leaves, and plants can be treated with the composition described by directly applying the compound or composition to the seeds, plant parts, leaves, or plants. In another embodiment, seeds, plant parts, leaves, or plants may be treated indirectly, for example, by treating the environment or habitat to which the seeds, plant parts, leaves, or plants are exposed. Conventional treatment methods may be used to treat the environment or habitat, including immersion, spraying, fumigation, chemigating, fogging, spraying, brushing, shank, or injection.
[0078] "Habitat" means the place where a plant or crop grows, or the place where a plant or crop grows. The composition can be used to treat plants, crops, or their habitats.
[0079] According to the present invention, treatment of plants and seeds with the compositions described herein can be carried out directly by conventional treatment methods, such as immersion, spraying, vaporization, atomization, injection, dripping, drenching, broadcasting or coating, and seed treatment.
[0080] The compositions described herein are not limited to but may take any variety of dosage forms, including suspension concentrates, aerosols, capsule suspensions, room temperature fogging agents, high temperature fogging agents, encapsulated granules, fine granules, flowable formulations for seed treatment, ready-to-use solutions, powders, emulsions, aqueous emulsions, oily emulsions, coarse granules, fine granules, oil-dispersible powders, oil-adsorbable flowable formulations, oil-adsorbable liquid formulations, foams, pest control-coated seeds, saspoemulsions, aqueous solutions, wettable powders, water-soluble powders, powders and granules, water-soluble granules or tablets, water-soluble powders for seed treatment, wettable powders, natural and synthetic substances impregnated with the compounds or compositions described herein, nets impregnated with the compounds or compositions described herein, and microencapsulated solutions in polymeric substances and coating materials for seeds, as well as ULV room temperature fogging and high temperature fogging formulations.
[0081] These compositions include not only compositions that are applied immediately to plants or seeds by means of suitable devices such as spraying or dusting equipment or drones, but also concentrated commercial compositions that must be diluted before being applied to crops.
[0082] The pest control composition of the present invention can be used to therapeutically or preventively control plant pathogenic fungi on crops, and to therapeutically or preventively control nematodes and / or insects.
[0083] The compositions according to the present invention are well tolerated by plants, possess desirable thermotoxicity, and are environmentally friendly; they are suitable for protecting plants and plant organs, increasing harvest yields, improving the quality of harvested materials, and controlling animal pests, particularly insects, arachnids, and nematodes encountered in agriculture, forests, gardens, and leisure facilities, stored products and materials, and in sanitation fields. It is preferably used as a crop protectant. It is typically active against susceptible and resistant species, and at all or some stages of development. Among the animal pests that can be controlled by the methods according to the present invention are:
[0084] Plant parasitic nematodes, such as species of the genera Aphelenchoides, Bursaphelenchus, Ditylenchus, Globodera, Heterodera, Longidorus, Meloidogyne, Pratylenchus, Radopholus, Trichodorus, Tylenchulus, and Xiphinema. spp.), Helicotylenchus spp., Tylenchorhynchus spp., Scutellonema spp., Paratricodorus spp., Meloinema spp., Paraphelenchus spp., Aglenchus spp., Belonolaimus spp., Nacobbus spp., Rotilenchulus spp., Rotilenchulus spp., Neotylenchus spp., Paraphelenchus spp.) Dolichodorus spp., Hopolaimus spp., Punctodera spp., Criconemella spp., Quinisulcius spp., Hemicycliophora spp., Anguina spp., Subanguina spp., Hemicriconemoides spp.), species of the genera Psilenchus, Pseudohalenchus, Criconemoides, and Cacopaurus.
[0085] Accordingly, a further aspect of the present invention provides a method for preventing or curatively controlling plant pathogenic fungi of crops, but also for curatively or curatively controlling nematode pests, characterized in that the above composition is applied to the area where the nematodes are controlled in an effective and non-phytotoxic amount.
[0086] The compositions according to the present invention can also be used against pests and diseases that tend to grow on or inside wood. The term “wood” means all kinds of wood and all kinds of workpieces made from this wood, e.g., solid wood, high-density wood, laminated wood, and plywood. Methods for treating wood according to the present invention mainly consist of contacting one or more compounds or compositions according to the present invention, which include, for example, direct application, spraying, immersion, injection, or any other suitable means.
[0087] The expression "effective and non-phytotoxic amount" means an amount of the composition according to the present invention that is sufficient to control or destroy pests and / or diseases present or likely to appear on a crop, without any recognizable signs of phytotoxicity to the crop. Such an amount can vary over a wide range depending on the pests and diseases being controlled or eliminated, the type of crop, climatic conditions, and the compounds contained in the composition according to the present invention.
[0088] This quantity can be determined by systematic field trials, which are within the capabilities of those skilled in the art.
[0089] The compositions described herein can be combined with fertilizers. Examples of fertilizers that can be used with the compositions and methods described herein include, for example, urea, ammonium nitrate, ammonium sulfate, calcium nitrate, diammonium phosphate, monoammonium phosphate, triple superphosphate, potassium nitrate, potassium nitrate, potassium nitrate (nitrate of potash), potassium chloride, potassium chloride (muriate of potash), dipotassium and monopotassium salts of phosphates / phosphonates, and other NPK fertilizers, such as 10-34-0, 6-24-6, etc. The fertilizer compositions may also contain micronutrients including Zn, Co, Mo, Mn, etc.
[0090] The following embodiments are intended to illustrate specific aspects of the Disclosure and are not intended to limit the Disclosure. [Examples]
[0091] Examples All tests were conducted according to the customary CIPAC method for crop protection (CIPAC = Collaborative International Pesticides Analytical Council; www.cipac.org). Long-term storage was carried out according to CIPAC MT 46.3, with a storage time of 40°C. The storage time and temperature are as shown in the table. Particle size was measured using the CIPAC MT 187 test method for pesticides. D90 particle size indicates increased crystal growth. General preparation of suspension concentrates: The active ingredients and formulation deactivators were added without any particular order. The mixture was pre-milled using a rotor stator until a particle size of 80–150 μm was achieved. The mixture was further milled using a bead mill until a final particle size of 2–10 μm was achieved. Finally, the thickening agent xanthan gum was added to adjust the final viscosity. In a preferred embodiment, the penetration enhancer is added after milling. Materials used: Difenoconazole: DMI fungicide, Syngenta Fluopyram: SDHI fungicide, Bayer AG Benecel KM 200: Hydroxypropyl Methylcellulose Ether, Ashland Aerosil R-972: Hydrophobic Modified Hydrogenated Dispersed Silica, Evonik Aerosil 200: Hydrophilic water-dispersible silica, Evonik Morwet D-425: Naphthalene sulfonic acid, formaldehyde polymer, Akzo Nobel Synperonic PE / F 127: EO-PO-Ether, Croda Soprophor 4D384: Tristyrene-ethoxylate, ammonium salt, Solvay Geropon T 36: Polycarboxylate-sodium salt of maleic anhydride and 2,4,4-trimethylpentene polymer, Solvay Atplus FA: Binder, Kuroda Crovol CR 70G: Ethoxylated rapeseed oil, Croda KATHON CG / ICP: Biocides, Rhom and Haas Proxel GXL: Biocide, Lonza Rhodopol 23: Xanthan gum, Solvay SAG 1572: Antifoaming agent, Momentive Silcolapse 426 R: Antifoaming agent, Solvay Table 1: Examples R3, R13, R14 and R29 (%w / w) [Table 2] TIFF0007871285000005.tif117153 R3 is an example that does not contain the penetration enhancer f. The amounts of dispersants d) and e) were slightly modified to match the final viscosity. No particle size growth was observed, and no aggregates were present during accelerated storage. However, since cuticular penetration is insufficient as seen below (Table 3), a penetration enhancer f) is necessary considering the biological performance of this formulation. R14 is hydroxypropyl methylcellulose ether (Benecel K 200M)Regarding fluoxypyroxad-based antibacterial preparations, xanthan gum is used as a thickening agent, as described in WO2015124330. Created based on the combination of However, the formulation was not stable, and although particle size growth was acceptable, there was separation of the two phases and the solid. R13 without additional Benecel K 200M was R15 It was even worse than that. R29 further used Aerosil R 972 as a crystal growth inhibiting support material. The particle size was slightly larger than that of R13 and R14, but the liquid remained fluid after mixing with the stored samples and could be further utilized. However, compared to R35, R36, and R37, the addition of additional hydroxypropyl methylcellulose ether to the formulation was less desirable. Table 2: Examples R30, R35, R36, and R37 [Table 3] TIFF0007871285000007.tif169145R30 uses Aerosil200 (hydrophilic silica) compared to R29. While crystal growth is extremely high, the formulation maintains fluidity even after storage. However, like R29, this formulation contains hydroxypropyl methylcellulose ether, which is less desirable. R35-R37 are preferred formulations because they exhibit very low crystal growth, and the formulations remain fluid without separation or precipitation during accelerated storage. Bioavailability / Penetration Enhancement Evaluation The spray mixture (0.5 g of active ingredient / L) is added to each of the three apple cuticles. The amount of active substance in the cuticles is measured; measured by HPLC 0, 24, and 72 hours after drying. Table 3: Penetration of fluopyram through the apple cuticle (weight -%) [Table 4] The penetration enhancer exhibits more than four times the penetration of the active ingredient.
Claims
1. A concentrated aqueous suspension composition of pesticides: a) At least one SDHI bactericide, b) At least one DMI fungicide, c) at least one crystal growth inhibitory carrier c1) selected from the group consisting of clay, minerals and synthetic silica, and any crystal growth inhibitor, at least one further crystal growth inhibitor c2) selected from the group consisting of polycarboxylates and / or one further crystal growth inhibitor c3) selected from cellulose ether. d) At least one ionic dispersant selected from lignin and / or naphatalene-based sulfonates and their polymer condensates, Unlike e), d), and f), and if c2), also different from c2), at least one further emulsifier and / or dispersant, f) Oils of plant, mineral, and animal origin, and alkyl esters of these oils, ethoxylated branched alcohols, methyl end-capped ethoxylated branched alcohols, ethoxylated coconut alcohol, ethoxylated C12 / 15 alcohols, branched or linear propoxy-ethoxylated alcohols, Me end-capped propoxy-ethoxylated fatty acids, alkyl ether citrate surfactants, ethoxylated monoesters of glycerin containing fatty acids having 8 to 18 carbon atoms and an average of 10 to 40 EO units At least one penetration enhancer selected from esters or diesters, castor oil ethoxylates containing an average of 5 to 40 EO units, ethoxylated oleic acid, ethoxylated sorbitan fatty acid esters containing fatty acids having 8 to 18 carbon atoms and an average of 10 to 50 EO units, methyl-terminated propoxy-ethoxylated fatty acids, organically modified polysiloxanes, monoesters and diesters of sodium sulfosuccinate salts having branched or linear alcohols having 1 to 10 carbon atoms, and / or ethoxylated diacetylenediol. g) Optionally, further additives selected from colorants, thickeners, defoamers and / or antifreezes, which are different from c2) and c3) if c2) and / or c3) are present. h) Optionally, additional pest control agents different from a) and b), i) Water up to 100% The composition comprising the above.
2. The composition according to claim 1, characterized in that component a) is selected from the group comprising fluopyram and isoflucipram.
3. The composition according to claim 1 or 2, characterized in that component b) is difenoconazole.
4. The composition according to claim 1, characterized in that components a) and b) have a mixed melting point of 50 to 90°C.
5. The composition according to any one of claims 1 to 4, characterized in that the composition comprises one crystal growth inhibitory support c1) and one crystal growth inhibitory support c2).
6. The composition according to any one of claims 1 to 5, characterized in that the composition comprises one crystal growth inhibitory carrier c1), one crystal growth inhibitory carrier c2), and one crystal growth inhibitory carrier c3).
7. The composition according to any one of claims 1 to 6, characterized in that the composition contains component g) as an essential component.
8. The composition according to any one of claims 1 to 7, characterized in that the total of a) and b) and any further pest control agents is 15 to 80% by weight.
9. The composition according to any one of claims 1 to 8, characterized in that compounds a) and b) are present in a weight ratio of 4:1 to 1:
2.
10. The ingredients are, a) 2-80% by weight, b) 2-50% by weight, c1) 0.1 to 10% by weight, c2) 0.1-8% by weight d) 0.2-5% by weight, e) 0.5-10% by weight, f) 3-25% by weight, g) 0-12% by weight, h) 0-20% by weight, i) Up to 100% A composition according to any one of claims 1 to 9, characterized in that it exists in the form of a composition.
11. The ingredients are, a) 2-80% by weight b) 2-50% by weight c1) 0.1-10% by weight c2) 0.1-8% by weight d) 0.2-5% by weight e) 0.5-10% by weight f) 3-25% by weight g) 0.1-10% by weight h) 0-15% by weight i) Up to 100% The composition according to any one of claims 1 to 10, characterized in that it exists as follows.
12. The ingredients are, a) 10-30% by weight b) 8-20% by weight c1) 0.4-1.5% by weight c2) 0.4-1.5% by weight d) 0.8-2% by weight e) 2-4% by weight f) 7-11% by weight g) 1-6% by weight h) 0-15% by weight i) Up to 100% The composition according to any one of claims 1 to 11, characterized in that it exists as follows.
13. The ingredients are, a) 10-30% by weight b) 8-20% by weight c1) 0.4-1.5% by weight c2) 0.4-1.5% by weight c3) 0.1-1% by weight d) 0.8-2% by weight e) 2-4% by weight f) 7-11% by weight g) 1-6% by weight h) 0-15% by weight i) Up to 100% The composition according to any one of claims 1 to 12, characterized in that it exists as follows.
14. A method for controlling fungi, comprising applying an effective amount of the composition according to any one of claims 1 to 13 to a plant, a part of a plant, a seed, or an area where a plant grows.
15. Use of the composition according to any one of claims 1 to 13 for controlling fungi in useful plants.