A method of protecting plants using a mixture containing sulfur and selected terpenes.

Abstract

The present invention relates to a method for protecting plants using a mixture containing sulfur and a selected terpene, as well as a mixture of sulfur and a selected terpene and a fungicidal composition containing such a mixture.

Description

[Technical Field]

[0001] The present invention relates to a method for protecting plants using a mixture containing sulfur and a selected terpene, as well as a mixture of sulfur and a selected terpene and a fungicidal composition containing such a mixture. [Background technology]

[0002] Crop plants are constantly threatened by plant pathogens and plant pests. Therefore, there is a constant need to develop a comprehensive toolkit of alternative pesticides to protect crop plants and overcome the shortcomings of existing pesticides. One area of ​​interest is the development of naturally occurring compound-based pesticides that exhibit similar performance and ease of application to comparable synthetic compound-based pesticides.

[0003] One of the oldest naturally occurring fungicides, and still widely used, is elemental sulfur. Elemental sulfur is considered to have very little environmental impact and is one of the few compounds permitted as a pesticide in organic farming. Sulfur is primarily used to protect fruit, vegetable, and grapevines from plant pathogenic fungi, mites, and insects such as aphids. Sulfur fungicides are generally formulated as wettable powders or water-dispersible granules. Wettable powder formulations of sulfur are dusty and pose risks to users, mainly due to eye irritation, inhalation risk, and skin irritation. Granular formulations are less dusty but more expensive to manufacture. An improved formulation type is a suspension concentrate. However, aqueous suspension concentrates of sulfur often exhibit sedimentation during storage, are difficult to resuspend, and tend to form a supernatant. Sulfur particles formed during storage can clog spray nozzles. Another problem with aqueous suspension concentrates is their low injectability and high viscosity, which reduces the ease of application for users of these formulations. International Publication No. 03 / 086073 describes variations of aqueous suspension concentrates containing different types of fatty acids or terpene vegetable oils, and describes a composition for controlling powdery mildew (Uncinula necator) on grapevines, containing sulfur and 40% soybean oil in an aqueous emulsion.

[0004] Sulfur has limited applications in crops such as wheat, barley, rye, rye, oats, sugar beets, and fodder beets. While sulfur adequately protects these crops from powdery mildews such as Blumeria graminis (also known as Erysiphe graminis), it requires high application rates of 6-8 kg of sulfur per hectare (ha) per application. Even at such high application rates, sulfur is insufficiently effective against other plant pathogenic fungi in these crops. Therefore, there is a need in the art to identify methods of sulfur application in these crops that can improve the protective effect of sulfur-based fungicides against other plant pathogenic fungi and / or reduce application rates per hectare and per year.

[0005] Another type of compound used as a natural fungicide is terpenes. Terpenes are a diverse group of natural compounds and are part of many plant essential oils. Their basic structure can be visualized as being formed by the "head-to-tail" linkage of isoprene (C5H8) units to form chains and rings. They are further classified according to the amount of isoprene units used in their basic structure. Examples of these subgroups are monoterpenes, sesquiterpenes, and diterpenes. Monoterpenes have two isoprene units and C in their basic structure. 10 H 16 Sesquiterpenes contain three isoprene units, while diterpenes contain four.

[0006] International Publication No. 2022 / 101613 describes a biofungicidal composition containing microencapsulated essential oils or isolated terpenes.

[0007] Despite the fact that sulfur and terpenes have long been used as pesticides, their combined effects and the conditions for obtaining positive effects or overcoming technical obstacles arising from their combinations are not well known. International Publication No. 2019 / 207112 describes a fungicidal mixture of limonene, cinnamaldehyde, and one or more terpinenes, which can be used to replace other fungicides, thereby making it possible to reduce the amount of other fungicides such as sulfur and copper in a spray regime for protecting plants. It describes that by using a specific terpene mixture in a spray regime, the total amount of sulfur in the spray regime can be reduced from 100-120 kg to 10-12 kg per season.

[0008] International Publication No. 2016 / 004326 discloses a seed, soil, or plant treatment composition comprising one or more essential oils and one or more emulsifiers, wherein one or more essential oils are present as an emulsion, and the average particle size of one or more essential oils in the emulsion is less than approximately 25 microns. International Publication No. 2016 / 004326 states that this plant treatment composition may be combined with several biological agents, including fungicides such as sulfur.

[0009] These documents describe the effects of sulfur and terpenes on protecting plants from fungal attacks, but they do not describe how these compounds can be used together without reducing the effectiveness of sulfur against fungi or pests, or to avoid enhanced phytotoxic effects based on the combination of these compounds. These documents do not describe how a combination of sulfur and a terpene selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol provides a synergistic antifungal effect against fungal plant pathogens.

[0010] Combinations of sulfur and terpenes are being produced. French Patent No. 2599592 describes an antifungal composition (Heliosulfre®) comprising a pine root oil and water emulsion and particulate sulfur suspended in one or more surfactants. One liter of this suspension concentrate typically contains 60-170 g of pine root oil, 25-70 g of surfactants, and 400-1000 g of particulate or pulverized sulfur. A combination of nanoparticle sulfur and orange essential oil is described as Oro Solve®. In Cesar et al. 2019, “Nanoparticulated Sulfur and Essential Orange Oil (Oro Solve®) Increases Efficiency of Euschistus Heroes Control”, Egypt.Acad.J.Biolog.Sci.,12(6):111-120, it is stated that Oro Solve® consists of orange essential oil + 45% nanoparticle elemental sulfur, and a concentration of 585g per liter was obtained.

[0011] However, Oro Solve® was not commercially successful and has been discontinued. This highlights a common problem in the art: the difficulty in producing stable formulations containing particulate sulfur and mineral or vegetable oil. See, for example, paragraph

[0007] of European Patent No. 2904903, lines 33-55 of the right column of U.S. Patent No. 6835719, and paragraphs

[0006] -

[0017] of U.S. Patent Application Publication 2014 / 0044765. These problems include the stability of the formulation itself, reduced effectiveness of sulfur against fungi or pests, increased plant toxicity, and degradation of organic oils. For these reasons, many sulfur product labels advise against using them in tank mixes with oil-containing products and against applying sulfur and oil separately to plants within a 30-day timeframe. In addition to the well-known problems with formulations containing liquid sulfur, such as poor storage stability due to precipitation, crystal growth, and phase separation, further problems can be anticipated with sulfur-terpenes, as they tend to oxidize while sulfur promotes the oxidation of other compounds.

[0012] High concentrations of sulfur typically lead to high viscosity formulations, reducing their injectability, and especially when combined with sulfur precipitation, can cause serious problems during the preparation and application of spray suspensions, potentially leading to uneven application of the active compound to crops and clogging of valves and spray nozzles in crop protection sprayers. Another problem is that, because terpenes typically have high vapor pressure, the combined action of terpenes and sulfur against corresponding plant pathogens or pests may be too short-lived to provide any additional positive effect for protecting plants. [Overview of the Initiative] [Means for solving the problem]

[0013] The present invention provides solutions to these problems. In addition, it has been found that combining sulfur with selected terpenes provides a synergistic effect for controlling plant pathogenic fungi.

[0014] A method for controlling plant pathogenic fungi selected from the genera Puccinia, Erysiphe, Blumeria, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, Diplocarpon, and Podosphaera is described herein, using a mixture of sulfur and at least one terpene selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, preferably a mixture of sulfur and limonene. [Modes for carrying out the invention]

[0015] sulfur: The sulfur present in a composition may be elemental sulfur. Elemental sulfur can exist in several different allotropes, including rubbery (amorphous) sulfur, monoclinic sulfur, and rhombic sulfur composed of cyclic molecules. The most common form is a cyclic structure of eight atoms (S8), usually accompanied by a smaller ring of seven (S7) or six (S6) atoms. Elemental sulfur can be extracted from fossil-based sulfur deposits of salt domes or volcanic ejecta, but it is most often produced as a by-product of desulfurization of natural gas and petroleum. The most important process in desulfurization is the Kraus process, which involves oxidizing hydrogen sulfide (H2S) to sulfur dioxide (SO2) and then catalytically reacting H2S with SO2 to form elemental sulfur (S°) (Schreiner, B.30 2008. Chemie in unserer Zeit 42;378). Another form of elemental sulfur is sulfurous powder, which is an extremely fine, bright yellow sulfur powder produced by the sublimation and precipitation of sulfur.

[0016] A further source of elemental sulfur is, for example, the oxidation of hydrogen sulfide from gas streams by microorganisms, whereby small particles of elemental sulfur are produced. This type of sulfur is referred to as "biological sulfur" and is distinguished from chemically produced sulfur by its lower density compared to orthorhombic sulfur. While orthorhombic sulfur is known to be hydrophobic, biological sulfur particles also have hydrophilic properties.

[0017] The sulfur used in the present invention may be chemically produced sulfur, preferably orthorhombic sulfur, or may be biological sulfur.

[0018] The particle diameter of sulfur is important for the efficacy of the product as a pesticide on crops. The particulate sulfur has a D of less than 100 micrometers, preferably less than 50 micrometers, more preferably less than 10 micrometers, even more preferably less than 8 micrometers, and most preferably less than 3 micrometers 50 preferably has a particle size diameter. D 10 The particle size diameter and D 90 The particle size diameter is usually D 10 is 1 micrometer and D 90 is 80 micrometers, preferably D 10 is 1 micrometer and D 90 is 50 micrometers, more preferably D 10 is 1 micrometer and D 90 is 30 micrometers, even more preferably D 10 is 1 micrometer and D 90 is 20 micrometers, most preferably D 10 is 1 micrometer and D 90is 10 micrometers. Particles with a diameter of 1 to 8 microns are optimal, particles with larger diameters have much lower toxicity to fungi, and particles smaller than 1 micron may be prone to causing phytotoxic effects such as chlorosis and necrosis (Emmett et al., 2003. "Sulphur formulations, particle size and activity-a review" in "Strategic Use of Sulphur in Integrated Pest and Disease Management (IPM) Programs for Grapevines". Therefore, in a very preferred embodiment, sulfur has a D 10 value of 1 micrometer and a D 90 value of 8 micrometers, more preferably a D 50 value of a diameter particle size of less than 3 micrometers.

[0019] The D of the particles [4;3] value is preferably 1 to 8 micrometers, more preferably 1 to 4 micrometers.

[0020] The average diameter particle size of biological sulfur particles is usually even smaller. Biological sulfur particles with an average diameter of less than 1 micrometer also have lower phytotoxicity than orthorhombic sulfur particles of similar size. Preferably, the D of the diameter particle size of biological sulfur 50 is less than 10 micrometers, more preferably less than 9 micrometers, more preferably less than 8 micrometers, more preferably less than 7 micrometers, more preferably less than 6 micrometers, less than 5 micrometers, less than 4 micrometers, less than 3 micrometers, more preferably less than 2.5 micrometers, more preferably less than 2 micrometers, more preferably less than 1 micrometer, most preferably less than 0.8 micrometer. Preferably, the biological sulfur has a D with an average diameter particle size of 0.1 micrometer 10 and a D with an average diameter particle size of 8 micrometers 90 .

[0021] D10 , D 50 , D90 and D [4;3] The values ​​are commonly used in the art to represent the particle size distribution. Methods for determining these values ​​are known in the art and include, for example, the use of actual particle size and morphology using a camera system, as well as the use of laser diffraction and dynamic light scattering methods. A preferred method is to utilize laser diffraction by using, for example, an ANALYSETTE 22 MicroTec plus particle size analyzer. Methods available in the art, such as grinding, can be used to fit the average particle size of sulfur particles to a desired particle size distribution.

[0022] Selected terpenes: The suspension emulsion formulation or suspension concentrate formulation of the present invention contains at least one terpene selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol. References to the names of terpenes also include references to the naturally occurring enantiomers of each terpene. For example, a reference to limonene includes references to the (R)-enantiomer D-limonene and the (S)-enantiomer L-limonene.

[0023] The selected terpenes can be chemically synthesized or isolated from plant essential oils. Methods for synthesizing the selected terpenes are well known in the art. However, the selected terpenes can also be isolated, for example, from plant essential oils by centrifugation or steam distillation.

[0024] Those skilled in the art will know which plant essential oils contain one or more of the following: limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol. Suitable examples of plant essential oils are orange oil, tangerine oil, grapefruit oil, lemon oil, and mandarin oil, which contain large amounts of D-limonene. Thyme oil typically contains 23%–60% thymol, 18%–50% γ-terpinene, 8%–44% p-cymene, and 2%–8% carvacrol. Oregano oil contains large amounts of thymol and carvacrol. Pinene can be isolated from pine root oil. p-cymene can be found in cumin and thyme oils. Eugenol can be isolated from cinnamon oil. Geraniol is a component of citronella oil, rose oil, and palmarosa oil.

[0025] The content of a given terpene in a particular essential oil can vary and depends on the source of the plant material, including the plant's genotype, environmental conditions during plant growth, harvesting conditions, extraction method, and other factors.

[0026] In one embodiment of the present invention, limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, or carvacrol is isolated from or provided as part of a plant essential oil. When provided as part of a plant essential oil, the amount of limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, or carvacrol, or the total amount of limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, or carvacrol in the final mixture, rather than the amount of each essential oil, is a determinant amount for the amount of terpenes selected for the method of controlling plant pathogenic fungi.

[0027] The mixture used in the described method may contain only one of limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, or carvacrol, for example, only limonene, preferably only D-limonene, but may also contain one or more selected terpenes.

[0028] The preferred mixtures of selected terpenes are as follows: a) A mixture of limonene, preferably D-limonene, and at least one of α-terpinene, p-cymene, carvacrol, eugenol, geraniol, and thymol. b) A mixture of limonene, preferably D-limonene, and at least one of α-terpinene, p-cymene, and carvacrol. c) A mixture of limonene, preferably D-limonene, and at least one of eugenol, geraniol, and thymol. Preferably, the weight / weight ratio between limonene, preferably D-limonene, and one terpene selected from terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol is 75:1 to 1:1, or 50:1 to 1:1, or 25:1 to 1:1, or 10:1 to 1:1, or 8:1 to 1:1, or 5:1 to 1:1, or 2:1 to 1:1.

[0029] Preferably, the weight / weight ratio between limonene, preferably D-limonene, and the combined amount of one or more of terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol is 75:1 to 1:1, or 50:1 to 1:1, or 25:1 to 1:1, or 10:1 to 1:1, or 8:1 to 1:1, or 5:1 to 1:1, or 2:1 to 1:1.

[0030] Further preferred mixtures of selected terpenes are as follows: a) A mixture of α-terpinene, p-cymene, and limonene. b) A mixture of at least two of eugenol, geraniol, and thymol.

[0031] Terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol may be accompanied by other terpenes, in particular, when at least one of limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol is provided as part of a plant essential oil.

[0032] Preferably, the weight / weight ratio of the combined amount of terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol to the combined amount of other terpenes is 75:1 to 1:1, or 50:1 to 1:1, or 25:1 to 1:1, or 10:1 to 1:1, or 8:1 to 1:1, or 5:1 to 1:1, or 2:1 to 1:1.

[0033] In one embodiment, the weight / weight ratio of limonene, preferably D-limonene, to the combined amount of terpenes other than terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol is 75:1 to 1:1, or 50:1 to 1:1, or 25:1 to 1:1, or 10:1 to 1:1, or 8:1 to 1:1, or 5:1 to 1:1, or 2:1 to 1:1.

[0034] In one embodiment, the weight / weight ratio of limonene, preferably D-limonene, to the combined amount of terpenes including terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol is 75:1 to 1:1, or 50:1 to 1:1, or 25:1 to 1:1, or 10:1 to 1:1, or 8:1 to 1:1, or 5:1 to 1:1, or 2:1 to 1:1, preferably greater than 90:1 or more, 100:1 or more, 300:1 or more, 500:1 or more, or 1000:1 or more.

[0035] The following weight / weight ratios are preferred. a) The amount of sulfur to the combined amount of terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol is 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65:1 to 1:2, or 50:1 to 1:2, or 40:1 to 1:2, or 30:1 to 1:2 Is the ratio 25:1 to 1:2, or 24:1 to 2:1, or 24:1 to 2.5:1, or 24:1 to 3:1, or 24:1 to 4:1, or 24:1 to 5:1, or 24:1 to 6:1, or 24:1 to 8:1, or 24:1 to 12:1, or 20:1 to 1:2, or 15:1 to 1:2, or 10:1 to 1:2, or 20:1 to 5:1, or 20:1 to 10:1, or 20:1 to 12:1, or 20:1 to 6:1, or 8:1 to 1:2, or 6:1 to 1:2, or 6:1 to 2:2, or 5:1 to 2:1, or b) The amount of sulfur to the amount of limonene, preferably D-limonene, and the combined amount of terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol is 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65:1 to 1:2, or 50:1 to 1:2, or 40:1 to 1:2, or 30:1 to 1:2, Or 25 to 1 to 2, or 24 to 1 to 2 to 1, or 24 to 1 to 2.5 to 1, or 24 to 1 to 3 to 1, or 24 to 1 to 4 to 1, or 24 to 1 to 5 to 1, or 24 to 1 to 6 to 1, or 24 to 1 to 8 to 1, or 24 to 1 to 12 to 1, or 20 to 1 to 1 to 2, or 15 to 1 to 1 to 2, or 10 to 1 to 2, or 20 to 1 to 5 to 1, or 20 to 1 to 10 to 1, or 20 to 1 to 12 to 1, or 20 to 1 to 6 to 1, or 8 to 1 to 2, or 6 to 1 to 1 to 2, or 6 to 1 to 2 to 2, or 5 to 1 to 2, or c) The amount of sulfur to limonene, preferably D-limonene, is 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65:1 to 1:2, or 50:1 to 1:2, or 40:1 to 1:2, or 30:1 to 1:2, or 25:1 to 1:2, or 24:1 to 2:1. Or 24 to 1 to 2.5 to 1, or 24 to 1 to 3 to 1, or 24 to 1 to 4 to 1, or 24 to 1 to 5 to 1, or 24 to 1 to 6 to 1, or 24 to 1 to 8 to 1, or 24 to 1 to 12 to 1, or 20 to 1 to 1 to 2, or 15 to 1 to 1 to 2, or 10 to 1 to 2, or 20 to 1 to 5 to 1, or 20 to 1 to 10 to 1, or 20 to 1 to 12 to 1, or 20 to 1 to 6 to 1, or 8 to 1 to 2, or 6 to 1 to 1 to 2, or 6 to 1 to 2 to 2, or 5 to 1 to 2 to 1, or d) The amount of sulfur to limonene, preferably D-limonene, is 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65:1 to 1: 2, or 50 vs 1 to 1 to 2, or 40 vs 1 to 1 to 2, or 30 vs 1 to 1 to 2, or 25 vs 1 to 1 to 2, or 24 vs 1 to 2 to 1, or 24 vs 1 to 2.5 to 1, or 24 vs 1 to 3 to 1, or 24 vs 1 to 4 to 1, or 24 vs 1 to 5 to 1, or 24 vs 1 to 6 to 1, or 24 vs 1 to 8 to 1, or 24 vs 1 to 12 to 1, or 20 vs 1 to 1 to 2 , or 15:1 to 1:2, or 10:1 to 1:2, or 20:1 to 5:1, or 20:1 to 10:1, or 20:1 to 12:1, or 20:1 to 6:1, or 8:1 to 1:2, or 6:1 to 1:2, or 6:1 to 2:2, or 5:1 to 2:1, and the amount of limonene, preferably D-limonene, and terpinene, pinene, p-cymene, eugenol The combined amount of terpenes including ru, geraniol, thymol, and carvacrol is 75:1 to 1:1, or 50:1 to 1:1, or 25:1 to 1:1, or 10:1 to 1:1, or 8:1 to 1:1, or 5:1 to 1:1, or 2:1 to 1:1, preferably more than 90:1 or more, 100:1 or more, 300:1 or more, 500:1 or more, or 1000:1 or more.

[0036] Methods for controlling plant pathogenic fungi: This invention relates to the genera Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon (Dip A method for controlling plant pathogenic fungi selected from the genus *Locarpon*, comprising contacting the fungus, a plant or plant part to be protected from fungal attack with a fungicidal amount of a mixture comprising sulfur and at least one terpene selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol in a ratio of 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:1 0, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65:1 to 1:2, or 50:1 to 1:2, or 40:1 to 1:2, or 30:1 to 1:2, or 25:1 to 1:2, or 24:1 to 2:1, or 24:1 to 2.5:1, or 24:1 to 3:1, or 24:1 to 4:1, or 24:1 to 5:1, or 24:1 to 6:1, or 24:1 to 8:1 The method includes a weight / weight ratio of sulfur to limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol in the following order: 24:1 to 12:1, 20:1 to 1:2, 15:1 to 1:2, 10:1 to 1:2, 20:1 to 5:1, 20:1 to 10:1, 20:1 to 12:1, 20:1 to 6:1, 8:1 to 1:2, 6:1 to 1:2, 6:1 to 2:2, or 5:1 to 2:1.

[0037] The term "fungicidal effective amount" means the amount of a composition that is sufficient to control a harmful fungus and does not cause substantial damage to the treated plant, treated storage product or harvested product, or treated material. Such an amount can vary widely and depends on various factors such as the fungal species being controlled, the treated cultivated plant, storage product, harvested product or material, and climatic conditions.

[0038] Preferably, this method applies to a) the genera Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia and Dipterophyllum. a) Identifying plants or plants that are infected with or at risk of being infected with at least one fungus selected from the genus Diplocarpon; b) Contacting the fungus, the plant or plant part to be protected from fungal attack with a fungicidal effective amount of a mixture comprising sulfur and at least one terpene selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol in a ratio of 100 to 1 to 10, or 70 1 to 1 to 10, or 65 to 1 to 10, or 50 to 1 to 10, or 40 to 1 to 10, or 30 to 1 to 10, or 25 to 1 to 10, or 24 to 1 to 2 to 10, or 100 to 1 to 2, or 70 to 1 to 2, or 65 to 1 to 2, or 50 to 1 to 2, or 40 to 1 to 2, or 30 to 1 to 2, or 25 to 1 to 2, or 24 to 1 to 2, or 24 to 1 to 2, or 24 to 1 to 2, or 24 to 1 to 2, or 24 to 1 to 2.5 to 1, or 24 to 1 to 3 to 1, or 24 to 1 to 4 to 1, or 24 to 1 to 5 to 15 to 1, or 24 to 1 to 2.5 to 1, or 24 to 1 to 3 to 1, or 24 to 1 to 5 to 1, or 24 to 1 to 2.5 to 1, or 24 to 1 to 3 to 1, or 24 to 1 to 5 to The process includes a weight / weight ratio of sulfur to limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol in the following order: 6:1, or 24:1 to 8:1, or 24:1 to 12:1, or 20:1 to 1:2, or 15:1 to 1:2, or 10:1 to 1:2, or 20:1 to 5:1, or 20:1 to 10:1, or 20:1 to 12:1, or 20:1 to 6:1, or 8:1 to 1:2, or 6:1 to 1:2, or 6:1 to 2:2, or 5:1 to 2:1.

[0039] Preferably, the mixture contains limonene, preferably D-limonene, and the weight / weight ratio of sulfur to limonene is 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65:1 to 1:2, or 50:1 to 1:2, or 40:1 to 1:2, or 30:1 to 1:2, or 25:1 The ratios are approximately 1 to 2, or 24 to 1 to 2 to 1, or 24 to 1 to 2.5 to 1, or 24 to 1 to 3 to 1, or 24 to 1 to 4 to 1, or 24 to 1 to 5 to 1, or 24 to 1 to 6 to 1, or 24 to 1 to 8 to 1, or 24 to 1 to 12 to 1, or 20 to 1 to 1 to 2, or 15 to 1 to 1 to 2, or 10 to 1 to 2, or 20 to 1 to 5 to 1, or 20 to 1 to 10 to 1, or 20 to 1 to 12 to 1, or 20 to 1 to 6 to 1, or 8 to 1 to 2, or 6 to 1 to 1 to 2, or 6 to 1 to 2 to 2, or 5 to 1 to 2.

[0040] More preferably, at least one fungus is a fungus of a genus selected from Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon.

[0041] Preferably, at least one fungus is selected from the following species: Puccinia triticina, Puccinia striiformis, Erysiphe graminis, Septoria tritici, Cercospora beticola, Cercospora sojina, Sclerotinia sclerotiorum, Ramularia collo-cygni, Fusarium graminearum, Pyrenophora teres, and Venturia inequalis. More preferably, at least one fungus is from a species selected from Puccinia triticina, Puccinia striiformis, Erysiphe graminis, Septoria tritici, Cercospora beticola, Cercospora sojina, Sclerotinia sclerotiorum, Ramularia collo-cygni, and Fusarium graminearum.

[0042] In one embodiment, the mixture comprises limonene, preferably D-limonene, with a weight / weight ratio of sulfur to limonene of 25:1 to 1:1, or 24:1 to 1:1, or 12:1 to 1:1, and at least one fungus is from a genus selected from Puccinia, Blumeria, Uncinula, Cercospora, Septoria, Ramularia, Venturia, Rhynchosporium, and Sphaerotheca.

[0043] In one embodiment, the mixture contains limonene, preferably D-limonene, with a weight / weight ratio of sulfur to limonene of 25:1 to 1:1 or 24:1 to 1:1, and at least one fungus is Puccinia triticina, Puccinia recondita, Blumeria graminis, Uncinula necator, Cercospora beticola, Cercospora sojina, Septoria tritici, Ramularia collo-cygni, Venturia inaequalis, Rhynchosporium cecallis It is from a species selected from *Sphaerotheca secalis* and *Sphaerotheca fuliginea*.

[0044] In one embodiment, the mixture contains limonene, preferably D-limonene, with a weight / weight ratio of sulfur to limonene of 25:1 to 1:1 or 24:1 to 1:1, and at least one fungus is Puccinia triticina, Puccinia recondita, Blumeria graminis, Uncinula necator, Cercospora beticola, Cercospora sojina, Septoria tritici, Ramularia collo-cygni, Venturia inaequalis, Rhynchosporium cecallis It is from a species selected from *Sphaerotheca secalis* and *Sphaerotheca fuliginea*.

[0045] In one embodiment, the mixture comprises limonene, preferably D-limonene, with a weight / weight ratio of sulfur to limonene of 25:1 to 1:1 or 24:1 to 1:1, and at least one fungus is selected from Puccinia recondita, Cercospora sojina, and Sphaerotheca fuliginea.

[0046] In one embodiment, the mixture comprises limonene, preferably D-limonene, with a weight / weight ratio of sulfur to limonene of 18:1 to 1:1 or 16:1 to 1:1, and at least one fungus is selected from species of Cercospora beticola and Venturia inaequalis.

[0047] In one embodiment, the mixture comprises limonene, preferably D-limonene, with a weight / weight ratio of sulfur to limonene of 15:1 to 1:1 or 12:1 to 1:1, and at least one fungus is selected from Puccinia triticina, Blumeria graminis, Uncinula necator, Septoria tritici, Ramularia collo-cygni, and Rhynchosporium secalis.

[0048] Preferably, the mixture is applied when plant pathogenic fungi are present or when there is a possibility of infection due to weather conditions.

[0049] The present invention relates to a method for controlling or reducing Fusarium head blight (FHB) in wheat, barley, rye, or oats, comprising: a) identifying plants or groups of plants that are infected with or at risk of being infected with Fusarium head blight; and b) contacting a fungus, a plant or plant part infected with or at risk of being infected with Fusarium head blight, with a fungicidal amount of a mixture comprising sulfur, limonene, terpinene, pinene, p- At least one terpene selected from cymene, eugenol, geraniol, thymol, and carvacrol is mixed with a ratio of 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65:1 to 1:2 , or 50:1 to 1:2, or 40:1 to 1:2, or 30:1 to 1:2, or 25:1 to 1:2, or 24:1 to 2:1, or 24:1 to 2.5:1, or 24:1 to 3:1, or 24:1 to 4:1, or 24:1 to 5:1, or 24:1 to 6:1, or 24:1 to 8:1, or 24:1 to 12:1, or 20:1 to 1:2, or 15:1 to 1:2, or 10:1 to 1:2, or 20:1 to 5:1, or The method also includes contacting a substance containing sulfur in a weight / weight ratio of 20:1 to 10:1, or 20:1 to 12:1, or 20:1 to 6:1, or 8:1 to 1:2, or 6:1 to 1:2, or 6:1 to 2:2, or 5:1 to 2:1, with a combined amount of at least one terpene selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol.

[0050] In one embodiment, at least one of the selected terpenes is limonene, preferably D-limonene, and the weight / weight ratio between sulfur and limonene is 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65:1 to 1:2, or 50:1 to 1:2, or 40:1 to 1:2, or 30:1 to 1: 2, or 25:1 to 1:2, or 24:1 to 2:1, or 24:1 to 2.5:1, or 24:1 to 3:1, or 24:1 to 4:1, or 24:1 to 5:1, or 24:1 to 6:1, or 24:1 to 8:1, or 24:1 to 12:1, or 20:1 to 1:2, or 15:1 to 1:2, or 10:1 to 1:2, or 20:1 to 5:1, or 20:1 to 10:1, or 20:1 to 12:1, or 20:1 to 6:1, or 8:1 to 1:2, or 6:1 to 1:2, or 6:1 to 2:2, or 5:1 to 2:1.

[0051] In another preferred embodiment, a) The weight / weight ratio of sulfur to limonene, preferably D-limonene, and the combined amount of terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol is 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65:1 to 1:2, or 50:1 to 1:2, or 40:1 to 1:2, or 30:1 to 1 The ratio is 2 to 2, or 25 to 1 to 2, or 24 to 1 to 2 to 1, or 24 to 1 to 2.5 to 1, or 24 to 1 to 3 to 1, or 24 to 1 to 4 to 1, or 24 to 1 to 5 to 1, or 24 to 1 to 6 to 1, or 24 to 1 to 8 to 1, or 24 to 1 to 12 to 1, or 20 to 1 to 1 to 2, or 15 to 1 to 1 to 2, or 10 to 1 to 2, or 20 to 1 to 5 to 1, or 20 to 1 to 10 to 1, or 20 to 1 to 12 to 1, or 20 to 1 to 6 to 1, or 8 to 1 to 2, or 6 to 1 to 1 to 2, or 6 to 1 to 2 to 2, or 5 to 1 to 2, or b) The weight / weight ratio of sulfur to limonene, preferably D-limonene, is 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65:1 to 1:2, or 50:1 to 1:2, or 40:1 to 1:2, or 30:1 to 1:2, or 25:1 to 1:2, or 24:1 to 2 The ratio is 1 to 1, or 24 to 1 to 2.5 to 1, or 24 to 1 to 3 to 1, or 24 to 1 to 4 to 1, or 24 to 1 to 5 to 1, or 24 to 1 to 6 to 1, or 24 to 1 to 8 to 1, or 24 to 1 to 12 to 1, or 20 to 1 to 1 to 2, or 15 to 1 to 1 to 2, or 10 to 1 to 2, or 20 to 1 to 5 to 1, or 20 to 1 to 10 to 1, or 20 to 1 to 12 to 1, or 20 to 1 to 6 to 1, or 8 to 1 to 2, or 6 to 1 to 1 to 2, or 6 to 1 to 2 to 2, or 5 to 1 to 2, or c) The weight / weight ratio of sulfur to limonene, preferably D-limonene, is 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65: 1 to 1 against 2, or 50 to 1 to 2, or 40 to 1 to 2, or 30 to 1 to 2, or 25 to 1 to 2, or 24 to 1 to 2, or 24 to 1 to 2, or 24 to 1 to 2.5, or 24 to 1 to 3, or 24 to 1 to 4, or 24 to 1 to 5, or 24 to 1 to 6, or 24 to 1 to 8, or 24 to 12, or 20 to 1 to 2 , or 15:1 to 1:2, or 10:1 to 1:2, or 20:1 to 5:1, or 20:1 to 10:1, or 20:1 to 12:1, or 20:1 to 6:1, or 8:1 to 1:2, or 6:1 to 1:2, or 6:1 to 2:2, or 5:1 to 2:1, and the amount of limonene, preferably D-limonene, to terpinene, pinene, p-cymene, eugenol, gerani The combined weight / weight ratio of terpenes including ol, thymol, and carvacrol is 75:1 to 1:1, or 50:1 to 1:1, or 25:1 to 1:1, or 10:1 to 1:1, or 8:1 to 1:1, or 5:1 to 1:1, or 2:1 to 1:1, preferably more than 90:1 or higher, 100:1 or higher, 300:1 or higher, 500:1 or higher, or 1000:1 or higher.

[0052] Fusarium head blight is caused by several species of the fungus Fusarium. Fusarium graminearum is the species that causes the most serious damage to crops. Fungi of the Fusarium genus are known to produce mycotoxins. For example, Fusarium graminearum often produces zearalenone and trichothecenes, such as nivalenol, deoxynivalenol (DON), and / or acetylated derivatives of DON, such as 3-acetyl-DON and 15-acetyl-DON. Fungi of the Cercospora genus are known to produce mycotoxins called cercosporins.

[0053] Therefore, the present invention relates to a method for reducing the amount of mycotoxins present in plant material, comprising: a) identifying a plant or a group of plants that are infected with or at risk of being infected with a mycotoxin-producing fungus, preferably a fungus belonging to the genus Fusarium or Cercospora that produces mycotoxins; and b) identifying a plant or a group of plants that are infected with or at risk of being infected with a fungus, a mycotoxin-producing fungus. A step of contacting a material part with a fungicidal amount of a mixture, wherein the mixture comprises sulfur and at least one terpene selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, in a ratio of 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2 10 to 1, or 100 to 1 to 2, or 70 to 1 to 2, or 65 to 1 to 2, or 50 to 1 to 2, or 40 to 1 to 2, or 30 to 1 to 2, or 25 to 1 to 2, or 24 to 1 to 2, or 24 to 1 to 2, or 24 to 1 to 2.5, or 24 to 1 to 3, or 24 to 1 to 4, or 24 to 1 to 5, or 24 to 1 to 6, or 24 to 1 to 8, or 24 to 12, or 20 to 1 to 2, or 15 to 1 to 2, or The method includes a step of providing a solution containing a sum of sulfur in a weight / weight ratio of 10:1 to 1:2, or 20:1 to 5:1, or 20:1 to 10:1, or 20:1 to 12:1, or 20:1 to 6:1, or 8:1 to 1:2, or 6:1 to 1:2, or 6:1 to 2:2, or 5:1 to 2:1, or 5:1 to 2:1, with a sum of sulfur in a weight / weight ratio of at least one terpene selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol. In one embodiment, at least one of the selected terpenes is limonene, preferably D-limonene, and the weight / weight ratio between sulfur and limonene is 100:1 to 1:2, or 70:1 to 1:2, or 65:1 to 4:1, or 63:1 to 2:1, or 30:1 to 1:1, or 25:1 to 1:1, or 24:1 to 2:1, or 12:1 to 2:1, or 5:1 to 2:1.

[0054] In another preferred embodiment, a) The weight / weight ratio of sulfur to limonene, preferably D-limonene, and the combined amount of terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol is 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65:1 to 1:2, or 50:1 to 1:2, or 40:1 to 1:2, or 30:1 to 1 The ratio is 2 to 2, or 25 to 1 to 2, or 24 to 1 to 2 to 1, or 24 to 1 to 2.5 to 1, or 24 to 1 to 3 to 1, or 24 to 1 to 4 to 1, or 24 to 1 to 5 to 1, or 24 to 1 to 6 to 1, or 24 to 1 to 8 to 1, or 24 to 1 to 12 to 1, or 20 to 1 to 1 to 2, or 15 to 1 to 1 to 2, or 10 to 1 to 2, or 20 to 1 to 5 to 1, or 20 to 1 to 10 to 1, or 20 to 1 to 12 to 1, or 20 to 1 to 6 to 1, or 8 to 1 to 2, or 6 to 1 to 1 to 2, or 6 to 1 to 2 to 2, or 5 to 1 to 2, or b) The weight / weight ratio of sulfur to limonene, preferably D-limonene, is 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65:1 to 1:2, or 50:1 to 1:2, or 40:1 to 1:2, or 30:1 to 1:2, or 25:1 to 1:2, or 24:1 to 2 The ratio is 1 to 1, or 24 to 1 to 2.5 to 1, or 24 to 1 to 3 to 1, or 24 to 1 to 4 to 1, or 24 to 1 to 5 to 1, or 24 to 1 to 6 to 1, or 24 to 1 to 8 to 1, or 24 to 1 to 12 to 1, or 20 to 1 to 1 to 2, or 15 to 1 to 1 to 2, or 10 to 1 to 2, or 20 to 1 to 5 to 1, or 20 to 1 to 10 to 1, or 20 to 1 to 12 to 1, or 20 to 1 to 6 to 1, or 8 to 1 to 2, or 6 to 1 to 1 to 2, or 6 to 1 to 2 to 2, or 5 to 1 to 2, or c) The weight / weight ratio of sulfur to limonene, preferably D-limonene, is 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65: 1 to 1 against 2, or 50 to 1 to 2, or 40 to 1 to 2, or 30 to 1 to 2, or 25 to 1 to 2, or 24 to 1 to 2, or 24 to 1 to 2, or 24 to 1 to 2.5, or 24 to 1 to 3, or 24 to 1 to 4, or 24 to 1 to 5, or 24 to 1 to 6, or 24 to 1 to 8, or 24 to 12, or 20 to 1 to 2 , or 15:1 to 1:2, or 10:1 to 1:2, or 20:1 to 5:1, or 20:1 to 10:1, or 20:1 to 12:1, or 20:1 to 6:1, or 8:1 to 1:2, or 6:1 to 1:2, or 6:1 to 2:2, or 5:1 to 2:1, and the amount of limonene, preferably D-limonene, to terpinene, pinene, p-cymene, eugenol, gerani The combined weight / weight ratio of terpenes including ol, thymol, and carvacrol is 75:1 to 1:1, or 50:1 to 1:1, or 25:1 to 1:1, or 10:1 to 1:1, or 8:1 to 1:1, or 5:1 to 1:1, or 2:1 to 1:1, preferably more than 90:1 or higher, 100:1 or higher, 300:1 or higher, 500:1 or higher, or 1000:1 or higher.

[0055] Plant pathogenic fungi of the genus Puccinia include species Puccinia triticina, Puccinia graminis f.sp. avenae, Puccinia graminis f.sp. poae, Puccinia graminis f.sp. secalis, Puccinia graminis f.sp. tritici, Puccinia graminis subsp. graminicola, Puccinia helianthi, Puccinia hordei, and Puccinia sorghi. It is preferable to select from the species Puccinia striiformis f.sp.hordei, and the species Puccinia striiformis f.sp.tritici. In one embodiment, the plant pathogenic fungus is from the species Puccinia triticina.

[0056] Plant pathogenic fungi of the genus Podosphaera are selected from the species Podosphaera fuliginea, Podosphaera leucotricha, Podosphaera clandestina, Podosphaera pannosa, Podosphaera tridactyla, Podosphaera xanthii, Podosphaera mors-uvae, and Podosphaera aphanis, or Podosphaera leucotricha, Podosphaera clandestina, It is preferable to select from Podosphaera clandestina, Podosphaera pannosa, Podosphaera tridactyla, Podosphaera xanthii, Podosphaera mors-uvae, and Podosphaera aphanis. In one embodiment, the plant pathogenic fungus is from the species Podosphaera leucotricha. In another embodiment, the plant pathogenic fungus is from the species Podosphaera fuliginea.Plant pathogenic fungi of the genera Erysiphe and Blumeria include the species Blumeria graminis (also known as Erysiphe graminis), Blumeria graminis f.sp. avenae, Blumeria graminis f.sp. hordei, Blumeria graminis f.sp. secalis, Blumeria graminis f.sp. tritici, Erysiphe cruciferarum, Erysiphe necator, and Erysiphe ticolacearum. It is preferable to select from the species *Cichoracearum* and *Erysiphe betae*. In one embodiment, the plant pathogenic fungus is from the species *Blumeria graminis*.

[0057] Plant pathogenic fungi of the genus Septoria are preferably selected from the species Zymoseptoria tritici, also known as Septoria tritici, Septoria betae, Septoria glycines, Septoria helianthi, and Septoria secalis. In one embodiment, the plant pathogenic fungus is from the species Zymoseptoria tritici.

[0058] The plant pathogenic fungi of the genus Cercospora are preferably selected from the species Cercospora beticola, Cercospora brassicola, Cercospora janseana, Cercospora sojina, Cercospora kikuchii, Cercospora concors, Cercospora solani, Cercospora solani-tuberosi, Cercospora sorghi, and Cercospora zeae-maydis. In one embodiment, the plant pathogenic fungus is from the species Cercospora beticola. In another embodiment, the plant pathogenic fungus is from the species Cercospora sojina.

[0059] Plant pathogenic fungi of the genus Sclerotinia are preferably selected from the species Sclerotinia sclerotiorum.

[0060] The plant pathogenic fungi of the genus Ramularia are preferably selected from the species Ramularia collo-cygni and Ramularia beticola. In one embodiment, the plant pathogenic fungus is from the species Ramularia collo-cygni.

[0061] The plant pathogenic fungi of the genus Fusarium are preferably selected from the species Fusarium graminearum, Fusarium culmorum, Fusarium avenaceum, Microdochium nivale, Fusarium verticilloides, Fusarium oxysporum, and Fusarium poae.

[0062] In one embodiment, the plant pathogenic fungus is from the species Fusarium graminearum.

[0063] The plant pathogenic fungi of the genus Pyrenophora are preferably selected from the species Pyrenophora teres, Pyrenophora tritici-repentis, Pyrenophora graminea, and Pyrenophora avenae. In one embodiment, the plant pathogenic fungi are selected from the species Pyrenophora teres and Pyrenophora tritici-repentis.

[0064] The plant pathogenic fungi of the genus Venturia are preferably selected from the species Venturia inaequalis, Venturia carpophila, Venturia cerasi, Venturia nashicola, Venturia pyrina, and Venturia oleaginea. In one embodiment, the plant pathogenic fungus is selected from the species Venturia inaequalis.

[0065] The plant pathogenic fungi of the genus Diplocarpon are preferably selected from the species Diplocarpon mali (anamorph Marssonina coronaria), Diplocarpon mespili, and Diplocarpon fragariae. In one embodiment, the plant pathogenic fungus is selected from the species Diplocarpon mali.

[0066] In one embodiment, the plant or plant part to be protected is from the genus Triticum, preferably the species Triticum aestivum or Triticum durum, more preferably from the species Triticum aestivum, and the plant pathogenic fungus is Puccinia triticina, Puccinia graminis f.sp. tritici, Puccinia striiformis f.sp. tritici, Erysiphe graminis, Blumeria graminis f.sp. tritici, Zymoseptoria The protection is from a species selected from Pyrenophora tritici and Pyrenophora tritici-repenti. Preferably, the plant or plant part is protected from Puccinia triticina and Erysiphe graminis. More preferably, the plant or plant part is protected from Puccinia triticina, Erysiphe graminis, and at least one of Zymoseptoria tritici and Pyrenophora tritici-repentis.

[0067] In one embodiment, the plant or plant part to be protected is from the species Hordeum vulgare, and the plant pathogenic fungus is from a species selected from Pyrenophora teres, Blumeria graminis f.sp.hordei, and Ramularia collo-cygni. Preferably, the plant or plant part is protected from at least two of Pyrenophora teres, Blumeria graminis f.sp.hordei, and Ramularia collo-cygni.

[0068] In one embodiment, the plant or plant part to be protected is from the species Secale cereale, and the plant pathogenic fungus is from a species selected from Puccinia graminis f.sp. secalis, Blumeria graminis f.sp. secalis, and Septoria secalis. Preferably, the plant or plant part is protected from Puccinia graminis f.sp. secalis and Blumeria graminis f.sp. secalis.

[0069] In one embodiment, the plant or plant part to be protected is from the species Avena sativa, and the plant pathogenic fungus is from a species selected from Puccinia graminis f.sp.avenae, Blumeria graminis f.sp.avenae, and Pyrenophora avenae. Preferably, the plant or plant part is protected from Puccinia graminis f.sp.avenae and Blumeria graminis f.sp.avenae.

[0070] In one embodiment, the plant or plant part to be protected is from the species Zea mays, and the plant pathogenic fungus is from a species selected from Puccinia sorghi and Cercospora zeae-maydis.

[0071] In one embodiment, the plant or plant part to be protected is from the species Beta vulgaris, and the plant pathogenic fungus is from a species selected from Cercospora beticola, Septoria betae, and Ramularia beticola. Preferably, the plant or plant part is protected from Cercospora beticola and at least one of Septoria betae and Ramularia beticola.

[0072] In one embodiment, the plant or plant part to be protected is from the Brassica napus species, and the plant pathogenic fungus is from a species selected from Sclerotinia sclerotiorum and Erysiphe cruciferarum. Preferably, the plant or plant part is protected from Sclerotinia sclerotiorum.

[0073] In one embodiment, the plant or plant part to be protected is from the Glycine max species, and the plant pathogenic fungus is from a species selected from Cercospora kikuchii, Cercospora sojina, Septoria glycines, and Sclerotinia sclerotiorum. Preferably, the plant or plant part is protected from Sclerotinia sclerotiorum or Cercospora sojina.

[0074] In one embodiment, the plant or plant part to be protected is from the species Solanum tuberosum, and the plant pathogenic fungus is from a species selected from Erysiphe cichoracearum, Cercospora concors, Cercospora solani, Cercospora solani-tuberosi, and Sclerotinia sclerotiorum. Preferably, the plant or plant part is protected from Sclerotinia sclerotiorum.

[0075] In one embodiment, the plant or plant part to be protected is from the species Helianthus annuus, and the plant pathogenic fungus is from a species selected from Puccinia helianthi, Septoria helianthi, and Sclerotinia sclerotiorum. Preferably, the plant or plant part is protected from Sclerotinia sclerotiorum.

[0076] In one embodiment, the plant or plant part to be protected is from the genera Triticum, Hordeum, Secale, or Zea, preferably Triticum aestivum, Triticum Durum, Hordeum vulgare, Secale cereale, or Zea mays, more preferably from Triticum aestivum, and the plant pathogenic fungus is a species selected from the genus Fusarium, preferably Fusarium graminearum, Fusarium culmorum, or Fusarium avenaceum. These are derived from the species Fusarium avenaceum, Fusarium verticilloides, Fusarium oxysporum, and Fusarium poae, more preferably Fusarium graminearum.

[0077] In one embodiment, the plant or plant part to be protected is from the genus Malus, preferably Malus domestica, and the plant pathogenic fungus is from the species Venturia inaequalis, Podosphaera leucotricha, or Diplocarpon mali.

[0078] In one embodiment, the plant or plant part to be protected is from the genus Pyrus, preferably the species Pyrus communis or Pyrus pyrifolia, and the plant pathogenic fungus is from the species Venturia pyrina, Venturia nashicola, or Diplocarpon mespili.

[0079] In one embodiment, the plant or plant part to be protected is from the genera Malus, Prunus, Pyrus, or Olea, preferably Malus domestica, Prunus persica, Prunus domestica, Prunus domestica, Prunus armeniaca, Prunus avium, Prunus cerasus, Pyrus pyrifolia, Pyrus communis, or Olea europaea. The plant pathogenic fungus is a species of the genus Venturia, preferably Venturia inaequalis, Venturia carpophila, Venturia cerasi, Venturia nashicola, Venturia pyrina, or Venturia oleaginea.

[0080] In one embodiment, the plant or plant part to be protected is from banana or plantain, and the plant pathogenic fungus is from a species selected from Mycosphaerella fijiensis, Mycosphaerella musicola, Cercospora hayi, Sclerotinia sclerotiorum, or Septoria eumusae.

[0081] The plant species listed above include, but are not limited to, cereals such as wheat and barley, as well as winter and spring varieties of rapeseed, such as winter wheat, spring wheat, and winter barley. They are understood to further include all subspecies, variants, varieties, and / or hybrids belonging to each plant species, including dwarf, semi-dwarf, and fully dwarf varieties and / or hybrids that are short in height and have thick, short stems.

[0082] Corn, also known as Indian corn or maize (Zea mays), includes all types of maize, such as field corn and sweet corn. According to the present invention, all soybean cultivars or varieties are included, in particular cultivars or varieties of indeterminate and determinate inflorescence.

[0083] The mixture can be combined with a biopesticide. The biopesticide may be added to the mixture as a tank mix to prepare a spray suspension, or it may be added directly as an integral part of a pesticide formulation containing the mixture. Alternatively, the biopesticide may be applied immediately before or after application of the spray suspension containing the mixture to protect the fungus, the plant, or the plant part to be protected from fungal attack.

[0084] The following list of biocides can be used in combination with the mixtures described herein. This list is intended to illustrate possible combinations, but is not limited to them: Biochemical pesticides L1) Microbial pesticides having fungicidal, bactericidal, virucidal and / or plant defense activating activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. amyloliquefaciens subspecies plantarum ssp. plantarum) (also called B. velezensis), B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, B. velezensis, Candida oleophila, C. saitoana, Clavibacter machinanensis michiganensis (bacteriophage), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f. catenulateP. catenulate (also known as Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, L. enzymes, Metschnikowia fructicola, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor albus, Paenibacillus alvei, Paenibacillus epiphyticus, P. polymyxa, Pantoea bagans vagans), Penicillium bilaiae, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas chloraphis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus T. flavus), Trichoderma asperelloides, T. asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T.T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia, Zucchini yellow mosaic virus (non-toxic strain), etc. L2) Biochemical pesticides having fungicidal, bactericidal, virucidal, and / or plant defense activating activity: Harpin protein, Reynoutria sachalinensis extract.

[0085] Another embodiment of the present invention is the mixture described above, used in a method for controlling plant pathogenic fungi. Preferably, the mixture comprises sulfur and at least one terpene selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol, wherein the weight / weight ratio of sulfur to the combined amount of all terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol is 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65:1 to 1:2, or 50:1 to 1:2, or 40:1 to 1:2, or 30:1 to 1:2, or 25:1 to 1:2, or 24:1 to 2:1, or 24:1 to 2.5:1, or 24:1 to 3:1, or 24:1 to 4:1, or 24:1 to 5:1, or 24:1 to 6:1, or 24:1 The ratio is ~8:1, or 24:1 to 12:1, or 20:1 to 1:2, or 15:1 to 1:2, or 10:1 to 1:2, or 20:1 to 5:1, or 20:1 to 10:1, or 20:1 to 12:1, or 20:1 to 6:1, or 8:1 to 1:2, or 6:1 to 1:2, or 6:1 to 2:2, or 5:1 to 2:1. Preferably, the mixture contains limonene with a sulfur-to-limonene weight / weight ratio of 25:1 to 1:1 or 20:1 to 12:1.

[0086] This invention relates to the genera Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, and Venturia. A mixture comprising sulfur and at least one terpene selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol for controlling plant pathogenic fungi selected from the genera *Uria* and *Diplocarpon*, wherein the sulfur is a mixture of all terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol. The weight / weight ratio of the added amount is 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65:1 to 1:2, or 50:1 to 1:2, or 40:1 to 1:2, or 30:1 to 1:2, or 25:1 to 1:2, or 24:1 to 2:1, or 24:1 to 2 This also includes the use of mixtures that are 0.5:1, or 24:1 to 3:1, or 24:1 to 4:1, or 24:1 to 5:1, or 24:1 to 6:1, or 24:1 to 8:1, or 24:1 to 12:1, or 20:1 to 1:2, or 15:1 to 1:2, or 10:1 to 1:2, or 20:1 to 5:1, or 20:1 to 10:1, or 20:1 to 12:1, or 20:1 to 6:1, or 8:1 to 1:2, or 6:1 to 1:2, or 6:1 to 2:2, or 5:1 to 2:1.

[0087] Preferably, the mixture contains limonene, more preferably D-limonene, and the sulfur-to-limonene weight / weight ratio is 100:1 to 1:10, or 70:1 to 1:10, or 65:1 to 1:10, or 50:1 to 1:10, or 40:1 to 1:10, or 30:1 to 1:10, or 25:1 to 1:10, or 24:1 to 2:10, or 100:1 to 1:2, or 70:1 to 1:2, or 65:1 to 1:2, or 50:1 to 1:2, or 40:1 to 1:2, or 30:1 to 1:2, or 25:1 The ratios are approximately 1 to 2, or 24 to 1 to 2 to 1, or 24 to 1 to 2.5 to 1, or 24 to 1 to 3 to 1, or 24 to 1 to 4 to 1, or 24 to 1 to 5 to 1, or 24 to 1 to 6 to 1, or 24 to 1 to 8 to 1, or 24 to 1 to 12 to 1, or 20 to 1 to 1 to 2, or 15 to 1 to 1 to 2, or 10 to 1 to 2, or 20 to 1 to 5 to 1, or 20 to 1 to 10 to 1, or 20 to 1 to 12 to 1, or 20 to 1 to 6 to 1, or 8 to 1 to 2, or 6 to 1 to 1 to 2, or 6 to 1 to 2 to 2, or 5 to 1 to 2. Preferably, the at least one fungal species to be controlled is selected from Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon.

[0088] The present invention also includes the use of a mixture comprising sulfur and limonene, more preferably D-limonene, for controlling plant pathogenic fungi selected from the genera Puccinia, Blumeria, Uncinula, Cercospora, Septoria, Ramularia, Venturia, Rhynchosporium, and Sphaerotheca, wherein the weight / weight ratio of sulfur to limonene is 25:1 to 1:1 or 24:1 to 1:1.

[0089] This invention relates to the species Puccinia triticina, Puccinia recondita, Blumeria graminis, Uncinula necator, Cercospora beticola, Cercospora sojina, Septoria tritici, Ramularia collo-cygni, Venturia inaequalis, Rhynchosporium secalis, and Sphaerotheca The use of a mixture comprising sulfur and limonene, more preferably D-limonene, for controlling plant pathogenic fungi selected from the species fuliginea, wherein the weight / weight ratio of sulfur to limonene is 25:1 to 1:1 or 24:1 to 1:1.

[0090] The present invention also includes the use of a mixture comprising sulfur and limonene, more preferably D-limonene, for controlling plant pathogenic fungi selected from the species Puccinia recondita, Cercospora sojina, and Sphaerotheca fuliginea, wherein the weight / weight ratio of sulfur to limonene is 25:1 to 1:1 or 24:1 to 1:1.

[0091] The present invention also includes the use of a mixture comprising sulfur and limonene, more preferably D-limonene, for controlling plant pathogenic fungi selected from the species Cercospora beticola and Venturia inaequalis, wherein the weight / weight ratio of sulfur to limonene is 18:1 to 1:1 or 16:1 to 1:1.

[0092] The present invention also includes the use of a mixture comprising sulfur and limonene, more preferably D-limonene, for controlling plant pathogenic fungi selected from the species Puccinia triticina, Blumeria graminis, Uncinula necator, Septoria tritici, Ramularia collo-cygni, and Rhynchosporium secalis, wherein the weight / weight ratio of sulfur to limonene is 15:1 to 1:1 or 12:1 to 1:1.

[0093] The methods for controlling plant pathogenic fungi described herein do not involve any preventive or therapeutic treatment of animals or humans.

[0094] Typically, the mixture is diluted with water to obtain a spray suspension, which is then applied to a method for controlling plant pathogenic fungi.

[0095] Preferably, the mixture is contained in the pesticide formulation, which is then diluted with water to prepare a spray suspension.

[0096] Suspension emulsion formulations and suspension concentrate formulations containing sulfur and selected terpenes Further embodiments of the present invention are suspension emulsion formulations and suspension concentrate formulations comprising a) sulfur, b) one or more terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, c) one or more carrier oils, and d) optionally further components.

[0097] Suspended emulsions of pesticides are also known as "SE" type pesticide formulations. Suspended emulsions typically comprise a continuous aqueous phase, a dispersed oil phase, and a suspended solid phase. The oil phase typically forms droplets within the aqueous phase. The oil phase typically contains a water-immiscible active ingredient. The oil phase typically contains at least one biocide that can be dissolved in a water-immiscible solvent. The solid phase typically consists of solid particles within the aqueous phase. The solid phase may contain at least one biocide suspended in the continuous aqueous phase. Further biocides are dissolved in the water-immiscible solvent. Preferably, further biocides are present in at least the dispersed oil phase of the suspended emulsion. The first biocide is suspended in the continuous aqueous phase. Preferably, the first biocide is present in at least the solid phase of the suspended emulsion.

[0098] Agricultural chemical suspensions and concentrates (also known as "SC" formulations) typically relate to compositions containing solid particles uniformly dispersed in a continuous aqueous phase. Agricultural chemical suspensions and concentrates are usually pre-formed commercially and conventionally diluted with a carrier such as water when forming spray mixtures (also known as tank mixes). The continuous aqueous phase of a suspension or concentrate typically does not contain any other dispersed phases other than the biological agent particles.

[0099] The suspension emulsion formulation and suspension concentrate formulation comprises a) sulfur, b) at least one terpene selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, wherein the combined weight / weight ratio of sulfur to limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol is 25:1 to 1:1 or 20:1 to 12:1, c) one or more carrier oils, and d) optionally further components.

[0100] Preferred suspension emulsion formulations and suspension concentrate formulations include a) sulfur, b) limonene having a weight / weight ratio of sulfur to limonene of 25:1 to 1:1 or 20:1 to 12:1, c) one or more carrier oils, and d) optionally further components.

[0101] Preferably, the suspension emulsion formulation and the suspension concentrate formulation do not contain silica such as precipitated silica.

[0102] A suitable carrier oil must have low solubility in water. It is preferable that the solubility at 20°C be less than 1 gram / liter, preferably less than 0.1 grams / liter. These may consist of only one type of carrier oil, or a mixture of at least two types of carrier oils. The carrier oil is preferably selected from one or more of the following groups.

[0103] A preferred group of carrier oils are terpenes that are liquid at 20°C and are not limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, or carvacrol.

[0104] Another preferred group of carrier oils includes vegetable oils and alkyl esters of such vegetable oils. Preferably, the esters are selected from methyl esters, ethyl esters, propyl esters, isopropyl esters, and butyl esters. The vegetable oils are preferably selected from soybean oil, rapeseed oil, sunflower oil, peanut oil, linseed oil, cottonseed oil, corn oil, castor oil, neem oil, and olive oil. Preferred mixtures of alkyl esters are C6-C10 fatty acid methyl esters, C8-C10 fatty acid methyl esters, and C16-C18 fatty acid methyl esters.

[0105] Preferred alkyl esters of single fatty acids are methyl oleate, methyl octanoate, methyl decanoate, methyl linolenate, ethyl hexanoate, ethyl octanoate, ethyl decanoate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, myristyl myristate, and butyl stearate. In one embodiment, the carrier oil is or contains ethoxylated castor oil. In one embodiment, the carrier oil is or contains methyl oleate. In one embodiment, the carrier oil is or contains isopropyl myristate. In one embodiment, the carrier oil is or contains soybean oil, rapeseed oil, sunflower oil, peanut oil, linseed oil, cottonseed oil, corn oil, or castor oil. In one embodiment, the carrier oil is or contains rapeseed oil and / or sunflower oil.

[0106] Further groups of carrier oils include C11-C14 alkyl acetates and decyl acetates, isobornyl acetate, and 2-ethylhexyl acetate.

[0107] Further groups include C12-C20 fatty alcohols, octanol, decyl alcohol, tridecanol, 2-ethylhexanol, oleyl alcohol, cetyl alcohol, and lauryl alcohol.

[0108] Further groups include dibutyl adipate, diisobutyl adipate, diisopropyl adipate, diethylhexyl adipate, diisodecyl adipate, diisotridecyl adipate, diethylhexyl sebacate, and dibutyl sebacate.

[0109] Further groups include ethyl cinnamate and propyl cinnamate.

[0110] Further groups include benzyl benzoate, benzyl acetate, benzyl butyl ester, isopropyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, heptyl benzoate, octyl benzoate, nonyl benzoate, decyl benzoate, propylene glycol dibenzoate, and dipropylene glycol dibenzoate.

[0111] Further groups include tall oil fatty acids, oleic acid, palmitic acid, 2-ethylhexyl octanoate, coconut oil alkyl caprylate, texanol diisobutyrate, 1,2-cyclohexanedicarboxylic acid diisononyl ester, di-n-butyl carbonate, alkylnaphthalene, and dioctyl ether.

[0112] Another group includes aromatic solvents such as naphtha (Solvesso grade), decane, petroleum, cyclohexane, methylcyclohexane, kerosene, tris-(2-ethylhexyl)phosphate, tris-(2-butoxyethyl)phosphate, 2-ethylhexyl lactate, tributyl citrate, acetyl tributyl citrate, tris-(ethylhexyl) trimellitate, dimethyloctanamide, dimethyldecanamide, dimethyldodecanamide, and mineral oil, preferably defatted mineral oil (CAS No. 64742-56-9). In one embodiment, the carrier oil is or contains defatted mineral oil (CAS No. 64742-56-9).

[0113] In one embodiment, the carrier oil comprises a mixture of at least two of methyl oleate, isopropyl myristate, rapeseed oil, and sunflower oil, or a mixture of at least two of methyl oleate, rapeseed oil, and sunflower oil.

[0114] The suspension emulsion formulation or suspension concentrate formulation contains elemental sulfur particles in the following concentrations, in descending order of preference: 10-1000 grams / liter, 100-900 grams / liter, 500-800 grams / liter, 550-700 grams / liter, or 600-700 grams / liter.

[0115] The combined amount of all terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol is preferably 10-300 grams / liter, 10-250 grams / liter, 10-200 grams / liter, 15-150 grams / liter, 20-150 grams / liter, 20-130 grams / liter, or 20-60 grams / liter.

[0116] The amount of limonene, preferably D-limonene, is 3-300 grams / liter, 5-300 grams / liter, 7-300 grams / liter, 10-300 grams / liter, 10-250 grams / liter, 10-200 grams / liter, 15-150 grams / liter, 20-150 grams / liter, 20-130 grams / liter, 20-60 grams / liter, 3-10 grams / liter, 5-10 grams / liter, 3-20 grams / liter, or 3-60 grams / liter, or 20-60 grams / liter.

[0117] In one embodiment, the amount of limonene, preferably D-limonene, is 10 to 70 grams / liter or 20 to 60 grams / liter.

[0118] The combined amount of all carrier oils is preferably 50-300 grams / liter, 70-250 grams / liter, 70-200 grams / liter, 80-250 grams / liter, 80-200 grams / liter, 80-170 grams / liter, 80-150 grams / liter, 80-120 grams / liter, 80-110 grams / liter, 90-250 grams / liter, 90-200 grams / liter, 90-170 grams / liter, 90-150 grams / liter, 90-120 grams / liter, and 90-110 grams / liter.

[0119] In one embodiment, the amount of limonene, preferably D-limonene, is 10 to 70 grams / liter or 20 to 60 grams / liter.

[0120] In one embodiment, the amount of limonene, preferably D-limonene, is 10 to 70 grams / liter, or 20 to 60 grams / liter, and the amount of carrier oil is 20 to 120 grams / liter, or 50 to 150 grams / liter.

[0121] The preferred weight / weight ratio of sulfur to the combined amount of at least one terpene selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol is 24:1 to 2:1, or 24:1 to 2.5:1, or 24:1 to 3:1, or 24:1 to 4:1, or 24:1 to 5:1, or 24:1 to 6:1, or 24:1 to 8:1, or 24:1 to 12:1, or 20:1 to 12:1.

[0122] In one embodiment, the weight / weight ratio of sulfur to limonene, terpinene, pinene, preferably D-limonene is 24:1 to 2:1, or 24:1 to 2.5:1, or 24:1 to 3:1, or 24:1 to 4:1, or 24:1 to 5:1, or 24:1 to 6:1, or 24:1 to 8:1, or 24:1 to 12:1, or 20:1 to 12:1.

[0123] In one embodiment, the weight / weight ratio of sulfur to limonene, terpinene, pinene, preferably D-limonene is 24:1 to 1:1, or 16:1 to 1:1, or 12:1 to 1:1. In another embodiment, it is 15:1 to 10:1 or 12:1.

[0124] The preferred weight / weight ratio of sulfur to the combined amount of all carrier oils is 7:1 to 2:1, or 7:1 to 3:1, or 7:1 to 4:1, or 7:1 to 4.5:1, or 7:1 to 5:1, or 6:1 to 2:1, or 6:1 to 3:1, or 6:1 to 3.6:1, or 6:1 to 4:1, or 6:1 to 4.5:1.

[0125] In one embodiment, the weight / weight ratio of sulfur to the total amount of all carrier oils is 12:1 to 4:1.

[0126] The preferred weight / weight ratio of the combined amount of at least one terpene selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol to the combined amount of all carrier oils is 1:6 to 1:1, or 1:5 to 1:1, or 1:4 to 1:1, or 1:5 to 1:2, or 1:4 to 1:2, or 1:5 to 1:2.5, or 1:4 to 1:2.5, or 1:5 to 1:3, or 1:4 to 1:3.

[0127] In one embodiment, the weight / weight ratio of the amount of limonene, preferably D-limonene, to the total amount of all carrier oils is 1:6 to 1:1, or 1:5 to 1:1, or 1:4 to 1:1, or 1:5 to 1:2, or 1:4 to 1:2, or 1:5 to 1:2.5, or 1:4 to 1:2.5, or 1:5 to 1:3, or 1:4 to 1:3.

[0128] In one embodiment, the weight / weight ratio of sulfur to the total amount of all carrier oils is 12:1 to 4:1, the weight / weight ratio of sulfur to limonene, preferably D-limonene, is 15:1 to 10:1, and the weight / weight ratio of limonene, preferably D-limonene, to the total amount of all carrier oils is 1:4 to 1:1.

[0129] The preferred weight / weight ratio of sulfur to the combined amount of all terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, and all carrier oils, is 12:1 to 6:1, or 6:1 to 2:1, or 5:1 to 2.2:1, or 4.8:1 to 2.4:1, or 5:1 to 2.4:1.

[0130] In one embodiment, the weight / weight ratio of sulfur to limonene, preferably D-limonene, and the combined amount of all carrier oils is 6:1 to 2:1, or 5:1 to 2.2:1, or 4.8:1 to 2.4:1, or 5:1 to 2.4:1.

[0131] In one embodiment, the suspension emulsion formulation or the suspension concentrate formulation is a) Weight ratio of sulfur to the total amount of all carrier oils combined, from 12:1 to 4:1. b) A weight / weight ratio of sulfur to limonene, preferably D-limonene, of 15:1 to 10:1. c) A weight / weight ratio of limonene, preferably D-limonene, to the combined amount of all carrier oils, in a ratio of 1:4 to 1:1, and d) A weight / weight ratio of sulfur to limonene, preferably D-limonene, and the total amount of all carrier oils, in a ratio of 8:1 to 2:1, or 6:1 to 2:1, or 6:1 to 3:1. It has.

[0132] Examples of exemplary but not limited to suspension emulsion formulations or suspension concentrate formulations are: a) comprising 500-700, preferably 600 grams / liter of sulfur, 25-250 grams / liter of one or more terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, 100-200, 100-175, 100-150, or 100-125 grams / liter of one or more carrier oils, optionally further components, and water up to a total volume of 1 liter, or b) comprising 500-700, preferably 600 grams / liter of sulfur, 25-125 grams / liter of one or more terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, 100-200, or 100-175, or 100-150, or 100-125 grams / liter of one or more carrier oils, optionally further components, and water up to a total volume of 1 liter, or c) comprising 500-700, preferably 600 grams / liter of sulfur, 25-100 grams / liter of one or more terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, 100-200, or 100-175, or 100-150, or 100-125 grams / liter of one or more carrier oils, optionally further components, and water up to a total volume of 1 liter, or d) comprising 500 to 700 grams, preferably 600 grams / liter of sulfur, 25 to 75 grams / liter of one or more terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, 100 to 200 grams, or 100 to 175 grams, or 100 to 150 grams, or 100 to 125 grams / liter of one or more carrier oils, optionally further components, and water up to a total volume of 1 liter.

[0133] Tables 1 to 3 provide further non-limiting examples regarding the amount of sulfur in a suspension emulsion or suspension concentrate formulation, the combined amount of terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, and the combined amount of carrier oil.

[0134] [Table 1]

[0135] [Table 2]

[0136] [Table 3]

[0137] In one embodiment, the suspension emulsion formulation or the suspension concentrate formulation is a) 500 to 700 grams of sulfur, preferably 600 grams / liter, b) 50-70 grams / liter of limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, preferably limonene, more preferably D-limonene, c) One or more carrier oils in a total amount of 40 to 180 grams / liter, d) Optionally, further constituent components, e) Water up to a total volume of 1 liter and Includes.

[0138] In one embodiment, the suspension emulsion formulation or the suspension concentrate formulation is a) 500 to 700 grams of sulfur, preferably 600 grams / liter, b) A combined amount of at least one terpene, 50 to 70 grams / liter, which is one or more terpenes selected from terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, preferably limonene, more preferably D-limonene, c) One or more carrier oils in a total amount of 40 to 180 grams / liter, d) Optionally, further constituent components, e) Water up to a total volume of 1 liter and Includes, 1) The weight / weight ratio of sulfur to the total amount of all carrier oils is 12:1 to 4:1. 2) The weight / weight ratio of sulfur to one or more terpenes selected from terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol is 15:1 to 10:1. 3) The weight / weight ratio of the combined amount of one or more terpenes selected from terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol to the combined amount of all carrier oils is 1:4 to 1:1. 4) The weight / weight ratio of sulfur to the combined amount of one or more terpenes selected from terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, and the combined amount of all carrier oils, is 8:1 to 2:1, or 6:1 to 2:1, or 6:1 to 3:1.

[0139] In one embodiment, the suspension emulsion formulation or the suspension concentrate formulation is f) 500-700, preferably 600 grams / liter of sulfur, g) 50-70 grams / liter of limonene, more preferably D-limonene, h) One or more carrier oils in a total amount of 40-180 grams / liter, i) Optionally, further constituent components, j) Water up to a total volume of 1 liter and Includes, 5) The weight ratio of sulfur to the total amount of all carrier oils is 12:1 to 4:1. 6) The weight / weight ratio of sulfur to limonene, more preferably D-limonene, is 15:1 to 10:1. 7) The weight / weight ratio of limonene, more preferably D-limonene, to the total amount of all carrier oils is 1:4 to 1:1. 8) The weight / weight ratio of sulfur to limonene, more preferably D-limonene and the combined amount of all carrier oils is 8:1 to 2:1, or 6:1 to 2:1, or 6:1 to 3:1.

[0140] The selected terpenes and carrier oils used in the suspension emulsion formulations or suspension concentrate formulations described in Tables 1 to 3 are preferably selected from limonene, α-terpinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, and carrier oils, and are particularly preferably formulations containing a combination of limonene and methyl oleate, or a combination of limonene and isopropyl myristate, or a combination of limonene and one or more carrier oils selected from soybean oil, rapeseed oil, sunflower oil, peanut oil, linseed oil, cottonseed oil, corn oil, or castor oil.

[0141] Preferably, the oil phase has an average oil droplet size of less than 25 microns, less than 15 microns, less than 10 microns, or less than 5 microns.

[0142] Suspension emulsion formulations or suspension concentrate formulations typically have a pH of 5.5 to 8.5, preferably 6.5 to 7.5.

[0143] The suspension emulsion formulations or suspension concentrate formulations described herein are selected based on their good storage stability.

[0144] Preferably, the change in the D50, D90, and / or D[4;3] values, which relate to the percentage of sulfur particles larger than 2 micrometers after storage at 40°C for two weeks, should not exceed plus or minus 15%, preferably plus or minus 10%, and more preferably plus or minus 5%.

[0145] Preferably, the change in the D50, D90 and / or D[4;3] values, which relate to the percentage of sulfur particles larger than 2 micrometers after storage at 50°C for two weeks, should not exceed plus or minus 15%, preferably plus or minus 10%, and more preferably plus or minus 5%.

[0146] Preferably, the change in the D50, D90 and / or D[4;3] values, which relate to the percentage of sulfur particles larger than 2 micrometers, after storage for two weeks at a 12-hour cycle temperature of -10°C to +10°C, should not exceed plus or minus 25%, preferably plus or minus 20%, more preferably plus or minus 15%, and even more preferably plus or minus 10%.

[0147] Further components Suspension emulsion formulations or suspension concentrate formulations may contain further components, such as auxiliary agents, that are known to be suitable for use in pesticide formulations.

[0148] Suitable examples of auxiliary agents include liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, antioxidants, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericidal agents, antifreezes, defoamers, colorants, tackifiers, and binders.

[0149] The liquid carrier is preferably water.

[0150] Preferably, the suspension concentrate formulation or suspension emulsion formulation contains one or more of the following excipients: a) One or more dispersants in a concentration of 70-10 grams / liter, b) One or more antifreeze agents in an amount of 70-20 grams / liter, c) One or more anionic surfactants in an amount of 50-1 or 50-20 grams / liter d) One or more nonionic surfactants in an amount of 100-1 or 10-1 grams / liter. e) One or more biocides in a quantity of 10 to 2 grams / liter, f) One or more defoaming agents in a quantity of 10 to 1 gram / liter, g) 10 to 1 gram / liter of one or more antioxidants, h) One or more thickening agents in an amount of 10 to 1 gram / liter.

[0151] Suitable solid carriers or fillers include mineral soils such as silicate, silica gel, talc, kaolin, limestone, lime, white pigment, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide, polysaccharide powders such as cellulose, starch, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, plant-derived products such as grain flour, bark flour, wood flour, nut shell flour, and mixtures thereof.

[0152] Suitable surfactants are surface-active compounds such as anionic, cationic, nonionic, and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetration enhancers, protective colloids, or adjuvants. Examples of surfactants are described in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

[0153] Suitable anionic surfactants are sulfonates, sulfates, phosphates, alkali salts, alkaline earth salts, or ammonium salts of carboxylates, and mixtures thereof. Examples of sulfonates include alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates, or sulfosuccinates. Examples of sulfates include fatty acids and oils, ethoxylated alkylphenols, alcohols, ethoxylated alcohols, or fatty acid ester sulfates. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates.

[0154] Suitable nonionic surfactants include alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymer-based surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids, or fatty acid esters that are alkoxylated with 1 to 50 equivalents of ethylene oxide and / or propylene oxide and / or butylene oxide, preferably ethylene oxide, which can be used for alkoxylation. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters, or monoglycerides. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters, or alkyl polyglucosides. Examples of polymer-based surfactants are homopolymers or copolymers of vinylpyrrolidone, vinyl alcohol, or vinyl acetate.

[0155] Suitable cationic surfactants are quaternary surfactants, such as quaternary ammonium compounds having one or two hydrophobic groups or salts of long-chain primary amines. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are AB or ABA type block polymers composed of blocks of polyethylene oxide and polypropylene oxide, or ABC type block polymers composed of alkanols, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyhydric acids or polyhydric bases. Examples of polyhydric acids are alkali salts of polyacrylic acid or polyhydric comb polymers. Examples of polyhydric bases are polyvinylamine or polyethyleneamine.

[0156] Suitable thickeners include polysaccharides (e.g., xanthan gum, carboxymethylcellulose), inorganic clay (organically modified or unmodified), polycarboxylates, and silicates.

[0157] Suitable bactericides include bronopol and isothiazolinone derivatives, such as alkylisothiazolinone and benzisothiazolinone.

[0158] Suitable antifreezes are ethylene glycol, propylene glycol, urea, and glycerin.

[0159] Suitable defoaming agents include silicones, long-chain alcohols, and fatty acid salts.

[0160] Suitable colorants (e.g., red, blue, or green) are low water-soluble pigments and water-soluble dyes. Examples include inorganic colorants (e.g., iron oxide, titanium dioxide, iron hexacyanoferrate) and organic colorants (e.g., alizarin colorants, azo colorants, and phthalocyanine colorants).

[0161] Suitable tackifiers or binders include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylate, biological or synthetic waxes, and cellulose ethers.

[0162] When the intention is to enhance antioxidant capacity beyond the level provided by other components, for example, by terpenes and / or carrier oils that are liquid at 20°C, the antioxidant is preferably a suspension concentrate formulation or a suspension emulsion formulation. Such additional antioxidants are preferably selected from tocopherols, e.g., vanillin, α-tocopherol, ascorbic acid, ascorbates, carotenoids, e.g., β-carotene, n-propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), and tert-butylhydroquinone (TBHQ).

[0163] More preferred are n-propyl gallate, ascorbic acid, sodium sulfite, tocopherol acetate, and butylated hydroxyanisole (BHA).

[0164] Antioxidant activity can be measured by methods known in the art, for example, the methods discussed in Munteanu and Apetrei, Int. J. Mol. Sci.; Analytical Methods Used in Determining Antioxidant Activity; A Review; 2021, 22, 3380. https: / / doi.org / 10.3390 / ijms22073380.

[0165] Preferably, the suspension emulsion formulation or suspension concentrate formulation contains one or more antioxidants in an amount of 20 to 0.5, 15 to 1, 10 to 1, 8 to 1, or 5 to 1 gram / liter, which are not terpenes or carrier oils that are liquid as pure substances at 20°C. In one embodiment, the antioxidant is vanillin.

[0166] In one embodiment, the suspension concentrate formulation or suspension emulsion formulation comprises a) to f). a) One or more dispersants in a concentration of 50-20 grams / liter (e.g., Morwet D 425, CAS 577773-56-9), b) 50-20 grams / liter of one or more antifreeze agents (e.g., 1,2-propylene glycol), c) One or more anionic surfactants in an amount of 50-1 or 50-20 grams / liter (e.g., Wethol NT1 CAS 211565-27-4 or Wethol EM 1, CAS 26264-06-2), d) One or more nonionic surfactants in an amount of 100 to 1 or 10 to 1 gram / liter (e.g., Agnique SPO 40 and Wethol EM 31, CAS 61791-12-6), e) One or more biocides in amounts of 5 to 3 grams / liter (e.g., Acticide MV and Acticide B 20), and f) One or more defoaming agents (e.g., SRE-PFL) in a concentration of 10 to 1 gram / liter.

[0167] CAS numbers are defined by the Chemical Information Retrieval Service (CAS).

[0168] In one embodiment, the suspension concentrate formulation or suspension emulsion formulation also includes a) to g), preferably h). a) One or more dispersants in an amount of 70-10 or 50-20 grams / liter, b) One or more antifreeze agents in an amount of 70-20 or 50-20 grams / liter, c) One or more anionic surfactants in an amount of 50-1 or 50-20 grams / liter d) One or more nonionic surfactants in an amount of 100-1 or 10-1 grams / liter. e) One or more biocides in a quantity of 10-2 or 5-3 grams / liter, f) One or more defoaming agents in a quantity of 10 to 1 gram / liter, g) 10 to 1 gram / liter of one or more antioxidants, h) One or more thickening agents in an amount of 10 to 1 gram / liter g) 10 to 1 gram / liter of one or more antioxidants, h) One or more thickening agents in an amount of 10 to 1 gram / liter.

[0169] In one embodiment, the excipient in the suspension concentrate formulation or suspension emulsion formulation includes an excipient selected from the following group. a) Fatty alcohol alkoxylates, b) Silicone adjuvant, c) Sulfosuccinate, d) A mixture of at least two of a-c).

[0170] Preferred fatty alcohol alkoxylates are Plurafac LF 221 (CAS 208350-19-0), Plurafac LF 901 (CAS 166736-08-9), Lutensol TO 8 and Lutensol ON 60 (CAS 123897-56-3), Plurafac LF 1312, Dehydol LT 7, or Lutensol AT 18.

[0171] Even more preferred fatty alcohol alkoxylates include C12-C18 alkyl alcohol ethoxylates.

[0172] Preferred silicone adjuvants are Silwet HS 604 (CAS 2524826-13-7) and Silwet HS 312 (CAS 1012786-03-6).

[0173] The preferred sulfosuccinate is Lutensit A-BO (CAS 577-11-7).

[0174] In some embodiments, the auxiliary agent selected from group a) to c) or a combination thereof is 1) One or more sulfosuccinates, preferably at least one sulfosuccinate being a salt of bis(2-ethylhexyl)sulfosuccinate, more preferably sodium bis(2-ethylhexyl)sulfosuccinate, and even more preferably Lutensit A-BO. 2) One or more fatty alcohol alkoxylates, preferably at least one fatty alcohol alkoxylate selected from Plurafac LF 221, Plurafac LF 901, Lutensol TO 8 and Lutensol ON 60. 3) One or more silicone adjuvants, preferably selected from Silwet HS 604 and Silwet HS 312. 4) A mixture of one or more sulfosuccinates and one or more fatty alcohol alkoxylates, preferably a salt of bis(2-ethylhexyl)sulfosuccinate, more preferably sodium bis(2-ethylhexyl)sulfosuccinate, and even more preferably a mixture containing Lutensit A-BO, wherein the preferred fatty alcohol alkoxylates are selected from Plurafac LF 221, Plurafac LF 901, Lutensol TO 8 and Lutensol ON 60. 5) A mixture of one or more fatty alcohol alkoxylates and one or more silicone adjuvants. Preferably, at least one of the fatty alcohol alkoxylates is selected from Plurafac LF 221, Plurafac LF 901, Lutensol TO 8, and Lutensol ON 60. Preferably, one or more of the silicone adjuvants are selected from Silwet HS 604 and Silwet HS 312.

[0175] Preferably, the weight / weight ratio of the combined amount of sulfosuccinate to the combined amount of fatty alcohol alkoxylate is 5:1 to 1:5, 3:1 to 1:3, 2:1 to 1:2, or 1:1.

[0176] Preferably, the weight / weight ratio of the combined amount of fatty alcohol alkoxylate to the combined amount of silicone adjuvant is 5:1 to 1:5, 3:1 to 1:3, 2:1 to 1:2, or 1:1.

[0177] In one embodiment, the weight / weight ratio of the combined amount of fatty alcohol alkoxylate, preferably C12-C18 alkyl alcohol ethoxylate, to limonene, preferably D-limonene, is 1:1 to 1:4, and preferably the amount of C12-C18 alkyl alcohol ethoxylate is 1:2 to 1:4.

[0178] In one embodiment, the suspension emulsion formulation or suspension concentrate formulation comprises sulfur, limonene, preferably D-limonene, carrier oil, and fatty alcohol alkoxylate, preferably C12-C18 alkyl alcohol ethoxylate. a) The combined weight / weight ratio of sulfur to all carrier oils is 12:1 to 4:1. b) The amount of sulfur to limonene, preferably D-limonene, is in a weight / weight ratio of 15:1 to 10:1. c) Limonene, preferably D-limonene, to the combined amount of all carrier oils in a weight / weight ratio of 1:4 to 1:1. d) The combined amount of sulfur to limonene, preferably D-limonene, and the combined amount of all carrier oils are in a weight / weight ratio of 8:1 to 2:1, or 6:1 to 2:1, or 6:1 to 3:1. e) Fatty alcohol alkoxylate, preferably C12-C18 alkyl alcohol ethoxylate, in a combined weight / weight ratio of limonene, preferably D-limonene, to 1:1 to 1:2. It has.

[0179] In one embodiment, the suspension emulsion formulation or the suspension concentrate formulation is a) 500 to 700 grams of sulfur, preferably 600 grams / liter, b) 50-70 grams / liter of limonene, more preferably D-limonene, c) One or more carrier oils in a total amount of 40 to 180 grams / liter, d) 25-70 grams / liter of fatty alcohol alkoxylate, preferably C12-C18 alkyl alcohol ethoxylate, e) Optionally, further constituent components, f) Water up to a total volume of 1 liter and Includes, 1) The weight / weight ratio of sulfur to the total amount of all carrier oils is 12:1 to 4:1. 2) The weight / weight ratio of sulfur to limonene, more preferably D-limonene, is 15:1 to 10:1. 3) The weight / weight ratio of limonene, more preferably D-limonene, to the total amount of all carrier oils is 1:4 to 1:1. 4) The weight / weight ratio of sulfur to limonene, more preferably D-limonene and the combined amount of all carrier oils is 8:1 to 2:1, or 6:1 to 2:1, or 6:1 to 3:1. 5) The combined weight / weight ratio of fatty alcohol alkoxylate, preferably C12-C18 alkyl alcohol ethoxylate, to limonene, preferably D-limonene, is 1:1 to 1:4, and preferably the amount of C12-C18 alkyl alcohol ethoxylate is 1:2 to 1:4.

[0180] The total amount of the auxiliary agent selected from the following groups: fatty alcohol alkoxylates, silicone adjuvants, and sulfosuccinates in the suspension concentrate or suspension emulsion formulation is preferably 100-1 gram / liter, 80-1 gram / liter, 70-1 gram / liter, 60-1 gram / liter, 50-1 gram / liter, 40-1 gram / liter, 30-1 gram / liter, 20-1 gram / liter, or 10-1 gram / liter.

[0181] The total amount of the auxiliary agent selected from the following groups: fatty alcohol alkoxylates, silicone adjuvants, and sulfosuccinates in the suspension concentrate or suspension emulsion formulation is preferably 100-10 g / liter, 90-15 g / liter, 80-20 g / liter, 75-20 g / liter, or 60-40 g / liter.

[0182] The suspension concentrate formulation or suspension emulsion formulation of the present invention typically has good injectability, low viscosity, and low plant toxicity.

[0183] The injectability of suspension concentrate formulations or suspension emulsion formulations can be measured according to the injectability of suspension concentrates of the CIPAC method MT 148. The International Council on Pesticide Analysis and Methods (CIPAC) is an international non-profit organization that promotes unified methods for the analysis of pesticides and physicochemical testing methods for pesticides.

[0184] The amount of product remaining in the packaging after emptying is preferably less than 15%, more preferably less than 10%, and most preferably less than 5%.

[0185] The viscosity of a suspension emulsion can be measured using a rheometer. A typical value for the viscosity of such a suspension emulsion is 100 s. -1 Less than 300 mPas, more comfortable 100s -1 less than 250 mPas, more preferably 100 s -1 less than 200 mPas, even better 100 s -1 less than 150 mPas or for another 100 seconds -1 And it is less than 100 mPas.

[0186] The present invention further relates to a spray suspension obtained by mixing water with a suspension concentrate or suspension emulsion according to the present invention. Spray suspensions are usually formed spontaneously upon mixing. The mixed weight / weight ratio of water to concentrate may range from 1000:1 to a maximum of 1:1, preferably from 400:1 to a maximum of 3:1, and more preferably from 200:1 to a maximum of 3:1. The spray suspension is preferably characterized by a weight / weight ratio of sulfur to the combined amount of all terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol of 24:1 to 2:1 or 20:1 to 12:1. Preferably, the weight / weight ratio is 6:1 to 1:1, more preferably from 5:1 to 2:1. Even more preferably, the weight / weight ratio of sulfur to limonene, preferably D-limonene, is 6:1 to 1:1, more preferably from 5:1 to 2:1.

[0187] Preparation method: The suspension concentrate formulation or suspension emulsion formulation of the present invention may be produced using methods known in the art, such as those described in Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001, or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

[0188] One method for preparing a suspension concentrate formulation or suspension emulsion formulation of the present invention is carried out by grinding crystalline sulfur in water containing a suitable wetting agent and dispersant using a bead mill known to those skilled in the art. The resulting suspension is stabilized by adding further additives such as antifreezes, defoamers, biocides, and thickeners, and optionally further additives such as buffer salts. To such a suspension, one or more terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, preferably limonene, are added by an emulsification process. The one or more selected terpenes, preferably limonene, can be emulsified directly to a suspension concentrate if the dispersant and wetting agent used in the preparation of the sulfur suspension are also suitable for emulsifying the one or more selected terpenes. Otherwise, an additional emulsifier specific to use with the one or more selected terpenes is added to the one or more selected terpenes to form an oil phase, which is then added to the sulfur suspension using shear energy. This emulsifies the oil phase containing one or more selected terpenes in a sulfur suspension.

[0189] Where appropriate, a conventional heating device may be used to prepare the mixture. For the preliminary grinding step, a mill operating on the rotor-stator principle, such as an Ultraturax homogenizer (e.g., IKA) or a toothed colloid mill (e.g., Puck), may be used. For the fine grinding step, suitable equipment may include, for example, a batch-operated bead mill (e.g., Drais) or a continuous-operated bead mill (e.g., Bachofen). The preparation process can be adapted according to the characteristics of the components used, process engineering and safety aspects, and economic reasons, and where appropriate, the preliminary grinding step or, if appropriate, the fine grinding step may be omitted.

[0190] Methods for controlling plant pathogenic fungi using the suspension concentrates or suspension emulsions described herein: The present invention provides a method for controlling plant pathogenic fungi, comprising contacting a fungus, a plant or plant part to be protected from fungal attack with a spray suspension obtained by mixing a fungicidal amount of water with a suspension concentrate or suspoemulsion described herein. Accordingly, the present invention provides a method for controlling plant pathogenic fungi, comprising a) identifying a plant or multiple plants that are infected with or at risk of being infected with at least one type of fungus, and b) contacting a fungicidal amount of water with a spray suspension obtained by mixing a fungicidal amount of water with a suspension concentrate or suspoemulsion described herein.

[0191] The suspension concentrates or ssupoemulsions and the spray suspensions prepared therefrom are suitable as effective fungicides against a broad spectrum of plant pathogenic fungi, including soilborne pathogens, particularly those from the classes Plasmodiophoromycetes, Peronosporomycetes (synonymous with Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes (synonymous with Fungi imperfecti). They can be used for crop protection as foliar fungicides, seed coating fungicides, and soil fungicides.

[0192] The suspension concentrate or suspension emulsion and the spray suspension prepared therefrom preferably contain grains, e.g., wheat, rye, barley, rye grain, oats or rice, beets, e.g., sugar beets or fodder beets, fruits, e.g., pome-like fruits (apples, pears, etc.), drupes (e.g., plums, peas, almonds, cherries) or soft fruits also called berries (strawberries, raspberries, blackberries, gooseberries, etc.), legumes, e.g., lentils, peas, alfalfa or soybeans, oil plants, e.g., rapeseed, mustard, olives, sunflowers, coconuts, cocoa beans, castor beans, oil palms, peanuts or soybeans, cucurbits, e.g., pumpkins, cucumbers or melons, fiber plants, e.g., cotton, flax, hemp or jute, citrus fruits, etc. For example, it is useful for controlling plant pathogenic fungi in various cultivated plants such as oranges, lemons, grapefruits or mandarins, vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, cucurbits or bell peppers, laurels such as avocados, cinnamon or camphor, energy and raw material plants such as corn, soybeans, rapeseed, sugarcane or oil palm, corn, tobacco, nuts, coffee, tea, bananas, grapes (table grapes and grapes for grape juice), hops, turfgrass, stevia, natural rubber plants, or ornamental and forest plants such as flowers, shrubs, broad-leaved trees or evergreen trees (conifers, eucalyptus, etc.), plant propagation materials such as seeds, and crop materials of these plants.

[0193] More preferably, the suspension concentrate or suspend emulsion and the spray suspension prepared therefrom are used to control fungi in crops such as potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee or sugarcane, fruits, grapes, ornamental plants or vegetables such as cucumbers, tomatoes, legumes or pumpkins.

[0194] The term "plant propagation material" is understood to refer to all plant reproductive parts such as seeds, as well as all plant materials capable of growth that can be used for plant propagation, such as cuttings and tubers (e.g., potatoes). Plant propagation material includes other parts of plants, including seeds, roots, fruits, tubers, bulbs, rhizomes, buds, shoots, and seedlings and young plants that are transplanted after germination or after emerging from the soil.

[0195] Preferably, treatment of plant propagation material with suspension concentrates or saspoemulsions and spray suspensions prepared therefrom is used to control fungi in cereals such as wheat, rye, barley, and oats, rice, maize, cotton, sunflower, rapeseed, soybeans, and fruits, as well as fruit trees such as apples, pears, and peaches.

[0196] According to the present invention, all of the above-mentioned cultivated plants include, but are not limited to, winter and spring varieties of grains such as wheat and barley, and rapeseed, such as winter wheat, spring wheat, and winter barley, and further include all species, subspecies, variants, varieties, and / or hybrids belonging to each cultivated plant, including dwarf, semi-dwarf, fully dwarf varieties and / or hybrids that are short in height and have thick, short stems, such as low-growing maize (also called "smart corn"), semi-dwarf wheat, and dwarf rice.

[0197] Corn, also known as Indian corn or maize (Zea mays), includes all types of maize, such as field corn and sweet corn. According to the present invention, all maize or subspecies and / or varieties of maize include, in particular, flower corn (Zea mays var. amylacea), popcorn (Zea mays var. everta), dent corn (Zea mays var. indentata), flint corn (Zea mays var. indurata), sweet corn (Zea mays var. saccharata and var. rugosa), waxy corn (Zea mays var. ceratina), amylomaize (high-amylose Zea mays varieties), pod corn or wildmaize (Zea mays var. tunicata), and variegated maize (Zea mays var. japonica).

[0198] Most soybean cultivars are classified as having indefinite or finite growth characteristics, although the wild ancestor of soybeans, Glycine soja, is indefinite (PNAS 2010, 107(19)8563-8568). Indefinite growth characteristics (maturity groups, MG00~MG4.9) are characterized by continued plant growth after flowering begins, while finite soybean varieties (MG5~MG8) are characterized by the fact that most of their plant growth is completed by the time flowering begins. According to the present invention, all soybean cultivars or varieties, in particular indefinite and finite cultivars or varieties, are included.

[0199] The term "cultivated plants" is understood to include plants that have been modified by mutagenesis or genetic engineering to confer new traits to plants or alter existing traits. Mutagenesis includes not only random mutagenesis using X-rays or mutagenic chemicals, but also targeted mutagenesis to induce mutations at specific loci in the plant genome. Targeted mutagenesis often uses oligonucleotides or proteins such as CRISPR / Cas, zinc finger nucleases, TALENs, or meganucleases. Genetic engineering typically uses recombinant DNA techniques to introduce modifications to the plant genome that are not readily obtainable in the natural environment through crossbreeding, mutagenesis, or natural recombination. Typically, one or more genes are incorporated into the plant genome to add a trait or to improve or alter an existing trait. These incorporated genes are also called transgenes, and plants containing such transgenes are called transgenetic plants. The process of plant transformation usually involves several transformation events in which the transgenes are incorporated into different genomic loci. Plants containing a specific transgene at a particular genomic locus are typically described as containing a specific “event” and referred to by the name of that event. Traits introduced or modified in plants include herbicide resistance, insect resistance, high yield, and tolerance to abiotic conditions such as drought.

[0200] Herbicide resistance can be induced using mutagenesis and genetic engineering. Plants resistant to acetolactate synthase (ALS) inhibitor herbicides through mutagenesis and breeding are available, for example, under the name Clearfield®. Herbicide resistance to oxynyl herbicides such as glyphosate, glufosinate, 2,4-D, dicamba, bromoxynil, and ioxinil, sulfonylurea herbicides, ALS inhibitors, and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors such as isoxaflutol and mesotrione can be induced using transgenes.

[0201] Transgenes that confer herbicide resistance traits include: for resistance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621, goxv247; for resistance to glufosinate: pat and bar; for resistance to 2,4-D: aad-1, aad-12; for resistance to dicamba: dmo; for resistance to oxynyl herbicides: bxn; for resistance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA; for resistance to ALS inhibitors: csr1-2; and for resistance to HPPD inhibitors: hppdPF, W336, avhppd-03.

[0202] Genetically modified maize events containing herbicide resistance genes include, but are not limited to, DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHG0JG, HCEM485, VCO-Φ1981-5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507, and TC6275. Genetically modified soybean events containing herbicide resistance genes include, but are not limited to, GTS40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, SYHTΦH2, W62, W98, FG72, and CV127. Genetically modified cotton vents containing herbicide resistance genes include, but are not limited to, 19-51a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701, MON88913, GHB119, GHB614, LLCotton25, T303-3, and T304-40. Genetic transfection canola events containing herbicide resistance genes include, for example, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1, MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2, and RF3, but do not exclude others.

[0203] The transgenes conferring insect resistance are preferably toxin genes and synthetic variants thereof from Bacillus species, such as cry1A, cry1Ab, cry1Ab-Ac, cry1Ac, cry1A.105, cry1F, cry1Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1, cry34Ab1, cry35Ab1, cry9C, vip3A(a), and vip3Aa20. Furthermore, plant-derived transgenes, such as genes encoding protease inhibitors like CpTI and pinII, can be used. A further approach involves using transgenes such as dvsnf7 to induce double-stranded RNA production within plants.

[0204] Genetically modified maize events containing genes for insecticidal proteins or double-stranded RNA include, but are not limited to, Bt10, Bt11, Bt176, MON801, MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351, MIR162, DBT418, and MZIR098. Genetically modified soybean events containing genes for insecticidal proteins include, but are not limited to, MON87701, MON87751, and DAS-81419. Genetically modified cotton events containing genes for insecticidal proteins include, but are not limited to, SGK321, MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, Event1, COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS9124, 281-24-236, 3006-210-23, GHB119, and SGK321.

[0205] By using the transgene athb17 (e.g., maize event MON87403) or bbx32 (e.g., soybean event MON87712), cultivated plants with increased yields have been produced.

[0206] Cultivated plants with modified oil content are produced using the following transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A, and fatb1-A (e.g., soybean event 260-05, MON87705, and MON87769).

[0207] Tolerance to abiotic conditions such as drought can be induced by using the transgenes cspB (maize event MON87460) and Hahb-4 (soybean event IND-ΦΦ41Φ-5).

[0208] Traits are often combined by combining genes in a transformation event or by combining different events during the breeding process, resulting in cultivated plants with accumulated traits. Preferred combinations of traits include combinations of herbicide resistance traits to different groups of herbicides, insect resistance to different types of insects, particularly lepidopteran and coleopteran insects, combinations of herbicide resistance with resistance to one or more types of insects, combinations of herbicide resistance with yield increase, and combinations of herbicide resistance with resistance to abiotic conditions.

[0209] Plants containing single or stacked traits, as well as the genes and events that confer these traits, are well known in this art. For example, detailed information on mutant or integrating genes and their respective events is available from the websites of the International Service for the Acquisition of Agri-biotech Applications (ISAAA) (http: / / www.isaaa.org / gmapprovaldatabase) and the Center for Environmental Risk Assessment (CERA) (http: / / cera-gmc.org / GMCropDatabase). Further information regarding specific events and methods for detecting them can be found in International Publication Nos. 01 / 031042, 01 / 041558, 01 / 041558, 02 / 036831, 11 / 153186, 13 / 003558 for Canola events MS1, MS8, RF3, GT73, MON88302, KK179, and in International Publication Nos. 02 / 036831, 11 / 153186, 13 / 003558 for Wata events MON1445, MON15985, MON531 (MON15985), LLCotton25, MON88913, COT102, 281-24-236, 3006-210-23, COT67B, GHB614, T304-40, GHB119, MON88701, 81910. Regarding this, see International Publication No. 02 / 034946, International Publication No. 02 / 100163, International Publication No. 02 / 100163, International Publication No. 03 / 013224, International Publication No. 04 / 072235, International Publication No. 04 / 039986, International Publication No. 05 / 103266, International Publication No. 05 / 103266, International Publication No. 06 / 128573, International Publication No. 07 / 017186, International Publication No. 08 / 122406, International Publication No. 08 / 151780, International Publication No. 12 / 134808, International Publication No. 13 / 112527, Corn Event GA21, MON810, DLL25,For TC1507, MON863, MIR604, LY038, MON88017, 3272, 59122, NK603, MIR162, MON89034, 98140, 32138, MON87460, 5307, 4114, MON87427, DAS40278, MON87411, 33121, MON87403, and MON87419, see International Publication No. 98 / 044140, US Patent Application Publication No. 02 / 102582, US Patent Application Publication No. 03 / 126634, International Publication No. 04 / 099447, and International Publication Pamphlet No. 04 / 011601, International Publication Pamphlet No. 05 / 103301, International Publication Pamphlet No. 05 / 061720, International Publication Pamphlet No. 05 / 059103, International Publication Pamphlet No. 06 / 098952, International Publication Pamphlet No. 06 / 039376, US Patent Application Publication No. 2007 / 292854 Specification, International Publication Pamphlet No. 07 / 142840, International Publication Pamphlet No. 07 / 140256, International Publication Pamphlet No. 08 / 112019, International Publication Pamphlet No. 09 / 103049, International Publication Pamphlet No. 09 / 1 For brochures No. 11263, International Publication No. 10 / 077816, International Publication No. 11 / 084621, International Publication No. 11 / 062904, International Publication No. 11 / 022469, International Publication No. 13 / 169923, International Publication No. 14 / 116854, International Publication No. 15 / 053998, International Publication No. 15 / 142571, and for potato events E12, F10, J3, J55, V11, X17, Y9, see International Publication No. 14 / 178910. Regarding the Rice Events LLRICE06, LLRICE601, and LLRICE62, see the International Publications 00 / 026345, 00 / 026356, 00 / 026345 and Soybean Event H7-1.Regarding MON89788, A2704-12, A5547-127, DP305423, DP356043, MON87701, MON87769, CV127, MON87705, DAS68416-4, MON87708, MON87712, SYHT0H2, DAS81419, DAS81419×DAS44406-6, and MON87751, see International Publication No. 04 / 074492, International Publication No. 06 / 130436, International Publication No. 06 / 108674, International Publication No. 06 / 108675, International Publication No. 08 / 054747, and Country This can be found in International Publication No. 08 / 002872, International Publication No. 09 / 064652, International Publication No. 09 / 102873, International Publication No. 10 / 080829, International Publication No. 10 / 037016, International Publication No. 11 / 066384, International Publication No. 11 / 034704, International Publication No. 12 / 051199, International Publication No. 12 / 082548, International Publication No. 13 / 016527, International Publication No. 13 / 016516, and International Publication No. 14 / 201235.

[0210] By applying suspension concentrates or ssupoemulsions and spray suspensions prepared therefrom to cultivated plants, it is possible to induce plant-specific effects, including those involving specific transgenes or events. These effects may include changes in growth behavior or changes in resistance to biological or abiotic stressors. Such effects may include, in particular, increased yield, enhanced resistance or tolerance to entomopathogens, nematode pathogens, fungal pathogens, bacterial pathogens, mycoplasma pathogens, viral pathogens, or viroid pathogens, as well as changes in early vigor, early or delayed maturation, cold tolerance or heat tolerance, and the spectrum or content of amino acids or fatty acids.

[0211] Suspension concentrates or suspend emulsions and spray suspensions prepared therefrom are particularly suitable for controlling the pathogenic factors of the following plant diseases: Albugo species (for ornamental plants, vegetables (e.g., A. candida) and sunflowers (e.g., A. tragopogonis)) Alternaria species (spp.) (white rust), vegetables (e.g., A. dauci or A. porri), rapeseed (A. brassicicola or brassicae), sugar beet (A. tenuis), fruit (e.g., A. grandis), rice, soybean, potato and tomato (e.g., A. solani, A. grandis or A. alternata), tomato (e.g., A. solani or A. alternata) and wheat (e.g., A. triticina) (Alternaria spot disease), Aphanomyces spp. related to sugar beets and vegetables, Ascochyta spp. related to grains and vegetables, for example A. tritici (anthrax) related to wheat and A. hordei related to barley, Aureobasidium zeae (synonymous with Kapatiella zeae) related to maize, Bipolaris and Drechslera spp. (Teleomorph: Cochliobolus) spp.)), for example, sesame leaf spot (D. maydis) and sooty spot (B. zeicola) affecting corn, for example, leaf spot (B. sorokiniana) affecting grains, and for example, B. oryzae affecting rice and grass (B.Oryzae), Blumeria (formerly Erysiphe) graminis (powdery mildew) affecting grains (e.g., wheat or barley), Botrytis cinerea (teleomorph: Botryotinia fuckeliana: gray mold) affecting fruits and berries (e.g., strawberries), vegetables (e.g., lettuce, carrots, celery and cabbage), Alliaceae), rapeseed, ornamental plants (e.g., B eliptica), grapes, forest plants and wheat, white spot leaf blight (B. squamosa) or gray mold (B. allii), Bremia lactucae affecting lettuce Ceratocystis species (synonymous with Ophiostoma) affecting deciduous and evergreen trees (root rot or damping-off disease), such as C. ulmi (Ulmus dulcis) affecting elm trees, maize (e.g., gray spot disease: C. zeae-maydis), rice, sugar beet (e.g., C. beticola), sugarcane, vegetables, coffee, soybeans (e.g., C. sojina or C. kikuchii), and Cercospora species affecting rice. Cladobotryum species (synonymous with Dactylium) related to mushrooms (e.g., C. mycophilum (formerly Dactylium dendroides, teleomorph: Nectria albertinii, Nectria rosella, Hypomyces rosellus)), tomatoes (e.g., C. fulvum: leaf mold), and Cladosporium species (spp.) related to grains, e.g., C. herbarum related to wheat (C.herbarum) (black spot disease), Claviceps purpurea (Claviceps) affecting cereals Cochliobolus (anamorph: Helminthosporium of Bipolaris) species (leaf spot disease) related to cereals (e.g., C. sativus, anamorph: B. sorokiniana) and rice (e.g., C. miyabeanus, anamorph: H. oryzae), cotton (e.g., C. gossypii), maize (e.g., C. graminicola: anthracnose root rot), soft fruit, potato (e.g., C. coccodes: black spot disease), legumes Colletotrichum (teleomorph: Glomerella) species (anthracnose) related to various crops (e.g., C. lindemuthianum), soybeans (e.g., C. truncatum or C. gloeosporioides), vegetables (e.g., C. lagenarium or C. capsici), fruits (e.g., C. acutatum), coffee (e.g., C. coffeeum or C. kahawae), C. gloeosporioides related to various crops, and Corticium species related to rice. spp.), for example, C. sasakii (sheath blight), Corynespora cassiicola (leaf spot) related to soybeans, cotton and ornamental plants, Cycloconium species (Cycloconium spp.), for example, C. oleaginum related to olive trees, fruit trees, grapes (for example, C. liriodendrin (C.liriodendri), teleomorph: Neonectria liriodendri (black foot disease) and Cylindrocarpon spp. related to ornamental plants (e.g., fruit tree ulcer disease or young grape wilt, teleomorph: Nectria or Neonectria spp.), Dematophora (teleomorph: Roselinia) necatrix related to soybeans (root and stem rot), Diaporthe related to soybeans spp.), for example, D. phaseolorum (seedling blight), maize, cereals, for example, barley (for example, D. teres, reticulosis) and wheat (for example, D. tritici-repentis: yellow spot), rice and turf, Dreshlera species (Helminthosporium, teleomorph: synonymous with Pyrenophora), Formitiporia (synonymous with Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora The diseases caused by chlamydospora (formerly Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum, and / or Botryosphaeria obtusa include Esca disease (canker, apoplexy) in grapes, Elsinoe spp. in pears (E. pyri), soft fruits (E. veneta: anthracnose), and grapes (E. ampelina: anthracnose), Entyloma oryzae (sooty mold) in rice, and Epicoccum spp. in wheat.)(black mold), sugar beet (E. betae), vegetables (e.g., E. pisi), cucurbitaceous plants (e.g., E. cichoracearum), cabbage, rapeseed (e.g., E. cruciferarum) Erysiphe spp. (powdery mildew), fruit trees, grapes and ornamental trees Eutypa lata (Eutypa ulcer or canker, anamorph: Cytosporina lata, Libertella brepalis) This includes species such as *Exserohilum* (synonymous with *Helminthosporium*) related to maize (e.g., *E. turcicum*), *Fusarium* (teleomorph: *Gibberella*) related to various plants (damping-off, root or stem rot), *F. graminearum* or *F. culmorum* related to grains (e.g., wheat or barley) (root rot, black spot, or red mold), *F. oxysporum* related to tomatoes, and *F. solani* (differentiated form *Glycine*, now synonymous with *F. virguliforme*) related to soybeans, which cause sudden death syndrome. Furthermore, F. tucumaniae and F. brasiliense, F. verticillioides related to maize, Gaeumannomyces graminis (damping-off disease) related to cereals (e.g., wheat or barley) and maize, Gibberella species (e.g., G. zeae) and rice (e.g., G. fujikuroi: bakanae disease) related to gibberella, Glomerella cingulata related to grapes, pears and other plants, G. gossypii related to cotton, grain stain complex disease related to rice, and Guignardia bidwelli related to grapes. Gymnosporangium species (Gymnosporangium spp.) related to Rosaceae plants and junipers, for example G. sabinae (rust disease) related to pears, Helminthosporium species (Helminthosporium spp.) related to corn, grains, potatoes and rice (synonymous with Drechslera, teleomorph: Cochliobolus), Hemileia species (H. vastatrix) related to coffee (coffee rust disease), Isariopsis clavispora (synonymous with Cladosporium vitis) related to grapes, Macrophomina phaseolina related to soybeans and cotton Phaseolina (synonymous with phaseoli) (root rot and stem rot), Microdochium (synonymous with Fusarium) nivale (pink snow mold) affecting grains (e.g., wheat or barley), Microsphaera diffusa (powdery mildew) affecting soybeans, Monilinia spp. affecting berries and other Rosaceae plants, e.g., M. laxa, M.Mycosphaerella species related to grains, bananas, soft fruits and peanuts, such as M. graminicola (anamorph: Zymoseptoria tritici, formerly Septoria tritici: Septoria spot disease) related to wheat, or M. fijiensis (Pseudocercospora fijiensis) related to bananas. Synonymous with fijiensis: black sigatoka disease) and M. musicola, M. arachidicola (M. arachidis or Cercospora arachidis) related to peanuts Peronospora spp. (downy mildew) related to plants such as arachidis (synonymous), M. berkeleyi, M. pisi related to peas, M. brassiciola related to plants of the Brassicaceae family, Peronospora species (downy mildew) related to cabbage (e.g., P. brassicae), rapeseed (e.g., P. parasitica), onion (e.g., P. destroyer), tobacco (P. tabacina), and soybean (e.g., P. manshurica), and Phakopsora pachyrizi related to soybeans. Phialophora spp., related to grapes (e.g., P. tracheiphila and P. tetraspora) and soybeans (e.g., P. gregata: stem rot), Phoma lingam (Leptosphaeria biglobosa and L.) related to rapeseed and cabbage.Phomopsis species (P. maculans, synonymous with root and stem rot), P. betae (root rot, leaf spot, and seedling blight) related to sugar beets, and P. zeae-maydis (synonymous with Phyllostica zeae) related to maize, Phomopsis species related to sunflowers, grapes (e.g., P. viticola: leaf spot), and soybeans (e.g., stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum), Physoderma maydis (brown spot) related to maize, and Phytophthora species related to various plants. Plasmodiophora brassicae (club root disease), Plasmopara species, which are associated with Plasmopara, as well as bell peppers and cucurbits (e.g., P. capsici), soybeans (e.g., P. megasperma, synonymous with P. sojae), potatoes and tomatoes (e.g., P. infestans: leaf blight), and deciduous trees (e.g., P. ramorum: sudden death of oak), cabbage, rapeseed, radish and other plants. P. viticola (grape downy mildew), for example, P. halstedii, P. spp. (powdery mildew), P. leucotricha (apple downy mildew), P. xanthii (cucurbitaceous plants), P. xanthii (rosaceae plants), P. spp. (powdery mildew), Polymyxa (grainy mildew), for example, P. graminis (barley and wheat), and P. betae (sugar beet).) and the viral diseases transmitted thereby, Pseudocercosporella herpotrichoides (synonymous with Oculimacula yallundae, O. acuformis: eye spot disease, teleomorph: Tapesia yallundae) relating to grains, such as wheat or barley, Pseudoperonospora (downy mildew) relating to various plants, such as P. cubensis relating to cucurbitaceae plants or P. humili relating to hops, and Pseudopezicula tracheiphylla relating to grapes. Puccinia (Puccinia tracheiphila) (red fireworks disease or "rotbrenner", anamorph: phialophora), a species of plant related to various plants. P. triticina (brown rust or leaf rust), P. striiformis (striped rust or yellow rust), P. hordei (dwarf rust), P. graminis (stem rust or black rust), or P. recondita (brown rust or leaf rust) on grains such as wheat, barley, or rye; P. kuehnii (orange rust) on sugarcane; P. asparagi on asparagus; and Pyrenopeziza on rapeseed. P. spp.), for example, P. brassicae, Pyrenophora (anamorph: Drechslera) tritici-repentis (yellowish-brown spot disease) related to wheat, or P. teres (net spot disease) related to barley, Pyricularia spp. related to rice, for example, P. oryzae (teleomorph: Magnaporthe grisea: rice rot disease), and P. grisea (P.Pythium species (seedling blight) (e.g., P. ultimum or P. aphanidermatum) related to grass, rice, corn, wheat, cotton, rapeseed, sunflower, soybean, sugar beet, vegetables and various other plants, P. oligandrum related to mushrooms, Ramularia species (e.g., R. collo-cygni) related to barley (Ramularia leaf spot disease, physiological leaf spot disease), R. areola related to cotton (Teleomorph: Mycosphaerella areola) Rhizoctonia species (R. beticola) related to sugar beets, cotton, rice, potatoes, grass, corn, rapeseed, potatoes, sugar beets, vegetables and various other plants, such as R. solani (root and stem rot) related to soybeans, R. solani (sheath blight) related to rice, or R. cerealis (spring blight of Rhizoctonia) related to wheat or barley, Rhizopus stolonifer (black mold, soft rot) related to strawberries, carrots, cabbage, grapes and tomatoes, and Rhynchosporium cecallis related to barley, rye and rye. S. secalis) and R. commune (burn disease), Sarocladium oryzae and S. attenuatum (pod rot) related to rice, vegetables (S. minor and S. sclerotiorum) and crops, such as rapeseed, sunflower (e.g., S. sclerotiorum) and soybeans, specifically Sclerotinia species (stem rot or white mold), soybeans, peanuts, etc. S. rolfsii (synonymous with Athelia rolfsii) is associated with vegetables, corn, grains, and ornamental plants; Septoria spp. is associated with various plants, such as S. glycines (brown spot disease) in soybeans; S. tritici (synonymous with Zymoseptoria tritici, Septoria spot disease) in wheat; and S. nodorum (synonymous with Stagonospora) (Stagonospora spot disease) in grains; and Uncinula necator (synonymous with Erysiphe) (powdery mildew, anamorph: Oidium tuckeri) in grapes. Setosphaeria spp. (black leaf blight) on corn (e.g., S. turcicum, synonymous with Helminthosporium turcicum) and turfgrass, Sphacelotheca spp. (sooty mold) on corn (e.g., S. reiliana, synonymous with Ustilago reiliana: smut), Sphacelotheca spp. (sooty mold) on sorghum and sugarcane, Sphaerotheca fuliginea (synonymous with Podosphaera xanthii: powdery mildew) on cucurbitaceous plants, Spongospora subbreranea on potatoes Stagonospora subterranea (spore-forming crusting disease) and viral diseases transmitted therefrom, Stagonospora species (S. nodorum) in grains, for example, S. nodorum in wheat.(nodorum) (Stagonospora spot disease, teleomorph: Leptosphaeria [synonymous with Phaeosphaeria] nodorum, synonymous with Septoria nodorum), Synchytrium endobioticum (potato wart disease) related to potatoes, Taphrina spp. related to peaches, e.g. T. deformans (leaf curl disease) and T. pruni (plum pocket) related to plums, Thielaviopsis spp. related to tobacco, pears, vegetables, soybeans and cotton (black root rot), e.g. T. basicola (Chalara elegans) (Synonymous with elegans), Tilletia species (Tilletia spp.) related to grains (common smut or black smut), for example, T. tritici (synonymous with T. caries, wheat smut) and T. controversa (dwarf smut) related to wheat, Trichoderma harzianum related to mushrooms, Typhula incarnata (gray snow mold) related to barley or wheat, Urocystis species (Urocystis spp.) related to rye, for example, U. occulta (sooty stripe disease), Uromyces species related to vegetables (spp.) (rust disease), for example legumes (e.g., synonymous with U. appendiculatus and U. phaseoli), sugar beets (e.g., U. betae or U. beticola), and leguminous plants (e.g., U. vignae, U. pisi, U. viciae-fabae and U. fabae), cereals (e.g., U. nuda and U. avaenae), maize (e.g., U. mydis (U.Maydis: (maize sooty mold) and Ustilago spp. (naked smut) related to sugarcane; Venturia spp. (apple scab) related to apples (e.g., V. inaequalis) and pears; Verticillium spp. (damping-off) related to various plants such as fruits and ornamental plants, grapes, soft fruits, vegetables and crops; for example, V. longisporum related to rapeseed; V. dahliae related to strawberries, rapeseed, potatoes and tomatoes; V. fungicola related to mushrooms; and Zymoseptoria tritici related to grains.

[0212] Compound I and its compositions are particularly suitable for controlling the pathogenic factors of the following plant diseases: rust diseases affecting soybeans and grains (e.g., Phakopsora pachyrhizi and P. meibomiae affecting soybeans, and Puccinia tritici and P. striiformis affecting wheat); fungal diseases affecting special crops, soybeans, rapeseed, and sunflowers (e.g., Botrytis cinerea affecting strawberries and grapes, and Sclerotinia sclerotiorum, S. minor, and S. rolfsii affecting rapeseed, sunflowers, and soybeans); and Fusarium disease affecting grains (e.g., Fusarium crumorum affecting wheat). Downy mildew affecting special crops (e.g., Plasmopara viticola affecting grapes, Phytophthora infestans affecting potatoes), powdery mildew affecting special crops and grains (e.g., Uncinula necator affecting grapes, Erysiphe spp. affecting various special crops, Blumeria graminis affecting grains), and leaf spot diseases affecting grains, soybeans, and maize (e.g., Septoria tritici and S. nodorum affecting grains, S. glycines affecting soybeans, Cercospora spp. affecting maize and soybeans).

[0213] It has been observed that populations of plant pathogenic fungi that appear to consist solely of non-resistant strains can easily develop resistance. Compounds can be applied under such conditions to prevent both the formation of resistance and the spread of resistant strains. In this regard, it is useful that these compounds exhibit strong activity even against non-resistant plant pathogenic fungi.

[0214] Various fungicidal strains have been reported for plant pathogenic fungi, including strains resistant to the corresponding proteins (e.g., one or more fungicides derived from different classes of action, observed by target site mutations in the QoI (C3, according to the FRAC convention; see www.frac.info) gene; quinone external stigmatelin-binding subsite inhibitors (QoSI, C8) and quinone internal inhibitors (QiI, C4): CytB target protein; sterol demethylation (DMI, G1): Cyp51 / Erg11; carboxylic acid amides (CAA, H5): CesA3; SDHI (C2): SdhB, SdhC and SdhD; dicarboximide (E3): Os-1 (including Bos1, Daf1, etc.); ketoreductase inhibitors (KRI, class III SBI, G3): Erg27; and oxysterol-binding protein inhibitors (OSBPI, F9): ORP1).

[0215] Preferably, the fungi to be controlled are selected from the genera Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon.

[0216] The present invention relates to a method for controlling plant pathogenic fungi selected from the genera Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon, further comprising contacting the fungus, a plant or plant part to be protected from fungal attack with a fungicidal amount of a spray suspension prepared from one of the suspension concentrates or ssupoemulsions described herein.

[0217] Preferably, at least one fungus is selected from Puccinia triticina, Erysiphe graminis, Fusarium graminearum, Sclerotinia sclerotiorum, Cercospora beticola, Cercospora sojina, Septoria tritici, Ramularia collo-cygni, or Venturia inequalis.

[0218] Preferably, the spray suspension is applied when plant pathogenic fungi are present.

[0219] Therefore, the present invention relates to a method for controlling plant pathogenic fungi, comprising the steps of: a) identifying plants or multiple plants that are infected with or at risk of being infected with at least one fungus selected from the genera Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia and Diplocarpon; b) A step of contacting a fungus, an infected or potentially infected plant or plant part with a fungicidal amount of a spray suspension prepared from a suspension concentrate or ssupoemulsion as described herein. The method includes the following: Preferably, the plants are infected with or at risk of being infected with fungi of the genera Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon. More preferably, the plant is infected with or at risk of being infected with the fungi of the following species: Puccinia triticina, Erysiphe graminis, Fusarium graminearum, Sclerotinia sclerotiorum, Cercospora beticola, Cercospora sojina, Septoria tritici, Ramularia collo-cygni, or Venturia inequalis.

[0220] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by a person ordinary in the art to which this invention pertains. [Examples]

[0221] The present invention will be described in more detail by the following examples. The following examples are illustrative and are not intended to limit the scope of the present invention.

[0222] Example 1: Preventive control of apple ulcer disease caused by Venturia inaequalis (VENTIN P1) in greenhouses. Sulfur was used as an 80% experimental water-soluble granular formulation, sweet orange essential oil as an experimental 50% emulsion formulation, and (R)-limonene (also known as (D)-limonene or (+)-limonene) as an industrial-grade substance.

[0223] The sulfur and orange essential oil preparations were diluted with water to the dosages shown in the table below.

[0224] (R)-Limonene was dissolved in a mixture of acetone and Wetol, a wetting / emulsifying agent based on ethoxylated alkylphenol, in a solvent-emulsifier ratio of 99:1 (by volume), to a total volume of 5 mL. Then, water was added to a total volume of 100 mL.

[0225] Next, this stock solution was diluted with the solvent-emulsifier-water mixture described, resulting in the dosage shown in the table below.

[0226] The aforementioned spray solution was applied to the leaves of potted apple seedlings with 5-6 leaves developed, at a spray rate of 500 l / ha. The plants were then stored for one day in a growth chamber at 19°C and a relative humidity of 40% or higher.

[0227] Subsequently, the plants were inoculated with spores of Venturia inaequalis. To ensure successful artificial inoculation, the plants were transferred to a growth chamber at 21°C with a relative humidity of approximately 70-80%. After incubation in the dark for 24 hours, the plants were grown for 20 days in a greenhouse chamber at 21°C with a relative humidity of 70-80%. The degree of fungal attack on the leaves was visually evaluated as the percentage of diseased leaf area.

[0228] Disease damage score (or diseased leaf area) was converted into efficacy.

[0229] A efficacy of 0 means that the infection level of the treated plants is the same as that of the untreated control plants, while an efficacy of 100 means that the treated plants were not infected.

[0230] The expected efficacy of the active compound mixture was determined using Colby's formula [RSColby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared with the observed efficacy.

[0231] [Table 4]

[0232] Example 2: Preventive control of apple ulcer disease caused by Venturia inaequalis (VENTIN) in field trials. Field trials were set up in Limburgerhof, Germany, using the Gala apple variety. Five plants were replicated in four plots, and eight sprayings were conducted, starting with BBCH57, with spraying intervals of 5 to 14 days.

[0233] Sulfur was used as the active substance (as) at a dose of 5 L of product per hectare (3000 g as / ha) per liter of the experimental suspension concentrate. Sweet orange essential oil was used as a commercially available 60 g as / L microemulsion formulation at a dose of 3 L of product per hectare (180 g as / ha). The products were diluted with water and applied at a total spray volume of 640 L / ha.

[0234] The incidence of attack by Venturia inaequalis resulting from natural infection was assessed by scoring a total of 200 leaves per plot for disease severity on a 6-level scale from 1 (no infection) to 6 (infected leaf area exceeding 50%), and scoring a minimum of 100 fruits per plot for disease severity on a 4-level scale from 1 (no infection) to 4 (more than 10 Venturia scabs per fruit). These values were used to calculate the disease severity per plot. At the same time, the disease incidence was reported as percentage of infected leaves.

[0235] Disease severity and disease incidence were converted to efficacy.

[0236] An efficacy of 0 means that the infection level of the treated plants is equivalent to that of the untreated control plants, and an efficacy of 100 means that the treated plants were not infected.

[0237] The expected efficacy for the active compound mixtures was determined using Colby's formula [R.S. Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared with the observed efficacy.

[0238] The synergy factor is calculated by dividing the observed efficacy by the calculated efficacy. A synergy factor greater than 1 indicates that the mixture has a synergistic effect.

[0239] [Table 5]

[0240] [Table 6]

[0241] [Table 7]

[0242] [Table 8]

[0243] Example 3: Microtest The products were mixed according to the specified ratio, pipetted into a microtiter plate (MTP), and diluted with water until the specified concentration of the active compound was reached.

[0244] Sulfur: Granulated 80% WG or suspension concentrate (600g / L) as "liquid sulfur". Orange oil: 50% emulsion (EC) or commercially available formulation at 60g / l (ME) Limonene: 50% emulsion (EC)

[0245] 1. Activity of Cercospora beticula (CERCBE) in microtiter plate testing Next, a spore suspension of Cercospora beticula in biomalt or yeast-bacto-peptone-sodium acetate aqueous solution was added.

[0246] 2. Activity of Cercospora sojina (CERCSO) in microtiter plate tests Next, a spore suspension of Cercospora sojina in biomalt, yeast-bactone-glycerin, or DOB aqueous solution was added.

[0247] The plates were placed in a chamber saturated with water vapor at a temperature of 18°C. MTP was measured at 405 nm using an absorption spectrometer for 7 days after inoculation.

[0248] The measured parameters were compared with the growth of the control variant (100%) containing no active compound and the blank value containing no fungi, and the relative growth of the pathogen for each active compound was determined in percentage units.

[0249] These percentages were converted into efficacy values.

[0250] An efficacy value of 0 means that the pathogen growth level is equivalent to that of the untreated control, and an efficacy value of 100 means that no pathogen growth occurred.

[0251] The expected efficacy for the active compound mixture was determined using Colby's formula [R.S. Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared with the observed efficacy.

[0252] [Table 9]

[0253] [Table 10]

[0254] [Table 11]

[0255] [Table 12]

[0256] Example 4: Greenhouse Each product was used as a commercially available finished formulation or an experimental formulation, and diluted with water until the specified dosage of the active compound was reached.

[0257] 1. Preventive control of brown rust disease in wheat caused by Puccinia recondita (PUCCRT P1) The first two leaves to unfold in potted wheat seedlings were sprayed with the aforementioned spray solution containing concentrated active ingredients or mixtures thereof, as described below, until it ran down. The following day, the plants were inoculated with spores of Puccinia recondita. To ensure successful artificial inoculation, the plants were moved to a humid chamber for 24 hours under shade, with a relative humidity of 95-99% and a temperature of 20-24°C. The test plants were then grown for 6 days in a greenhouse chamber at 20-24°C and a relative humidity of 65-70%. The degree of fungal attack on the leaves was visually evaluated as the percentage of diseased leaf area.

[0258] 2. Control of powdery mildew in wheat caused by Blumeria graminis f.sp. tritici (ERYSGT P1) The first fully unfolded leaves of potted wheat plants were sprayed with the aforementioned spray solution containing concentrates of the active ingredients or mixtures thereof, as indicated in the table below, until it ran down. The following day, the treated plants were inoculated with spores of Blumeria graminis f.sp. tritici (synonymous with Erysiphe garminis f.sp. tritici) by shaking heavily infected mother plants over the treated pots. After culturing in a greenhouse at 21-23°C and 40-70% relative humidity for 7 days, the degree of fungal attack on the leaves was visually evaluated as the percentage of diseased leaf area.

[0259] 3. Control of powdery mildew in grapes caused by Uncinula necator (UNCINE P1) Grape cuttings were grown in pots until they reached the 4-5 leaf stage. These plants were sprayed with the aforementioned spray solution containing concentrates of the active ingredients or mixtures thereof, as indicated in the table below, until it ran down. The following day, the treated plants were inoculated with Uncinula necator spores by shaking heavily infected mother plants over the treated pots. After incubation in a greenhouse at 21-23°C and 40-70% relative humidity for 22 days, the degree of fungal attack on the leaves was visually evaluated as the percentage of diseased leaf area.

[0260] Disease damage score (or diseased leaf area) was converted into efficacy.

[0261] A efficacy of 0 means that the infection level of the treated plants is the same as that of the untreated control plants, while an efficacy of 100 means that the treated plants were not infected.

[0262] The expected efficacy of the active compound mixture was determined using Colby's formula [RSColby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared with the observed efficacy.

[0263] [Table 13]

[0264] [Table 14]

[0265] [Table 15]

[0266] [Table 16]

[0267] Example 5: Grains in field trials Field tests on winter wheat were conducted at different locations under actual field conditions, using a randomized block method with four repeated tests. All tests were carried out in accordance with EPPO standards, namely EPPO PP 1 / 026(4), EPPO PP 1 / 135(4), EPPO PP 1 / 152(4), EPPO PP 1 / 181(4), EPPO PP 1 / 223(2), and EPPO PP 1 / 239(2).

[0268] Winter wheat or winter barley was sown in rows and grown under standard conditions with sufficient nutrients supplied.

[0269] The objective of the experiment was to confirm the efficacy of sulfur and orange oil individually compared to a mixture of sulfur and orange oil.

[0270] The following products were used in the test.

[0271] [Table 17]

[0272] The test product was applied twice at a water flow rate of 200-300 l / ha. The first application was made at crop growth stage BBCH25-33 to protect the lower leaves. The second application was made at crop growth stage BBCH37-39, when the final flag leaf appeared, to protect the upper leaves. No other compounds were applied to control pathogens.

[0273] The incidence of disease after treatment with fungicides was evaluated and assessed individually at the leaf level. Disease levels were converted to efficacy. Efficacy of 0 means that the infection level of the treated plants was equivalent to that of the untreated control plants. Efficacy of 100% means that no infection was observed in the treated plants.

[0274] The synergistic effect was evaluated using Colby's formula. Colby's formula was performed as follows: potency of A + potency of B - (A*B / 100), where A is orange oil and B is liquid sulfur. A synergistic effect is indicated when the potency evaluated for the ready mix product (mixed SE) is greater than the value calculated according to Colby's formula.

[0275] Results and conclusions (wheat diseases): In the case of Septoria, each individual compound demonstrated poor to moderate efficacy. Sulfur dosage and formulation did not have a consistent effect on efficacy. However, when combined in a novel ready-mix formulation (mixed SE), a synergistic effect was demonstrated in improving Septoria control (Tables 13-16).

[0276] [Table 18]

[0277] [Table 19]

[0278] [Table 20]

[0279] [Table 21]

[0280] In the case of brown rust disease (Puccinia triticina), sulfur compounds showed poor to moderate activity, while orange oil acted moderately. When combined in a novel ready mix formulation (mixed SE), the control of brown rust disease was improved and the overall effect was good, demonstrating a synergistic effect (Table 17).

[0281] [Table 22]

[0282] Results and conclusions (barley diseases): Each compound exhibited varying levels of activity, sometimes poor, sometimes moderate. A higher amount of sulfur tended to increase efficacy. When combined in a novel ready-mix formulation (mixed SE), more reliable efficacy against Ramularia (Ramularia collo-cygni) was observed despite lower sulfur content. A synergistic effect for improved control was demonstrated (Tables 18 and 19).

[0283] [Table 23]

[0284] [Table 24]

[0285] In the case of Rhynchosporium (Rhynchosporium secalis), high doses of sulfur showed good efficacy, while low doses were only moderate, and orange oil was poor. When combined in a novel ready-mix formulation (mixed SE), control of Rhynchosporium improved, and good results were achieved even with low doses of sulfur, demonstrating a synergistic effect (Table 20).

[0286] [Table 25]

[0287] In barley powdery mildew (Blumeria graminis f.sp.hordei), sulfur showed good efficacy, while control with orange oil was only moderate. When combined in a novel ready-mix formulation (mixed SE), the control of powdery mildew was generally superior, achieving a synergistic effect (Table 21).

[0288] [Table 26]

[0289] Example 6: greenhouse: Preventive control of powdery mildew on cucumbers caused by Sphaerotheca fuliginea (SPHRFU P7) Sulfur was used as an experimental 80% water-soluble granular formulation, and sweet orange essential oil was used as an experimental 50% emulsion formulation.

[0290] The sulfur and orange essential oil preparations were diluted with water to the dosages shown in the table below.

[0291] The aforementioned spray solution was applied to the leaves of potted cucumber seedlings (BBCH11-12) that had fully developed their first true leaves and had already emerged second leaves, but were still growing, at a spray rate of 400 l / ha. The plants were stored for 7 days in a growth chamber at 21°C and a relative humidity of 50% or higher.

[0292] Seven days later, the plants were inoculated with spores of Sphaerotheca fuliginea. To ensure successful artificial inoculation, the plants were moved again to a growth chamber at approximately 50% relative humidity and 21°C. The plants were cultured in each greenhouse chamber for 15 days, and the degree of fungal attack on the first true leaves was visually evaluated as the percentage of diseased leaves.

[0293] Disease damage score (or diseased leaf area) was converted into efficacy.

[0294] A efficacy of 0 means that the infection level of the treated plants is the same as that of the untreated control plants, while an efficacy of 100 means that the treated plants were not infected.

[0295] The expected efficacy of the active compound mixture was determined using Colby's formula [RSColby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared with the observed efficacy.

[0296] [Table 27]

Claims

1. Selected from the genera Puccinia, Erysiphe, Blumeria, Podosphera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon. A method for controlling plant pathogenic fungi, comprising contacting the fungus, a plant or plant part to be protected from fungal attack with a fungicidal amount of a mixture, wherein the mixture contains sulfur and at least one terpene selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol in a weight / weight ratio of sulfur to the combined amount of limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol of 25 to 1 to 2.

2. a) Infected with or at risk of infection with at least one fungus selected from the genera Puccinia, Erysiphe, Blumeria, Podosphera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon. The method according to claim 1, comprising the steps of: a) identifying a hazardous plant or a group of plants; and b) contacting the fungus, the plant or plant part to be protected from fungal attack with a fungicidal amount of a mixture, wherein the mixture comprises sulfur and at least one terpene selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol in a weight / weight ratio of sulfur to the combined amount of limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol of 25 to 1 to 2.

3. The method according to claim 1 or 2, wherein the mixture comprises limonene.

4. The method according to claim 3, wherein the weight / weight ratio of limonene to the combined amount of other terpenes is 90 to 1 or more.

5. The fungi to be controlled are Puccinia triticina, Puccinia striiformis, Erysiphe graminis, Septoria tritici, Cercospora beticola, Cercospora sojina, Sclerotinia sclerotiorum, Ramularia collo-cygni, and Fusarium graminearum. The method according to any one of claims 1 to 4, wherein the method is based on a species selected from graminearum, Pyrenophora terres, and Venturia inequalis.

6. a) Sulfur and, b) One or more terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, c) One or more carrier oils, d) Optionally, further constituent components A suspension concentrate or suspension emulsion formulation containing the above.

7. a) 500-700 grams / liter of sulfur, b) 50-70 grams / liter of limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol, c) One or more carrier oils in a total amount of 40 to 180 grams / liter, d) Optionally, further constituent components The suspension concentrate or suspension emulsion formulation according to claim 6, wherein the amounts of a), b), c) and optionally d) total 1 liter.

8. a) The weight / weight ratio of sulfur to the combined amount of all terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol is 24:1 to 2:1, or b) The weight / weight ratio of sulfur to the total amount of all carrier oils is 7:1 to 2:1, or c) The weight / weight ratio of the combined amount of all terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol to the combined amount of all carrier oils is 1:6 to 1:1, or d) The weight / weight ratio of sulfur to all terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol, and all carrier oils combined, is 6:1 to 2:1, or e) The weight / weight ratio of sulfur to the combined amount of all terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol, and carvacrol is 24:1 to 2:1, and the weight / weight ratio of sulfur to the combined amount of all carrier oils is 7:1 to 2:1, or f) The weight / weight ratio of sulfur to the combined amount of all terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol is 24:1 to 2:1, and the weight / weight ratio of sulfur to the combined amount of all carrier oils is 7:1 to 2:1, and the weight / weight ratio of all terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol to the combined amount of all carrier oils is 1:6 to 1:1, or g) The weight / weight ratio of sulfur to the combined amount of all terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol is 24:1 to 2:1, and the weight / weight ratio of sulfur to the combined amount of all carrier oils is 7:1 to 2:1, and the weight / weight ratio of sulfur to the combined amount of all terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol and all carrier oils is 6:1 to 2:1, or h) The weight / weight ratio of sulfur to the combined amount of all terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol is 24:1 to 2:1, and the weight / weight ratio of sulfur to the combined amount of all carrier oils is 7:1 to 2:1, and the weight / weight ratio of all terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol to the combined amount of all carrier oils is 1:6 to 1:1, and the weight / weight ratio of sulfur to the combined amount of all terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol and all carrier oils is 6:1 to 2:1, the suspension concentrate formulation or suspension emulsion formulation according to claim 6 or 7.

9. The suspension concentrate or suspension emulsion formulation according to any one of claims 6 to 8, wherein at least one selected terpene is limonene.

10. A suspension concentrate formulation or suspension emulsion formulation according to claim 1, comprising 5 to 250 g of limonene per liter.

11. A suspension concentrate formulation or suspension emulsion formulation according to claim 1 or 10, comprising a sulfur-to-limonene weight / weight ratio of 6:1 to 1:

1.

12. The suspension concentrate formulation or suspension emulsion formulation according to any one of claims 1 to 11, wherein the weight / weight ratio of limonene to the combined amount of other terpenes is 90 to 1 or more.

13. Use of the mixture according to any one of claims 1 to 5 or the suspension concentrate formulation or suspension emulsion formulation according to any one of claims 6 to 12 for controlling plant pathogenic fungi selected from the genera Puccinia, Erysiphe, Blumeria, Podosphera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia and Diplocarpon.

14. The use according to claim 13, wherein the mixture, suspension concentrate formulation, or suspension emulsion formulation contains limonene in a sulfur-to-limonene weight / weight ratio of 25:1 to 1:

1.

15. At least one fungal species that will be controlled is Puccinia triticina, Puccinia striiformis, Erysiphe graminis, Septoria tritici, Cercospora beticola, Cercospora sojina, Sclerotinia sclerotiorum, Ramularia collo-cygni, and Fusarium graminearum. The use according to claim 13 or 14, selected from *graminea*, *Pyrenophora*, and *Venturia* inequalis.

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