A method for treating rice seeds with improved retention of agrochemicals, micronutrients, and colorants.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-01-28
- Publication Date
- 2026-08-11
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Figure BDA0004359660960000331 
Figure BDA0004359660960000332 
Figure BDA0004359660960000341
Abstract
Description
[0001] This application claims priority to Nr 21153954.9 filed in Europe on 28 January 2021, the entire contents of which are incorporated herein by reference for all purposes.
[0002] This invention relates to a method for preparing coated rice seeds, wherein a seed coating is applied at least partially to the surface of a dried rice seed, a coated rice seed, and a method for protecting newly formed rice seedlings from fungal diseases and / or pests before planting. Furthermore, this invention relates to a method for increasing the content of micronutrients in seeds by including micronutrients in the form of their salts within the coating.
[0003] Disease prevention treatments for transplanted rice and / or for controlling animal pests are known, involving the spraying or granulation of agricultural chemicals in paddy fields or seedling trays. However, this method of using agricultural chemicals in paddy fields after transplanting for disease prevention and / or pest control presents problems, resulting in the need for large quantities of agricultural chemicals or infrequently lasting effects. Even when spraying or applying granular agricultural chemicals to seedling trays reduces the amount of chemicals used compared to in paddy fields, in some cases, the amount still required is significant and the effects are not long-lasting.
[0004] Furthermore, zinc is an essential micronutrient for the normal growth, development, and health of both plants and humans. Currently, large areas of agricultural land are known to be zinc deficient, leading to a severe decline in crop productivity and the nutritional quality of food crops. Despite this, zinc deficiency remains unrecognized or underestimated and unaddressed in many countries. Therefore, there is an urgent need to understand and address zinc deficiency in these countries to promote both crop production and human health. Zinc is also particularly important for better tolerance of crop plants to various stressors such as drought, high temperatures, and salinity.
[0005] Applying zinc fertilizer to the soil and / or plant leaves provides a simple and highly effective solution to zinc deficiency in crops and to increasing zinc concentrations in food. This strategy greatly prevents unnecessary food production losses and helps improve public health. For example, zinc-rich rice and wheat grains can save the lives of up to 48,000 children in India each year.
[0006] For millions of people worldwide, an extra few milligrams of zinc daily can make a difference between illness or death and a healthy, productive life. By ensuring crops have an adequate supply of zinc, we can help address this global problem by providing significant health, social, and economic benefits (Zinc Fertilizer Brochure 2009, published by the International Zinc Association (IFA); see also Comparative Quantification / Global and Regional Burden of Diseases Attributable to Selected Major Risk Factors of Health Risks, Ezzati, Lopez, Rodgers, Murray (eds.), Chapter 5 - Zinc Deficiency, WHO, 2004).
[0007] Zinc is essential for the normal healthy growth and reproduction of plants, animals, and humans. When the supply of zinc available to plants is insufficient, crop yield and crop product quality are impaired. In plants, zinc plays a crucial role as a structural component or regulatory cofactor in many important biochemical pathways of various enzymes and proteins. When the zinc supply to plants is insufficient, zinc's physiological functions cannot be performed properly, thus adversely affecting plant growth. This can lead to obvious stress symptoms in plants, which vary by species and may include: stunted growth (reduced height), interveinal chlorosis (yellowing of leaves between veins), chlorotic leaves turning bronze, small and abnormally shaped leaves and / or stunted leaf development and whorled leaves (where leaves form whorls on shortened stems). So-called latent deficiency, without obvious visible symptoms, can result in a 20% loss in plant yield. Latent deficiency caused by zinc-deficient soils can cause significant economic losses for farmers. Therefore, it is necessary to identify zinc-deficient soils as early as possible through soil testing or crop plant analysis. Once identified, zinc-deficient soils can be readily treated with zinc fertilizers to provide crops with an adequate zinc supply, with zinc sulfate being the most widely used fertilizer to date (see BJ Alloway, Zinc in Soils and Crop Nutrition, 2nd ed., Brussels, Paris, 2008).
[0008] Rice seeds can be soaked and cultured before sowing. To protect rice seeds, pest control agents, especially fungicides, can be added to the soaking water or directly to the seeds after soaking or after germination and before transplanting (Japanese Patent Application Publication Nos. 9224424, 11028006, and 11049612). However, this strategy is not always satisfactory because the pest control agents used may not remain on the seeds at a sufficient concentration and be washed off after cultivation or transplanting, resulting in insufficient protection against diseases or pests.
[0009] When zinc is mentioned in this invention, it should be understood that it does not refer to the pure metal, but to zinc in its cation form in its salts and oxides.
[0010] EP 1 078 563 B1, for example, describes seed coating compositions for low-temperature application, wherein seeds are coated with a coating composition comprising a polymer and at least one active ingredient. These compositions can be used for rice seeds that are sown directly; however, if the rice seeds are first soaked and cultured before sowing, these compositions are not suitable for rice seeds because the coating is washed off.
[0011] WO 2016 / 055439 describes polymer coating with improved retention of active ingredients in the coating. However, as already shown, the retention of active ingredients and colorants still needs improvement, as the soaking water exhibits significant coloration after soaking, indicating the loss of colorants and possibly active ingredients on the seeds. Furthermore, the polymer does not exhibit sufficient flowability / viscosity, especially under cold conditions, making application and coating difficult.
[0012] Therefore, the object of this invention is to overcome these disadvantages and, compared with those agrochemicals used in conventional seedling tray treatments or other polymer coatings known in the art, to significantly reduce the amount of agrochemicals leached from the coating, and to provide a simple and inexpensive method for preventing diseases and / or controlling animal pests in transplanted rice, with long-lasting effects in paddy fields. Furthermore, the object of this invention is to improve zinc absorption into seeds for healthier plants and healthier grains that provide additional zinc upon consumption.
[0013] To solve the above problems, the inventors, through specialized research, discovered that treating rice seeds with a mixture of copolymers comprising the following components and at least one agrochemical can resolve the issue:
[0014] A copolymer of butyl acrylate with 1,4-divinylbenzene and styrene (a copolymer of 2-butyl acrylate with 1,4-divinylbenzene and vinylbenzene), and
[0015] A copolymer of butyl acrylate and styrene (a copolymer of 2-butyl acrylate and vinylbenzene),
[0016] Coated rice seeds can be obtained, which can be soaked in water and cultivated without washing away agricultural chemicals.
[0017] Further investigation revealed that if zinc was added to the coating in the form of its salt or oxide, the zinc content in the seeds increased.
[0018] It was also found that colorants from agrochemicals (a common practice in the art for marking and identifying seeds with specific treatments and corresponding agrochemicals) exhibited better retention during soaking due to the improved coating according to the invention.
[0019] Furthermore, the coating composition was found to be stable and have low viscosity, especially at low temperatures, which makes the coating process and application, as well as dosage adjustment, easier.
[0020] Surprisingly, the copolymer mixture was found to have sufficient permeability to allow soaking and cultivation to proceed without impeding germination, resulting in an improved germination rate compared to the polymer disclosed in WO 2016 / 055439, while showing little or no reduction in germination rate compared to untreated rice seeds. Furthermore, the copolymer mixture is insoluble in soaking water and can be used, for example, as a matrix or substrate for agrochemically active ingredients.
[0021] Therefore, a first embodiment of the present invention is a method for preparing coated rice seeds, wherein the seed coating is applied at least partially to the surface of dried rice seeds, wherein the method is characterized in that the seed coating comprises a mixture of copolymers and at least one agrochemical, the mixture of copolymers being composed of a copolymer of butyl acrylate with 1,4-divinylbenzene and styrene, and a copolymer of butyl acrylate with styrene (a copolymer of 2-butyl acrylate with vinylbenzene).
[0022] A second embodiment of the present invention is a method for preparing coated rice seeds, wherein the seed coating is applied at least partially to the surface of dried rice seeds, wherein the method is characterized in that the seed coating comprises a mixture of copolymers, at least one agrochemical and at least one zinc salt or zinc oxide, the mixture of copolymers being composed of a copolymer of butyl acrylate with 1,4-divinylbenzene and styrene, and a copolymer of butyl acrylate with styrene (a copolymer of 2-butyl acrylate with vinylbenzene).
[0023] In the third embodiment, the coating further contains a colorant and optionally other additives suitable for use in the coating.
[0024] The fourth embodiment relates to a seed coating comprising a mixture of copolymers and at least one agrochemical, the mixture of copolymers being composed of a copolymer of butyl acrylate with 1,4-divinylbenzene and styrene, and a copolymer of butyl acrylate with styrene (a copolymer of 2-butyl acrylate with vinylbenzene).
[0025] In the fifth embodiment, the seed coating further contains zinc salts or oxides, as well as optional colorants and additional coating aids, wherein in the preferred embodiment the colorant is mandatory.
[0026] In this invention, the term "polymer" is used for any polymer containing two or more different monomers. In particular, according to this invention, polymers containing two or three different monomers are also considered "polymers".
[0027] The term "dried rice seeds" refers to rice in a form suitable for storage for later use as seed. Rice seeds may have a typical residual moisture content for rice seeds, such as 20 wt.% or less, particularly 15 wt.% or less, preferably 14 wt.% or less. The moisture content can be determined by a moisture analyzer typically used for cereals (such as the Pfeuffer HE50) or by titration according to the Karl Fischer method.
[0028] Seeds may be coated once or several times, and the coating layers may have the same or different compositions. For example, the inner coating layer may contain a copolymer mixture and at least one fungicide, while the next outer layer may contain at least one insecticide, optionally together with an adhesive (like any suitable kind of polymer adhesive) or a copolymer mixture described in this invention.
[0029] According to a preferred embodiment of the present invention, the first copolymer is prepared by reacting at least the following monomers:
[0030] a) Butyl acrylate,
[0031] b) Styrene and 1,4-divinylbenzene
[0032] These monomers may preferably be present in the following amounts
[0033] 45 to 65 wt.%, particularly 50 to 70 wt.%, preferably 55 to 65 wt.%, of butyl acrylate;
[0034] 35-55% wt.-%, particularly 30 to 50 wt.-%, preferably 35 to 45 wt.-%, of styrene and 1,4-divinylbenzene.
[0035] According to a preferred embodiment of the present invention, the second copolymer is prepared by reacting at least the following monomers:
[0036] a) Butyl acrylate, and
[0037] b) Styrene
[0038] These monomers may preferably be present in the following amounts
[0039] 35 to 65 wt.%, particularly 40 to 60 wt.%, preferably 45 to 55 wt.%, of butyl acrylate;
[0040] Styrene of 35-65% wt.-%, particularly 40 to 60 wt.-%, preferably 45 to 55 wt.-%.
[0041] In a preferred embodiment, the copolymer consists only of the monomers described above.
[0042] The copolymer of butyl acrylate with 1,4-divinylbenzene and styrene is designated by CAS number 57516-68-4. The copolymer of butyl acrylate with styrene is designated by CAS number 25767-47-9.
[0043] These copolymer mixtures are advantageous because they effectively prevent agrochemicals from being washed away from the seeds during soaking and cultivation, while still maintaining sufficient water permeability. Furthermore, if these copolymer mixtures are used as water-based dispersions, most agrochemicals can be added and mixed to obtain stable dispersions, which facilitates further processing (i.e., seed coating). Finally, copolymers with the aforementioned amounts of monomers provide viscosity at room temperature, which is beneficial for fixing the coating to the seeds.
[0044] In a preferred embodiment, the copolymer does not contain acrylic acid.
[0045] The copolymers used in the methods of this invention can be prepared by any method known to those skilled in the art. In particular, by way of only one example, the copolymers can be prepared by free radical emulsion polymerization. The emulsion can be manufactured under pressure using a standard emulsion polymerization route, which is widely used to produce copolymers incorporating gaseous monomers, such as ethylene. The emulsion can be prepared using batch, semi-batch, or continuous batch feeding; all three techniques are used industrially.
[0046] The copolymers used in this invention can have a glass transition temperature (Tg) ranging from -100°C to 20°C, defined according to DIN 53 765 as the midpoint temperature using the tangential method with nitrogen as the inert gas, measured by dynamic differential scanning calorimetry. The Tg is particularly preferably -60°C to 20°C, preferably -10°C or lower, more preferably -20°C or lower. Particularly preferred Tgs are from -60°C to 0°C, -60°C to -20°C, or -60°C to -40°C. This is advantageous because the copolymer retains elasticity and viscosity under normal storage temperatures for rice seeds, allowing for good coating fixation and preventing coating delamination.
[0047] The copolymer can be applied to the seeds in any form known to those skilled in the art, preferably in the form of a dispersion. Aqueous dispersions are preferred because there is no concern about the negative impact of the solvent on germination rate. Rice seeds can be dried after coating. This can be achieved at room temperature or slightly higher temperatures, such as 30°C or 35°C. Techniques such as warm air drying or spray drying can also be used. In an alternative embodiment, the rice seeds are not dried.
[0048] To achieve the desired coating thickness, the coating process can be repeated once or several times, with a drying step following each coating step, until the desired coating thickness is reached. One or more additional coating layers may also be free of agrochemicals, thus serving as a protective layer.
[0049] In one embodiment, the copolymer of butyl acrylate with 1,4-divinylbenzene and styrene of the present invention may have a weight-average molecular weight Mw in the range of 400,000 to 800,000 g / mol, preferably 500,000 to 700,000 g / mol, and more preferably 550,000 to 650,000 g / mol.
[0050] In one embodiment, the butyl acrylate-styrene copolymer of the present invention may have a weight-average molecular weight Mw in the range of 25,000 to 125,000 g / mol, preferably 30,000 to 100,000 g / mol, and more preferably 40,000 to 80,000 g / mol.
[0051] In one particular embodiment, the copolymer of butyl acrylate with 1,4-divinylbenzene and styrene of the present invention may have a weight-average molecular weight Mw in the range of 400,000 to 800,000 g / mol, preferably 500,000 to 700,000 g / mol, and more preferably 550,000 to 650,000 g / mol, and the monomer may preferably be present in the following amounts: 45 to 65 wt.-%, particularly 50 to 70 wt.-%, preferably 55 to 65 wt.-%, of butyl acrylate; and 35 to 55 wt.-%, particularly 30 to 50 wt.-%, preferably 35 to 45 wt.-%, of styrene and 1,4-divinylbenzene.
[0052] In one particular embodiment, the butyl acrylate-styrene copolymer of the present invention may have a weight-average molecular weight Mw in the range of 25,000 to 125,000 g / mol, preferably 30,000 to 100,000 g / mol, and more preferably 40,000 to 80,000 g / mol, and the monomer may preferably be present in the following amounts: 35 to 65 wt.-%, particularly 40 to 60 wt.-%, preferably 45 to 55 wt.-%, of butyl acrylate; and 35 to 65 wt.-%, particularly 40 to 60 wt.-%, preferably 45 to 55 wt.-%, of styrene.
[0053] The weight-average molecular weight (Mw) can be determined by gel permeation chromatography (GPC) using THF (tetrahydrofuran) as a solvent and polystyrene as a standard. Unless otherwise specified in this invention, Mw is measured by this method.
[0054] The ratio of the first polymer to the second polymer can be in the range of 3:1 to 1:3, preferably in the range of 2:1 to 1:2, more preferably in the range of 1.5:1 to 1:1.5, and most preferably 1:1.
[0055] The dispersion may, for example, have a solids content of 30 to 80 wt.%, particularly 50 to 70 wt.%, preferably 55 to 65 wt.%, as measured according to DIN EN ISO 3251, at 130°C for 30 minutes. When using a dispersion with such a solids content, the preferred dosage of the dispersion relative to the entire coating formulation containing one or more agrochemicals is 1 to 20 wt.%, more preferably 2 to 15 wt.%, and most preferably 3 to 12 wt.%.
[0056] To improve film-forming properties, it is advantageous for the dispersion to have a minimum film-forming temperature of >=0°C as measured according to DIN ISO 2115.
[0057] According to a further preferred embodiment of the invention, the dispersion is substantially free of plasticizers and / or nonionic detergents, and in particular substantially free of alkylphenol ethoxylates. This is advantageous because the copolymers of the invention can be provided as water-based dispersions without the need for the aforementioned additives that may cause environmental problems. This is especially true for nonionic detergents, particularly alkylphenol ethoxylates.
[0058] For the purposes of this invention, any agricultural chemical can be used to provide the coating. Therefore, the agricultural chemical can be selected from the group consisting of: insecticides, fungicides, bactericides, viricides, acaricides, molluscicides, nematicides, ovicides, repellents, rodenticides, herbicides, safeners, fertilizers, biological agents, or mixtures thereof.
[0059] Agricultural chemicals, or referred to as “active ingredients” (“ai”) below, are specified in this document by their “common name”, as is known and described, for example, in the Pesticide Manual (“The Pesticide Manual”, 14th edition, UK Crop Protection Council 2006), or can be searched on the Internet (e.g., http: / / www.alanwood.net / pesticides).
[0060] Where compound (A) or compound (B) may exist in tautomeric forms, such compound shall be understood, in both the foregoing and the following text, to include, where applicable, the corresponding tautomeric forms, even if these are not specifically mentioned in each case.
[0061] 1) Ergosterol biosynthesis inhibitors, such as (1.001) cyclophosphamide, (1.002) difenoconazole, (1.003) flutriafol, (1.004) cyclophosphamide, (1.005) benzyl benzoate, (1.006) butyl morpholine, (1.007) pyraclostrobin, (1.008) fluquinazole, (1.009) fenazate, (1.010) imazalil, (1.011) imazalil sulfate, (1.012) tebuconazole, (1.013) tebuconazole, (1.014) cyproconazole, (1.015) paclobutrazol, (1.016) prochloraz, (1.017) propiconazole, (1.018) prothioconazole, (1.019) azoxystrobin, (1 .020) Spirocyclohexane, (1.021) Tebuconazole, (1.022) Flufenoxuron, (1.023) Triazophos, (1.024) Tridemorpholine, (1.025) Mefenoxuron, (1.026) (1R,2S,5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.027) (1S,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.028) (2R)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl] -1-(1H-1,2,4-triazol-1-yl)but-2-ol, (1.029)(2R)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)but-2-ol, (1.030)(2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)prop-2-ol, (1.031)(2S)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)but-2-ol, (1.032)(2S)-2-(1 (-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)but-2-ol, (1.033)(2S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)prop-2-ol, (1.034)(R)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.035)(S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-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-dioxolane-2-yl}methyl)-1H-1,2,4-triazole, (1.038) 1-({(2S,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolane-2-yl}methyl)-1H-1,2,4-triazole, (1.039) 1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)ethylene oxide-2-yl] methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.040)1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)epoxyethylene-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.041)1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)epoxyethylene-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.042)2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1, 2,4-Triazol-3-thione, (1.043)2-[(2R,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.044)2-[(2R,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.045)2-[(2R,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol- 3-Thione, (1.046)2-[(2S,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.047)2-[(2S,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.048)2-[(2S,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.049) 2-[(2S,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.050) 2-[1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.051) 2-[2-chloro-4-(2,4-dichlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)prop-2-ol, (1.052) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)prop-2-ol (1.053)2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)but-2-ol, (1.054)2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)pentan-2-ol, (1.055)chlorfluazol, (1.056)2-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)ethyleneoxy-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.057)2-{[rel(2R,3R)-3-(2-chlorophenyl)]methyl}-2,4-dihydro-3H-1,2,4-triazol-3-thione] )-2-(2,4-difluorophenyl)epoxyethylene-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.058)2-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)epoxyethylene-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.059)5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.060)5-(allylthioalkyl)-1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)epoxyethylene-2-yl]methyl 1H-1,2,4-triazole, (1.061)5-(allylthioalkyl)-1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)epoxyethylene-2-yl]methyl}-1H-1,2,4-triazole, (1.062)5-(allylthioalkyl)-1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)epoxyethylene-2-yl]methyl}-1H-1,2,4-triazole, (1.063)N'-(2,5-dimethyl-4-{[3-(1,1,2,2-tetrafluoroethoxy)phenyl]thioalkyl}phenyl)-N-ethyl-N-methylformamidinium, (1.064) N'-(2,5-dimethyl-4-{[3-(2,2,2-trifluoroethoxy)phenyl]thioalkyl}phenyl)-N-ethyl-N-methylformamidin, (1.065) N'-(2,5-dimethyl-4-{[3-(2,2,3,3-tetrafluoropropoxy)phenyl]thioalkyl}phenyl)-N-ethyl-N-methylformamidin, (1.066) N'-(2,5-dimethyl-4-{[3-(pentafluoroethoxy)phenyl]thioalkyl}phenyl)-N-ethyl-N-methylformamidin, (1.067) N'-(2,5-dimethyl-4-{3-[(1,1,2,2-tetrafluoroethyl)thioalkyl]phenoxy}phenyl)-N-ethyl-N-methylformamidin, (1.068) N'- (2,5-Dimethyl-4-{3-[(2,2,2-trifluoroethyl)thioalkyl]phenoxy}phenyl)-N-ethyl-N-methylformamidinium, (1.069)N'-(2,5-dimethyl-4-{3-[(2,2,3,3-tetrafluoropropyl)thioalkyl]phenoxy}phenyl)-N-ethyl-N-methylformamidinium, (1.070)N'-(2,5-dimethyl-4-{3-[(pentafluoroethyl)thioalkyl]phenoxy}phenyl)-N-ethyl-N-methylformamidinium, (1.071)N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidinium, (1.072)N'-(4-{[3-(difluoromethoxy)phenyl]thioalkyl}-2,5-dimethylphenyl) (1.073)N'-(4-{3-[(difluoromethyl)thioalkyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methylformamidinium, (1.074)N'-[5-bromo-6-(2,3-dihydro-1H-indene-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylformamidinium, (1.075)N'-{4-[(4,5-dichloro-1,3-thiazo-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylformamidinium, (1.076)N'-{5-bromo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N -Methylformamidinium, (1.077)N'-{5-bromo-6-[(1S)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylformamidinium, (1.078)N'-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylformamidinium, (1.079)N'-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylformamidinium, (1.080)N'-{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylformamidinium, (1.081) Ipfentrifluconazole, (1.082) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)prop-2-ol, (1.083) 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)prop-2-ol, (1.084) 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)prop-2-ol, (1.085) 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl] Imidazole-4-carboxynitrile, (1.086)4-[[6-[racemic-(2R)-2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thio-4H-1,2,4-triazol-1-yl)phenyl]-3-pyridyl]oxy]benzonitrile, (1.087)N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenylethyl)phenyl]-N-methylformamidin, (1.088)N'-{5-bromo-2-methyl-6-[(1-propoxypropyl-2-yl)oxy]pyridin-3-yl}-N-ethyl-N-methylformamidin, (1.089) hexazolol, (1.090) tebuconazole, (1.091) nitrilobenzazole.
[0062] 2) Inhibitors of respiratory chain complex I or II, such as (2.001) benzovindiflubenzuron, (2.002) bifenpyroxime, (2.003) cyazofamid, (2.004) carbendazim, (2.005) fluopyram, (2.006) fluopyram, (2.007) fluopyram, (2.008) fluopyram, (2.009) isopyraclostrobin, (2.010) pyraclostrobin (trans-episode enantiomers 1R, 4S, 9S), (2.011) pyraclostrobin (trans-episode enantiomers 1S, 4R, 9R), (2.012) pyraclostrobin (trans-episode racemic mixture 1RS, 4SR, 9SR), (2.013) pyraclostrobin (cis-episode racemic mixtures 1RS, 4SR, 9SR), (2.014) pyraclostrobin (cis-episode racemic 1R,4S,9R), (2.015) pyraclostrobin (cis-episode racemic 1S,4R,9S), (2.016) pyraclostrobin (cis-episode racemic 1RS,4SR,9RS), (2.017) fluopyram, (2.018) pyraclostrobin, (2.019) fluopyram, (2.020) bifenpyrazinamide, (2.021) fluopyram, (2.022) 1,3-dimethyl-N-(1,1,3-trimethyl-2,3- (2.023) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-indene-4-yl]-1H-pyrazole-4-carboxamide, (2.024) 1,3-dimethyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-indene-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-indene-4-yl) (2.027) 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-indene-4-yl)-1H-pyrazole-4-carboxamide, (2.028) inpyrfluxam, (2.029) 3-(difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-indene-4-yl]-1H-pyrazole-4-carboxamide, (2.030) fluopyram, (2.031) 3-(difluoromethyl)-N-[(3R)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-indene-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.032) 3-(difluoromethyl)-N-[(3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-indene-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.033) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-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 Amides, (2.036)N-(2-tert-butylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-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-bridged methylenenaphthalene-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.040)N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-bridged methylenenaphthalene-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.041)N-[1-(2,4-dichlorophenyl)-1-methoxypropyl-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-(difluoromethyl)-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-thiocarboxamide, (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- ... (2.054)N-cyclopropyl-N-(2-cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (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 (2.057) cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.058) pyrapropoyne, (2.059) N-[racemic-(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)nicotinamide.
[0063] 3) Inhibitors of respiratory chain complex III, such as (3.001) azoxystrobin, (3.002) indoxam, (3.003) pyraclostrobin, (3.004) fenvalerate, (3.005) eugenol, (3.006) cyazofamid, (3.007) azoxystrobin, (3.008) oxadiazon, (3.009) oxadixyl, (3.010) imidacloprid, (3.011) fluopyram, (3.012) fluopyram, (3.013) azoxystrobin, (3.014) fenoxystrobin, (3.015) azoxystrobin. (3.016) azoxystrobin, (3.017) azoxystrobin, (3.018) azoxystrobin, (3.019) azoxystrobin, (3.020) oxadiazon, (3.021) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylvinyl]oxy}phenyl)ethylene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylacetamide, (3.022) (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2- (Methoxyimino)-N,3-dimethylpent-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) fenpicoxamid, (3.026) mandestrobin, (3.027) N-(3-ethyl-3, 5,5-Trimethylcyclohexyl)-3-carbamate-2-hydroxybenzamide, (3.028)(2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.029){5-[3-(2,4-dimethylphenyl)-1H-pyrazol-1-yl]-2-methylbenzyl}carbamate, (3.030)methyltetraprole, (3.031)pyridinediamide.
[0064] 4) Inhibitors of mitosis and cell division, such as (4.001) carbendazim, (4.002) ethoxysulfuron, (4.003) thiamethoxam, (4.004) fluopyram, (4.005) pendimethalin, (4.006) thiabendazole, (4.007) thiophanate-methyl, (4.008) benzylpyridinium, (4.009) pyridachlometyl, (4.010) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (4.011) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine, (4.012) 4 -(2-bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.013)4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.014)4-(2-bromo-4-fluorophenyl)-N-(2-bromophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.015)4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.016)4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl -1H-pyrazole-5-amine, (4.017)4-(2-bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.018)4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.019)4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.020)4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.021)4-(2-chloro-4-fluorophenyl)-N- (2-Fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.022)4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (4.023)N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.024)N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.025)N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.026) Fluorosulfuron.
[0065] 5) Compounds capable of multi-site action, such as (5.001) Bordeaux mixture, (5.002) captan, (5.003) chlorothalonil, (5.004) copper hydroxide, (5.005) copper naphthenate, (5.006) copper oxychloride, (5.007) copper oxide, (5.008) copper oxychloride, (5.009) copper sulfate (2+), (5.010) dithiazolinone, (5.011) dextrin, (5.012) captan, (5.013) mancozeb, (5.01) 4) Mancozeb, (5.015) Mancozeb, (5.016) Zinc Mancozeb, (5.017) Copper Quinoline, (5.018) Propineb, (5.019) Sulfur and sulfur preparations (including calcium polysulfides), (5.020) Thiram, (5.021) Zinc Mancozeb, (5.022) Zinc Thiram, (5.023) 6-Ethyl-5,7-dioxo-6,7-dihydro-5H-pyrrolo[3',4':5,6][1,4]dithiacino[2,3-c][1,2]thiazolyl-3-carboxynitrile.
[0066] 6) Compounds that can induce host defense, such as (6.001) aramid-benzene-S-methyl, (6.002) isothiazine, (6.003) thiabendazole, and (6.004) thiamethoxam.
[0067] 7) Inhibitors of amino acid and / or protein biosynthesis, such as (7.001) pyrimethanil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) tetracycline, (7.005) pyrimethanil, (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinoline-1-yl)quinoline.
[0068] 8) ATP production inhibitors, such as (8.001) silthiamethoxam.
[0069] 9) Cell wall synthesis inhibitors, such as (9.001) benzimidazole, (9.002) dimethomorph, (9.003) flumethomorph, (9.004) isopropiconazole, (9.005) dimethomorph, (9.006) butylpyrromorph, (9.007) cymoxanil, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one.
[0070] 10) Lipid and membrane synthesis inhibitors, such as (10.001) cymoxanil, (10.002) cymoxanil hydrochloride, and (10.003) methyl thiophanate.
[0071] 11) Inhibitors of melanin biosynthesis, such as (11.001) tricyclazole and (11.002) tolprocarb.
[0072] 12) Nucleic acid synthesis inhibitors, such as (12.001) Benzoyl, (12.002) Benzoyl-M (refined Benzoyl), (12.003) Metalaxyl, and (12.004) Metalaxyl-M (refined Metalaxyl).
[0073] 13) Signal transduction inhibitors, such as (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) propoxyquin, (13.005) quinoxalic acid, and (13.006) vinclozolin.
[0074] 14) Compounds that can be used as uncoupling agents, such as (14.001) fluazinam and (14.002) chlorpyrifos.
[0075] 15) Other fungicides selected from the group consisting of: (15.001) abscisic acid, (15.002) bethoxazine, (15.003) bethoxazine, (15.004) carbadoxam, (15.005) carvone, (15.006) chlorfenapyr, (15.007) thiophanate-methyl, (15.008) cycloflufenicol, (15.009) cymoxanil, (15.010) cyclopropanesulfonamide, (15.011) fluoxastrobin, (15.012) aluminum tris(ethyl phosphonate), (15.013) calcium tris(ethyl phosphonate), (15.014) sodium tris(ethyl phosphonate), (15.015) methyl isothiocyanate, (15.016) benomyl, (15 .017) Midomycin, (15.018) Natamycin, (15.019) Nickel dimethyl dithiocarbamate, (15.020) Phthalosporin, (15.021) Oxamocarb, (15.022) Fluoxetine, (15.023) Oxyfenthiin, (15.024) Pentachlorophenol and its salt, (15.025) Phosphorous acid and its salt, (15.026) Fibromophosphonate, (15.027) Chlazafenone, (15.028) Tebufloquin, (15.029) Phthalosporin, (15.028) Tebufloquin, (15.029) Phthalosporin, (15.020 ... 030) Methamidosulfuron, (15.031) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazolyl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetone, (15.032) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazolyl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetone, (15.033) 2-(6-benzylpyridin-2-yl)quinazolin, (15 .034) dipymetitrone, (15.035) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl] acetone, (15.036) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl] acetone, (15.037) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazolyl)piperidin-1-yl]acetone, (15.038) 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazolin, (15.039) 2-{(5R)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazolyl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenylmethanesulfonate, (15.040)2-{(5S)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazo-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenylmethanesulfonate, (15.041) isoflurnoquine, (15.042)2-{2-fluoro-6-[(8-fluoro-2-methylquinolin-3-yl)oxy]phenyl}prop-2-ol, (15.043) fluoxapiprolin, (15.044)2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3- [-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl]phenylmethanesulfonate, (15.045) 2-phenylphenol and its salt, (15.046) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinoline-1-yl)quinoline, (15.047) quinofumelin, (15.048) 4-amino-5-fluoropyrimidin-2-ol (tautomer form: 4-amino-5-fluoropyrimidin-2(1H)-one), (15.049) 4-oxo-4-[(2-phenylethyl)amino]butyric acid, (15.050) 5-amino-1,3,4-thiadiazole-2-thiol, (15.051) 5-chloro-N'-phenyl- N'-(prop-2-yn-1-yl)thiophene-2-sulfonylhydrazine, (15.052)5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4-amine, (15.053)5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine, (15.054)9-fluoro-2,2-dimethyl-5-(quinolin-3-yl)-2,3-dihydro-1,4-benzoxazheptanine, (15.055){6-[({[(Z)-(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate butyl-3-yn-1-yl ester, (15.056)(2Z)-3-amino-2-cyano-3-phenyl acrylate ethyl ester, (15.057) Phenazin-1-carboxylic acid, (15.058) Propyl 3,4,5-trihydroxybenzoate, (15.059) Quinoline-8-ol, (15.060) Quinoline-8-ol sulfate (2:1), (15.061) {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl} tert-butyl carbamate, (15.062) 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one, (15.063) aminopyrifen, (15.064) (N'-[2-chloro-4-(2-fluorobenzene)] (15.065)(N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidin), (15.066)(2-{2-[(7,8-difluoro-2-methylquinoline-3-yl)oxy]-6-fluorophenyl}prop-2-ol), (15.067)(5-bromo-1-(5,6-dimethylpyridin-3-yl)-3,3-dimethyl-3,4-dihydroisoquinoline), (15.068)(3-(4,4-difluoro-5,5-dimethyl-4,5-dihydrothieno[2,3-c]pyridin-7-yl)quinoline), (15.069)(1-(4,5-dimethyl) (15.070) 8-fluoro-3-(5-fluoro-3,3-dimethyl-3,4-dihydroisoquinoline), (15.071) 8-fluoro-3-(5-fluoro-3,3-dimethyl-3,4-dihydroisoquinoline-1-yl)quinolone, (15.072) 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline-1-yl)-8-fluoroquinoline, (15.073) (N-methyl-N-phenyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide), (15.074){4- [5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}carbamate, (15.075)(N-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}cyclopropanecarboxamide), (15.076)N-methyl-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.077)N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.078)N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.079) N-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]cyclopropane formamide, (15.080) N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.081) 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, (15.082) N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]acetamide, (15.083) N-[(E)-N-methoxy-C-methyl-carboimino]-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]cyclopropane formamide, (15.083) N-[(E)-N-methoxy-C-methyl-carboimino]-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]cyclopropane formamide, (15.080) N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, (15.082) N-[(E)-N-methoxy-C-methyl-carboimino]-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]cyclopropane formamide, (15.083 ... 4-Oxadiazol-3-yl]benzamide, (15.084)N-[(Z)-N-methoxy-C-methyl-carboimino]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.085)N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide, (15.086)4,4-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidone-2-one, (15.087)N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiobenzamide, (15.088)5-methyl -1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidone-2-one, (15.089)N-((2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-3,3,3-trifluoropropionamide, (15.090)1-methoxy-1-methyl-3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.091)1,1-diethyl-3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.092)N-[[4-[5-(trifluoromethyl)-1,2,4-difluoromethyl]phenyl]methyl]urea (15.093) N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropane formamide, (15.094) 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.095) N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl)cyclopropane formamide, (15.096) N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propane, (15.097) N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]propionamide, (15.098) 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.099) 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.100) 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.101) 1-[[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.102)4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidine-3-one, (15.103)5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidine-3-one, (15.104)3,3-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.105)1-[[3-fluoro-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one (15.106) 4,4-dimethyl-2-[[4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidine-3-one, (15.107) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidine-3-one, (15.108) 1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-pyrazole-4-carboxylic acid ethyl ester, (15.109) N,N-dimethyl-1-{4-[5-(trifluoromethyl)-1, 2,4-Oxadiazol-3-yl]benzyl}-1H-1,2,4-triazol-3-amine, (15.110)N-{2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}butyramide, (15.111)N-(1-methylcyclopropyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.112)N-(2,4-difluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.113)1-(5,6-dimethylpyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.114) 1-(6-(difluoromethyl)-5-methyl-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.115) 1-(5-(fluoromethyl)-6-methyl-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.116) 1-(6-(difluoromethyl)-5-methoxy-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.117) 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl dimethylcarbamate, (15.118) (15.119) 3-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazo-4-yl]-1,5-dihydro-2,4-benzodioxane-6-yl methanesulfonate, (15.120) 9-fluoro-3-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazo-4-yl]-1,5-dihydro-2,4-benzodioxane-6-yl methanesulfonate, (15.121)3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazole-1-yl]acetyl}piperidin-4-yl)-1,3-thiazo-4-yl]-1,5-dihydro-2,4-benzodioxane-6-yl methanesulfonate, (15.122)3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazole-1-yl]acetyl}piperidin-4-yl)-1,3-thiazo-4-yl]-9-fluoro-1,5-dihydro-2,4-benzodioxane-6-yl methanesulfonate, (15.123)1-(6,7-dimethylpyrazolo[1,5-a]) (15.124)8-fluoro-N-(4,4,4-trifluoro-2-methyl-1-phenylbut-2-yl)quinoline-3-carboxamide, (15.125)8-fluoro-N-[(2S)-4,4,4-trifluoro-2-methyl-1-phenylbut-2-yl]quinoline-3-carboxamide, (15.126)N-(2,4-dimethyl-1-phenylpent-2-yl)-8-fluoroquinoline-3-carboxamide, and (15.127)N-[(2S)-2,4-dimethyl-1-phenylpent-2-yl]-8-fluoroquinoline-3-carboxamide.
[0076] All named mixed pairs of categories (1) to (15) may optionally form salts with suitable bases or acids, particularly in the form of biologically acceptable salts such as sodium, potassium, ammonium, etc., if their functional groups are capable of doing so.
[0077] Regarding insecticides, acaricides, and nematicides, the following substances may be used:
[0078] 1) Acetylcholinesterase (AChE) inhibitors, such as carbamates, including carbofuran, aldicarb, chlorpyrifos, carbofuran, thiamethoxam, carbofuran sulfonate, carbofuran, carbofuran, thiamethoxam, ethylcarbide, sec-butylcarbide, amitraz, furazolidone, isoprocarb, thiophanate-methyl, methomyl, chlorpyrifos, propoxur, thiamethoxam, thiamethoxam, thiamethoxam, pymetrozine, thiamethoxam, XMC, and methomyl; or organophosphates, such as acephate, methyl pyrazophos, ethyl glutathione, methyl glutathione, thion, oxychlorpyrifos, chlorpyrifos, chlorpyrifos, methyl chlorpyrifos, phosmet, pyridaben, demeton-S-methyl, diazinon, dichlorvos / DDVP, and chlorpyrifos. Phosphorus, dimethoate, methyl chlorpyrifos, phorate, EPN, ethion, phosmet, phosmet, phosmet, phosmet, thiamethoxam, phosmet, thiamethoxam, heptamethrin, neonicotinoids, isofenphos, O-(methoxyaminothiophosphoryl)salicylic acid isopropyl ester, isoxazolium, malathion, phosmet, methamidophos, chlorpyrifos, phosmet, dibromophos, dimethoate, sulfoxide, parathion, methyl parathion, phosmet, phorate, phosmet, phosmet, phosmet, phosmet, phosmet, phosmet, phosmet, phosmet, phosmet, phosmet, methyl pyrimidine phosphate, phosmet, phosmet, phosmet, phosmet, phosmet, phosmet, methyl pyrimidine phosphate, phosmet, phosmet, phosmet, phosmet, phosmet, phosmet, methyl phorate, triazophos, trichlorfon and phosmet.
[0079] 2) GABA-gated chloride channel antagonists, such as cyclopentadiene organochlorines, such as chlordane and thiodine; or phenylpyrazoles (fiproles), such as (16.1) acetamiprid and (16.2) fipronil.
[0080] 3) Sodium channel modulators / voltage-dependent sodium channel blockers, such as pyrethroids, including flufenoxuron, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, biobenzylfuran, cypermethrin, lambda-cyhalothrin, β-cyhalothrin, cyhalothrin, λ-cyhalothrin, γ-cyhalothrin, cypermethrin, α-cypermethrin, β-cypermethrin, θ-cypermethrin, ζ-cypermethrin, and deltamethrin [(1R)] -trans isomer], deltamethrin, dextromethorphan [(EZ)-(1R) isomer), cypermethrin, fenvalerate, cypermethrin, fenvalerate, flufenoxuron, flufenoxuron, t-flumethrin, fenvalerate, fenvalerate, fenvalerate, fenvalerate, fenvalerate, fenvalerate, fenvalerate [(1R)-trans isomer], dextromethorphan, pyrethroid (pyrethrum), fenvalerate, flusilyl, fenvalerate, fenvalerate [(1R)-trans isomer], fenvalerate and fenvalerate, or DDT or methoxydichlorophenoxyacetic acid.
[0081] 4) Nicotinic acetylcholine receptor (nAChR) agonists, such as neonicotinoids, such as (17.1) acetamiprid, (17.2) thiamethoxam, (17.3) dinotefuran, (17.4) imidacloprid, (17.5) acetamiprid, (17.6) thiamethoxam and (17.7) thiamethoxam, or (17.8) nicotine or (17.9) flonicamid.
[0082] 5) Nicotinic acetylcholine receptor (nAChR) allosteric activators, such as spinosads, such as (18.1) ethyl spinosad and (18.2) spinosad.
[0083] 6) Chloride channel activators, such as avermectin / milbemycin, such as avermectin, emamectin benzoate, rapamectin and mibamectin.
[0084] 7) Juvenile hormone analogues, such as juvenile hormone analogues, such as acetamiprid, acetamiprid and acetamiprid, or phenoxycarb or pyriproxyfen.
[0085] 8) Mixed nonspecific (multi-site) inhibitors, such as haloalkanes, such as methyl bromide and other haloalkanes; or chloropicrin or thiocyanate or borax or tartaric acid.
[0086] 9) Selective feeding blockers for homoptera, such as pymetrozine or flonicamid.
[0087] 10) Mite growth inhibitors, such as tetradifon, thiamethoxam, flufenoxam, or etoxazole.
[0088] 11) Insect midgut microbial disruptors, such as Bacillus thuringiensis subsp. Israel, Bacillus coccidioides, Bacillus thuringiensis subsp. niger, Bacillus thuringiensis subsp. Kurstak, Bacillus thuringiensis subsp. Tenebrionis, and BT crop proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Ab1.
[0089] 12) Inhibitors of mitochondrial ATP synthase, such as bufenozide or organotin acaricides, such as triazole tin, tricyclic tin and fenbutatin, or propargite or trichlorfon.
[0090] 13) Oxidative phosphorylation uncoupling agents that interrupt the proton gradient, such as chlorfenapyr, DNOC and fipronil.
[0091] 14) Nicotinic acetylcholine receptor (nAChR) channel blockers, such as chlorpyrifos, batan hydrochloride, chlorpyrifos ring and chlorpyrifos.
[0092] 15) Chitin biosynthesis inhibitors, type 0, such as bis(triflufenoxuron), flufenoxuron, diflubenzuron, flucyclobenzuron, flufenoxuron, flufenoxuron, fenflurfen, flufenoxuron, fluorobenzoate, polyfluorourea, flufenoxuron and chlorfenapyr.
[0093] 16) Chitin biosynthesis inhibitors, type 1, such as thiamethoxam.
[0094] 17) Ecdyskin disruptors, such as cyromazine.
[0095] 18) Ecdysone receptor agonists, such as cyclotetracycline, chlorfenapyr, methoxyfenozide and tebufenozide.
[0096] 19) Octopus receptor agonists, such as dimethicone.
[0097] 20) Inhibitors of electron transport in mitochondrial complex III, such as fludioxon or pyrimethanil.
[0098] 21) Inhibitors of electron transport in mitochondrial complex I, such as METI acaricides, such as quinclorac, azoxystrobin, pyrimethanil, pyridaben, and acetamiprid or rotenone (Rotenone).
[0099] 22) Voltage-dependent sodium channel blockers, such as indoxacarb or cyfluthrin.
[0100] 23) Acetyl-CoA carboxylase inhibitors, such as quaternium and teratogen derivatives, such as spirodiclofen, spirodiclofen and spirotetramat.
[0101] 24) Inhibitors of electron transport in mitochondrial complex IV, such as phosphine derivatives, such as aluminum phosphide, calcium phosphide, phosphine and zinc phosphide; or cyanides.
[0102] 25) Inhibitors of electron transport in mitochondrial complex II, such as cypermethrin and diflubenzuron.
[0103] 28) Lanni base receptor modulators, such as diamides, such as (19.1) chlorantraniliprole, (19.2) bromocyanamide and (19.3) flufenoxuron.
[0104] Other active ingredients with unknown or undetermined modes of action include, for example, bispyribac-methyl, azadirachtin, benclothiazide, benzoxazine, bifenazate, bromopropylate, manganese chlorpyrifos, cryolite, trichlorfon, flufenoxuron, flufenoxuron sulfone, flometoquinone, pyrimethanil, flufenoxuron, difenoconazole, fluopyram, flupyrflufenoxuron, furazolidone, heptamethrin, chlorthalidone, iprodione, chlorfluazuron, piperazine, pyribac-sodium, fipronil, pyrimethanil, tetrafluoroethylene, and iodomethacin; in addition, products based on Bacillus stolonifer (including but not limited to strain CNCM I-1582, such as VOTiVO) TM, BioNem) or one of the following known active compounds: 3-bromo-N-{2-bromo-4-chloro-6-[(1-cyclopropylethyl)carbamoyl]phenyl}-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide (known from WO2005 / 077934) and 1-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine (known from WO2006 / 043635), {1'-[ (2E)-3-(4-chlorophenyl)prop-2-en-1-yl]-5-fluorospiro[indol-3,4'-piperidin]-1(2H)-yl}(2-chloropyridin-4-yl)methyl ketone (known from WO2003 / 106457), 2-chloro-N-[2-{1-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]piperidin-4-yl}-4-(trifluoromethyl)phenyl]isonicotinamide (known from WO2006 / 003494), 3-(2,5-dimethylphenyl)-4-hydroxy-8-methoxy-1,8- Diazaspiro[4.5]dec-3-en-2-one (known from WO2009 / 049851), 3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-ylethyl carbonate (known from WO2009 / 049851), 4-(but-2-yn-1-yloxy)-6-(3,5-dimethylpiperidin-1-yl)-5-fluoropyrimidine (known from WO2004 / 099160), 4-(but-2-yn-1-yloxy)-6-(3-chlorophenyl) Pyrimidine (known from WO2003 / 076415), PF1364 (CAS Registry No. 1204776-60-2), 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl]-2-methyl-N-{2-oxo-2-[(2,2,2-trifluoroethyl)amino]ethyl}benzamide (known from WO2005 / 085216), 4-{5-[3-chloro-5-(trifluoromethyl)phenyl]-5-(trifluoromethyl)-4,5-dihydro-1,2-Oxazol-3-yl}-N-{2-oxo-2-[(2,2,2-trifluoroethyl)amino]ethyl}-1-naphthylcarboxamide (known from WO2009 / 002809), methyl 2-[2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)-5-chloro-3-methylbenzoyl]-2-methylhydrazine carboxylate (known from WO2005 / 085216), methyl 2-[2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)-5-cyano-3-methylbenzoyl]-2-ethylhydrazine carboxylate (known from WO2005 / 085216), methyl 2-[2-({[3- methyl bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)-5-cyano-3-methylbenzoyl]-2-methylhydrazine carboxylate (known from WO2005 / 085216), methyl 2-[3,5-dibromo-2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)benzoyl]-2-ethylhydrazine carboxylate (known from WO2005 / 085216), methyl 1-(3-chloropyridin-2-yl)-N-[4-cyano-2-methyl-6-(methylcarbamoyl)phenyl]-3-{[5-(trifluoromethyl)-2H-tetrazole-2-yl]methyl}-1H-pyrazol-5-carboxamide (known from WO2010) / 069502 known), N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide (known from CN102057925), 3-chloro-N-(2-cyanopropyl-2-yl)-N-[4-(1,1,1,2,3,3,3-heptafluoropropyl-2-yl)-2-methylphenyl]phthalamide (known from WO2012 / 034472), 8-chloro-N-[(2-chloro-5-methoxyphenyl)sulfonyl]-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxamide (known from WO2010 / 129500), 8-chloro- N-[(2-chloro-5-methoxyphenyl)sulfonyl]-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxamide (known from WO2009 / 080250), N-[(2E)-1-[(6-chloropyridin-3-yl)methyl]pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide (known from WO2012 / 029672), 1-[(2-chloro-1,3-thiazo-5-yl)methyl]-4-oxo-3-phenyl-4H-pyrido[1,2-a]pyrimidin-1-onthium-2-ol (known from WO2009 / 099929), 1-[(6-chloropyridin-3-yl)methyl]-4-oxo-3-phenyl-4H-pyrido[1,2-a]pyrimidin-1-onthium-2-ol salt (known from WO2009 / 099929), 1-[(6-chloropyridin-3-yl)methyl]-4-oxo-3-phenyl-4H-pyrido[1,2-a]pyrimidin-1-onthiol (known from WO2009 / 099929), (5S,8R)-1-[(6-chloropyridin-3-yl)methyl]-9-nitro-2,3,5,6,7,8-hexahydro-1H-5,8-epoxyimidazo[1,2-a]azapyrrolidone (known from WO2010 / 069266), (2E)-1-[(6-chloropyridin-3-yl)methyl]-N'-nitro-2-pentylhydrazine formamidinium (known from WO2010 / 069266) 60231 (known), 4-(3-{2,6-dichloro-4-[(3,3-dichloroprop-2-en-1-yl)oxy]phenoxy}propoxy)-2-methoxy-6-(trifluoromethyl)pyrimidine (known from CN101337940), N-[2-(tert-butylcarbamoyl)-4-chloro-6-methylphenyl]-1-(3-chloropyridin-2-yl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide (known from WO2008 / 134969).
[0105] While one or more agrochemicals may be independently selected from the substances mentioned above and combined in any possible manner, it is preferred that at least one agrochemical is selected from isothiazamide, fluoxastrobin, fluoxastrobin aniline, azole fungicides (especially tebuconazole, cyproconazole, propiconazole, or difenoconazole), methoxyacrylates (especially azoxystrobin, pyraclostrobin, or pyrimethanil), pyraclostrobin, metalaxyl, fludioxonil, thiamethoxam, fipronil, flufenoxuron, chlorantraniliprole, bromuconamide, imidacloprid, thiamethoxam, thiamethoxam, spinosad, tetrazole, acetamiprid, or mixtures thereof, preferably combinations of isothiazamide and azoxystrobin, isothiazamide and fluoxastrobin aniline, or fluoxastrobin aniline and azoxystrobin. Particularly preferred are fluoxastrobin aniline, isothiazamide, chlorantraniliprole, azoxystrobin, tetrazole, and acetamiprid. In one embodiment, the agrochemical is isothiazamide. According to another embodiment, the agricultural chemical is chlorantraniliprole. These agricultural chemicals are particularly preferred for coating rice seeds according to the present invention because they are suitable for diseases and pests specific to rice, and because the copolymers of the present invention effectively prevent these substances from being washed off the coated seeds.
[0106] Seed coatings may further comprise at least one colorant, surfactant, organic solvent, and / or additional polymers or copolymers. The addition of colorants, such as red, green, blue, etc., has the advantage that it is obvious to everyone that the rice seeds have been treated, thus greatly reducing the risk of the coated rice being unintentionally used for food purposes. Furthermore, the colorant can indicate whether the coating remains on the seed during soaking and cultivation. For example, the colorant can be selected not only by its color but also by its exudation behavior from the coating, provided it is similar to the agrochemical used in the coating. Thus, the applicator can actually see that no coating wash-off has occurred. In this case, the colorant can be used as a semi-quantitative benchmark for exudation behavior, for example, by comparing the color of the seeds before and after soaking with a color chart indicating the relationship between color and agrochemical content. Spectroscopic methods can also be used for the purpose of assessing the color intensity before and after soaking. Additionally, the colorant can indicate the quality of the coating, showing the uniformity of the coating on or among all seeds.
[0107] The colorant used can be a visible color or a UV dye. If an inorganic colorant is used, it can also serve as a source of trace elements.
[0108] The coating can have any possible structure or layer sequence. According to a preferred embodiment, the copolymer and agrochemical are mixed before application to the seeds, particularly coated rice seeds, which are then treated with another agrochemical, preferably an insecticide. The agrochemical mixed with the copolymer is an advantageous fungicide.
[0109] Alternatively, the copolymer and agrochemical can be applied to the seeds in a sequential manner, with the seeds preferably first coated with at least one agrochemical and then coated with the copolymer.
[0110] The application rate of the copolymer can vary over a wide range. For example, the application rate relative to the weight of untreated seeds is 0.001 to 2.5 wt.%, particularly 0.01 to 1.25 wt.%, preferably 0.025 to 1 wt.%.
[0111] The application rate of agricultural chemicals depends primarily on dosage requirements and can be determined by a technician. As just one example, the application rate of agricultural chemicals relative to the weight of untreated seeds is 0.001 to 5 wt.%, particularly 0.01 to 2.5 wt.%, preferably 0.05 to 1 wt.%. To give non-limiting examples of specific fungicides, the application rate of isothiazamide can be selected from 0.05 to 2 wt.%, particularly 0.1 to 1 wt.%, and the application rate of azoxystrobin can be selected from 0.01 to 1 wt.%, particularly 0.05 to 0.5 wt.%, each relative to the weight of untreated seeds.
[0112] Agricultural chemicals can be used in any available form or formulation, such as as solids (wettable) powders, water-soluble formulations, liquid formulations, applyable liquids, aqueous suspensions, dispersions or emulsions, microcapsule formulations, to name just a few. Formulations can be obtained by known methods, such as by mixing the agricultural chemical with a developer (i.e., a liquid or solid diluent or carrier), and in some cases with a surfactant (i.e., an emulsifier and / or dispersant). In cases where water is used as the developer, organic solvents can be used as auxiliary solvents, for example.
[0113] In this invention, from an operability point of view, aqueous suspensions of agricultural chemicals are preferred. From the viewpoint of the persistence of effect, aqueous suspension compositions comprising, in addition to agricultural chemicals, water, surfactants, liquid diluents (organic solvents), and polymer resins, particularly acrylic resins (including (co)polymer resins of alkyl acrylates and / or alkyl methacrylates), are especially preferred as aqueous suspending agents.
[0114] Defoamers, preservatives, thickeners, dispersants, antifreeze agents, etc., may be added to the aqueous suspension of the agrochemicals as needed. The preferred content of the agrochemicals in the aqueous suspension composition is from 1 to 50 wt.%, particularly from 5 to 40 wt.%. The preferred content of the surfactant is from 0.01 to 10 wt.%, particularly from 0.1 to 5 wt.%. The preferred content of the diluent is from 1 to 50 wt.%, particularly from 5 to 30 wt.%. The preferred content of the acrylic resin is from 0.1 to 20 wt.%, particularly from 1 to 10 wt.%. For other added components such as defoamers, preservatives, and thickeners, the preferred total content is from 0 to 10 wt.%, particularly from 0.1 to 5 wt.%. Particulate polymer resins are preferred as polymer resins in the aqueous suspension composition, and those finely pulverized by grinding or the like are particularly preferred.
[0115] Examples of liquid diluents or carriers that may be mentioned include aromatic hydrocarbons (e.g., xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons (e.g., chlorobenzene, dichloroethane, dichloromethane, etc.), aliphatic hydrocarbons [e.g., cyclohexane, alkanes (e.g., mineral oil fractions, etc.)], and alcohols (e.g., C14, C2 ... 2-10 Alcohols such as butanol, ethylene glycol, diols such as propylene glycol, and their ethers, esters, etc.), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strongly polar solvents (e.g., dimethylformamide, dimethyl sulfoxide, etc.), water, etc.
[0116] Examples of solid diluents or carriers include pulverized natural minerals (e.g., kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, etc.) and pulverized synthetic minerals (e.g., bentonite, silica, alumina, silicates, silica sand, etc.). Examples of solid carriers for granular formulations include pulverized and sorted rocks (e.g., calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic granules of inorganic and organic powders, and fine particles of organic matter (e.g., sawdust, coconut shells, corn cobs, tobacco stalks, etc.).
[0117] Examples of surfactants that can be mentioned include nonionic and anionic surfactants [e.g., polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (e.g., alkyl aryl glycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates), tristyrylphenol and its ethoxylates], albumin hydrolysates, etc.
[0118] Examples of dispersants may include lignin-sulfite waste liquid, methylcellulose, etc.
[0119] Adhesives can also be added to formulations (powder formulations, granule formulations, emulsions), and examples of such adhesives include carboxymethyl cellulose, natural and synthetic polymers (e.g., gum arabic, polyvinyl alcohol, polyvinyl acetate, etc.).
[0120] Colorants can also be used in formulations, and examples of such colorants include inorganic pigments (e.g., iron oxide, titanium oxide, Prussian blue, etc.) and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, as well as metal salts of trace elements such as iron, manganese, boron, copper, cobalt, molybdenum, zinc, etc.
[0121] The zinc compound can be any suitable and acceptable zinc salt (inorganic or organic) or oxide, such as ZnO (zinc oxide), zinc sulfate, zinc phosphate, zinc acetate, or zinc citrate. In a preferred embodiment, zinc oxide is used.
[0122] The amount of zinc salt or oxide in the coating can be from 5% to 25%, preferably from 7% to 17%, and more preferably from 10% to 20%. Unless otherwise specified in this invention, % refers to wt.-%.
[0123] There are no particular limitations on the method of applying the coating of the present invention to rice seeds. The coating composition may be in liquid form, or the agrochemical may be in solid form and the copolymer in liquid form. In this case, the agrochemical may be applied to the seed surface by any powder coating method, and then the copolymer may be applied to the seed surface by any liquid coating method. The coating may be applied in one step, but if additional coating layers are to be applied, it may be applied in two or more steps.
[0124] As a method of powder coating, for example, there is a method in which rice seeds and agricultural chemicals are placed in a rotating drum and the rice seeds are uniformly coated with agricultural chemicals by rotating the drum. As a method for spraying agricultural chemicals, copolymers or mixtures thereof, for example, there is (1) a method in which agricultural chemicals, copolymers or mixtures thereof are sprayed directly onto rice seeds falling from a hopper, etc., using appropriate nozzles; (2) a method in which a vibrating guide plate is connected from the hopper to a seedling box, and agricultural chemicals, copolymers or mixtures thereof are sprayed onto the rice seeds using appropriate nozzles as the rice seeds bounce across the plate; and (3) a method in which a drum through which rice seeds pass is installed in the middle of the hopper and above the seedling box, and agricultural chemicals, copolymers or mixtures thereof are sprayed onto the rice seeds passing through the drum.
[0125] As a method for spraying agricultural chemicals, copolymers, or mixtures thereof onto rice seeds on a small scale, another method is used in which rice seeds are placed in a rotating machine (such as a mortar mixer) and a predetermined dose of the agricultural chemicals, copolymers, or mixtures thereof is evenly sprayed onto the rice seeds using a suitable sprayer. Furthermore, another method is used in which rice seeds are placed in a plastic bag or suitable container with a volume two to three times that of the rice seeds, and after adding the agricultural chemicals, copolymers, or mixtures thereof, the container is sealed (for plastic bags, the entrance is sealed after the bag is filled with air, thus inflating the entire bag), shaken, and stirred to allow the agricultural chemicals, copolymers, or mixtures thereof to diffuse throughout the container or bag.
[0126] When spraying large quantities of rice seeds, a spray nozzle can be installed in the middle of the transport device of the seeder leading to the seedling box to spray agricultural chemicals, copolymers, or mixtures of both. This can be followed by a mixing step and an optional drying step.
[0127] Another embodiment of the present invention is a rice seed treatment agent, characterized in that the treatment agent comprises
[0128] a) A mixture of copolymers comprising a copolymer of butyl acrylate with 1,4-divinylbenzene and styrene, and a copolymer of butyl acrylate with styrene.
[0129] b) At least one agricultural chemical.
[0130] Rice seed treatment agents can, without exception, have any modifications as described above regarding the method of the present invention.
[0131] Another embodiment of the present invention is coated rice seeds coated at least partially with the rice seed treatment agent of the present invention.
[0132] As described above, the coating of the present invention protects seeds from diseases and pests without significantly affecting germination rate. Therefore, typical preparation of rice seeds known to the applicant can be maintained, including soaking in water and incubation before sowing. Preferably, compared to untreated rice seeds of the same variety and age, the coated rice seeds of the present invention, after soaking in water at 25°C and then incubating at 7°C for 144 hours (6 days), showed an average reduction in germination rate of 0 to 10%, preferably 0 to 5%. Seed soaking is performed, for example, by scattering 30 seeds on a piece of tissue paper and spraying the paper with 50 mL of water. The paper is then rolled up and placed in a sealed container and exposed to the aforementioned temperature and humidity conditions in the dark, such as in a refrigerator. Germination tests are conducted under the test conditions described above, and evaluation is performed by counting at least 30 randomly selected seeds. This test is conducted with samples soaked and incubated in at least three different containers, and the average germination rate is calculated.
[0133] In addition, coated rice seeds can be stored for months without significantly reducing germination rate and / or losing the activity of agrochemicals.
[0134] The coated rice seeds of this invention allow for soaking in water without significant loss of agrochemicals due to washing or leaching. In a preferred embodiment of the invention, during 24 hours of soaking the coated rice seeds in water at 30°C without stirring, the rice seeds showed a release rate of 3 wt.% or less, particularly 2 wt.% or less, of the agrochemicals relative to the total weight of the coating. The agrochemicals are particularly selected from fungicides and insecticides.
[0135] Another embodiment of the present invention is a method for protecting newly sprouted rice seedlings from fungal diseases and / or harmful organisms before planting, the method comprising the following steps:
[0136] a. Soaking the coated rice seeds according to the invention in water, particularly for at least 12 hours, preferably at a temperature of 10°C to 40°C, more preferably at 20°C to 30°C, and
[0137] b. If necessary, incubate the soaked rice seeds for at least 36 hours, especially at least 72 hours.
[0138] Optionally, at least one additional agrochemical is applied to the rice seeds during soaking and / or cultivation, and this additional agrochemical is particularly an insecticide, preferably thiamethoxam, imidacloprid, thiamethoxam, or mixtures thereof. This method allows for adjustment of the protection status according to actual requirements, for example, if the risk of insect pests is high. For example, rice seeds can be sown in seedling trays (e.g., 60cm × 30cm × 3cm) after soaking or optional cultivation steps. However, also within the scope of the invention is the direct sowing of rice seeds in the field for cultivation after soaking, or sowing them in a field seedling system for later transplanting.
[0139] There are no restrictions in principle on the soaking method for rice seeds, but it is preferable that the rice seeds absorb sufficient water and have a cumulative temperature of 60°C to 140°C per day (e.g., 7 to 10 days at 13°C to 14°C) in the methods described above for protecting new seedlings. For example, after soaking, cultivation can be carried out at 20°C to 40°C, preferably 25°C to 35°C, for at least 24 hours, preferably at least 72 hours, or even 132 hours.
[0140] There are no particular restrictions on the methods for cultivating rice seedlings after sowing rice seeds in seedling trays and covering them with soil, transplanting the seedlings to paddy fields, and cultivating rice after transplanting; commonly known methods can be used. For example, after covering the seeds with soil, each seedling tray is placed in a seedling cabinet to germinate the seeds, and then the seedling trays are moved to a seedling room for further cultivation. The cultivated seedlings can simply be transplanted to the paddy fields using a tiller or similar device. There are also no restrictions on the methods for cultivating rice after transplanting, and rice can be cultivated according to conventional methods.
[0141] Compared to seeds directly coated with appropriate agrochemicals, the coating of this invention typically allows for longer-lasting protection while requiring less agrochemical. For example, in the method of this invention for protecting newly sprouted rice seedlings, protection against diseases and / or pests can still be observed 50 days or more after transplanting the soaked and cultivated seeds, particularly 60 days or more. The typical diseases targeted for protection are caused by filamentous fungi and / or microorganisms. Diseases are particularly selected from rice blast (caused by *Bacillus oryzae*), rice brown spot or rice scab (caused by *Fusarium graminearum*), rice sheath blight (caused by *Rhizoctonia solani*), rice bacterial blight (caused by *Bacillus oryzae*), rice bacterial grain rot (caused by *Bacillus oryzae*), or combinations thereof.
[0142] In another aspect of the method for protecting newly sprouted seedlings according to the present invention, the pest is an animal pest, specifically selected from rice water weevils, rice leafhoppers, planthoppers, black-tailed leafhoppers, rice leafminers (Hydrellia griseola / rice leafminer), rice skippers (rice leafhoppers), rice stem borers, rice leaf rollers, rice stem borers, rice thrips (Stenchaetothrips biformis / rice thrips), or combinations thereof.
[0143] If any patent, patent application, or publication incorporated herein by reference conflicts with the description of this application to the extent that it may lead to ambiguity in terminology, then this description shall take precedence.
[0144] The present invention will be further illustrated based on the following examples.
[0145] The substances used:
[0146] Agricultural chemical formulations:
[0147] Formulation a) As an agricultural chemical, a water-based formulation containing isothiazamine (280 g / L) is used.
[0148] Formulation b) is an agrochemical, using an aqueous formulation containing isothiazamine (200 g / L) and azoxystrobin (80 g / L). The formulation has a total water content of approximately 60 wt.% and further contains 2.5 wt.% red pigment and a mixture of other additives such as defoamers, thickeners, etc. This is further referred to below as an "agrochemical formulation".
[0149] copolymer:
[0150] As a copolymer mixture, a non-plasticized aqueous mixture of copolymer dispersions is used, comprising a first copolymer (a copolymer of butyl acrylate with 1,4-divinylbenzene and styrene (CAS No. 57516-68-4)) and a second copolymer (a copolymer of butyl acrylate with styrene (CAS No. 25767-47-9)) in a ratio of 1:1.
[0151] Zinc:
[0152] Zinc oxide is used as the zinc source.
[0153] HPLC determination of the release of agricultural chemicals from flushing water
[0154] To determine the adhesion of agrochemicals to rice seeds, coated and dried seeds are typically soaked in water and cultured before sowing. During this procedure, samples of the soaking water are collected at fixed time points and analyzed by HPLC for their content of agrochemicals.
[0155] experiment:
[0156] Experiment 1) Absorption of zinc into seedlings and retention of agrochemicals and colorants in coating
[0157] formula
[0158]
[0159] method:
[0160] Rice was treated with 20 L / T of Routin Start SC280 (isothiabendazole).
[0161] -No membrane coating (Object 1)
[0162] Example 1 (Object 2) with a concentration of -1 ml / kg
[0163] Example 2 (Object 3) -2ml / kg
[0164] Soak the treated rice (20g rice in 100mL of water, within 12 hours):
[0165] The amount of zinc on the seeds before soaking and in the soaking water was analyzed (zinc in the soaking water was analyzed according to EN11885 / zinc in the seeds was analyzed by mineralization according to MO147 and then adjusted according to NFENISO6869).
[0166] The amount of isothiazamide on the seeds before and after soaking was analyzed (by HPMC determination).
[0167] Observe the color of the soaking water (visual inspection).
[0168] Measuring the effect of zinc on plant weight
[0169] Zinc analysis
[0170] Zinc on seeds before soaking:
[0171]
[0172]
[0173] Zinc release during immersion in water
[0174]
[0175] Isothiazine analysis
[0176]
[0177] Plant weight
[0178]
[0179] water coloring
[0180]
[0181] 0 = no coloring, + = weak coloring, ++ = strong coloring, +++ = very strong coloring
[0182] water coloring
[0183]
[0184] Liquidity
[0185]
[0186] Retention of various agricultural chemicals
[0187]
[0188]
[0189]
[0190] Germination test
[0191] Seeds were planted and kept at 25°C for 35 days, and the germination rate, seedling dry matter, seedling Zn concentration, and absolute Zn content were evaluated.
[0192]
[0193] Biological efficacy test
[0194] Seeds were treated with IST 500FS (Bayer), IST 200FS (Bayer), and EvergoreWide (undiluted, water-diluted) and the coating according to the present invention, and the efficacy against rice blast fungus and Rhizoctonia solani was tested for 25 to 30 days. The new seed coating was found to be as effective as conventional treatments.
Claims
1. A method for preparing coated rice seeds, wherein the seed coating is at least partially applied to the surface of dried rice seeds, characterized in that, The seed coating contains at least [amount missing] A mixture of a first copolymer of butyl acrylate with 1,4-divinylbenzene and styrene, and a second copolymer of butyl acrylate with styrene, and at least one agrochemical. The first copolymer is characterized in that it is prepared from at least the following: a. 45 to 65 wt.% butyl acrylate; b. 35-55 wt.% styrene and 1,4-divinylbenzene; The second copolymer is characterized in that it is prepared from at least the following: a) 35 to 65 wt.% butyl acrylate; b) 35-65 wt.% styrene.
2. A method for preparing coated rice seeds, wherein the seed coating is at least partially applied to the surface of dried rice seeds, characterized in that, The seed coating contains at least [amount missing] A mixture of a first copolymer of butyl acrylate with 1,4-divinylbenzene and styrene, and a second copolymer of butyl acrylate with styrene, and at least one agrochemical. The first copolymer is characterized in that it is prepared from at least the following: a. 50 to 70 wt.% butyl acrylate; b. 30 to 50 wt.% styrene and 1,4-divinylbenzene; The second copolymer is characterized in that it is prepared from at least the following: a) 35 to 65 wt.% butyl acrylate; b) 35-65 wt.% styrene.
3. The method according to claim 1, characterized in that, The second copolymer is prepared from at least the following: a) 40 to 60 wt.% butyl acrylate; b) 40 to 60 wt.% styrene.
4. The method according to claim 2, characterized in that, The second copolymer is prepared from at least the following: a) 40 to 60 wt.% butyl acrylate; b) 40 to 60 wt.% styrene.
5. The method according to any one of claims 1-4, characterized in that, The ratio of the first polymer to the second polymer is in the range of 3:1 to 1:
3.
6. The method according to claim 5, characterized in that, The ratio of the first polymer to the second polymer is in the range of 2:1 to 1:
2.
7. The method according to any one of claims 1-4, characterized in that, The first copolymer has a weight-average molecular weight Mw in the range of 400,000 to 800,000 g / mol.
8. The method according to claim 7, characterized in that, The first copolymer has a weight-average molecular weight Mw in the range of 500,000 to 700,000 g / mol.
9. The method according to any one of claims 1-4, characterized in that, The second copolymer has a weight-average molecular weight Mw in the range of 25,000 to 125,000 g / mol.
10. The method according to claim 9, characterized in that, The second copolymer has a weight-average molecular weight Mw in the range of 30,000 to 100,000 g / mol.
11. The method according to any one of claims 1-4, characterized in that, The seed coating further contains zinc salts or zinc oxide.
12. The method according to any one of claims 1-4, characterized in that, The seed coating is further colored with a pigment.
13. The method according to any one of claims 1-4, characterized in that, The copolymer was applied to the seeds in the form of a dispersion.
14. The method according to claim 13, characterized in that, The copolymer was applied to the seeds in the form of an aqueous dispersion.
15. The method according to claim 13, characterized in that, The dispersion has a solids content of 30 to 80 wt.% as measured at 130°C for 30 minutes, according to DIN EN ISO 3251.
16. The method according to claim 15, characterized in that, The dispersion has a solids content of 50 to 70 wt.%.
17. The method according to claim 13, characterized in that, This dispersion has a minimum film-forming temperature of >= 0°C as measured according to DIN ISO 2115.
18. The method according to claim 13, characterized in that, This dispersion does not contain plasticizers and / or nonionic detergents.
19. The method according to claim 18, characterized in that, This dispersion does not contain alkylphenol ethoxylates.
20. The method according to any one of claims 1-4, characterized in that, The agricultural chemical is selected from the group consisting of: insecticides, fungicides, bactericides, viricides, acaricides, molluscicides, nematicides, ovicides, repellents, rodenticides, herbicides, safety agents, fertilizers, biological agents, or mixtures thereof.
21. The method according to any one of claims 1-4, characterized in that, At least one agricultural chemical is selected from isothiazine, fluoxastrobin, fluoxastrobin aniline, azole fungicides, methoxyacrylates, pyrimethanil, metalaxyl, fludioxonil, thiamethoxam, fipronil, flufenoxuron, chlorantraniliprole, bromonoxane, imidacloprid, thiamethoxam, thiamethoxam, spinosad, acetamiprid, or a mixture thereof.
22. The method according to claim 21, characterized in that, The agrochemicals mentioned are tebuconazole, tebuconazole, propiconazole, or difenoconazole.
23. The method according to claim 21, characterized in that, The agrochemicals mentioned are oxadiazon, pyraclostrobin, or azoxystrobin.
24. The method according to claim 21, characterized in that, The agrochemicals are a combination of the following: a. Isothiazine and azoxystrobin, b. Isothiazine and fluopyram or c. Fluopyram and azoxystrobin.
25. The method according to any one of claims 1 to 4, characterized in that, The copolymer and the agrochemical are applied to the seed in a sequential manner.
26. The method according to claim 25, characterized in that, The seeds are first coated with at least one agricultural chemical and then coated with the copolymer.
27. The method according to any one of claims 1-4, characterized in that, The application rate of this copolymer relative to the weight of untreated seeds is 0.001 to 2.5 wt.-.
28. The method according to claim 27, characterized in that, The application rate of this copolymer relative to the weight of untreated seeds is 0.01 to 1.25 wt.-.
29. The method according to claim 27, characterized in that, The application rate of this copolymer relative to the weight of untreated seeds is 0.025 to 1 wt.-.
30. The method according to any one of claims 1-4, characterized in that, The application rate of this agrochemical is 0.001 to 5 wt.-% relative to the weight of untreated seeds.
31. The method according to claim 30, characterized in that, The application rate of this agrochemical is 0.01 to 2.5 wt.-% relative to the weight of untreated seeds.
32. A seed coating, wherein rice seeds coated with the seed coating are at least partially coated with a rice seed treatment agent, characterized in that, This rice seed treatment agent contains A mixture of a first copolymer of butyl acrylate with 1,4-divinylbenzene and styrene, and a second copolymer of butyl acrylate with styrene, and at least one agrochemical. The first copolymer is characterized by being prepared from 45 to 65 wt.% butyl acrylate, with 35 to 55 wt.% styrene and 1,4-divinylbenzene; and the second copolymer is prepared from at least a) 35 to 65 wt.% butyl acrylate, with b) 35 to 65 wt.% styrene.
33. The seed coating according to claim 32, characterized in that, The first copolymer is prepared from 55 to 65 wt.% butyl acrylate; and 35 to 45 wt.% styrene and 1,4-divinylbenzene; and the second copolymer is prepared from at least a) 45 to 55 wt.% butyl acrylate; and b) 45 to 55 wt.% styrene.
34. Seed coating according to any one of claims 32-33, characterized in that, The ratio of the first polymer to the second polymer is in the range of 3:1 to 1:
3.
35. The seed coating according to claim 34, characterized in that, The ratio of the first polymer to the second polymer is in the range of 2:1 to 1:
2.
36. The seed coating according to claim 34, characterized in that, The ratio of the first polymer to the second polymer is 1:
1.
37. The seed coating according to any one or more of claims 32-33, characterized in that, The first copolymer has a weight-average molecular weight Mw in the range of 400,000 to 800,000 g / mol; and the second copolymer has a weight-average molecular weight Mw in the range of 25,000 to 125,000 g / mol.
38. The seed coating according to any one of claims 32-33, characterized in that, The seed coating further contains zinc salts or zinc oxide.
39. The seed coating according to any one of claims 32-33, characterized in that, The seed coating further contains colorants and optional additional adjuvants.
40. Seed coating according to any one of claims 32-33, characterized in that, When the rice seeds were soaked in water at 25°C for 24 hours without stirring, the release rate of the agrochemical was 3 wt.% or less compared to the total weight of the agrochemical in the coating.
41. The seed coating according to claim 40, characterized in that, The agricultural chemicals selected include fungicides and insecticides.
42. The seed coating according to any one of claims 32-33, characterized in that, The at least one active ingredient is selected from the group consisting of fluopyram, isothiazamide, chlorantraniliprole, azoxystrobin, tetrazolium, and acetamiprid.
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