WO2015062353A1 - Fungicidal composition and the use thereof - Google Patents

Fungicidal composition and the use thereof Download PDF

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Publication number
WO2015062353A1
WO2015062353A1 PCT/CN2014/085369 CN2014085369W WO2015062353A1 WO 2015062353 A1 WO2015062353 A1 WO 2015062353A1 CN 2014085369 W CN2014085369 W CN 2014085369W WO 2015062353 A1 WO2015062353 A1 WO 2015062353A1
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WO
WIPO (PCT)
Prior art keywords
pyraclostrobin
calcium sulphate
copper calcium
fungicidal
active compound
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PCT/CN2014/085369
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French (fr)
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WO2015062353A9 (en
Inventor
James Timothy Bristow
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Rotam Agrochem International Company Limited
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Publication of WO2015062353A1 publication Critical patent/WO2015062353A1/en
Publication of WO2015062353A9 publication Critical patent/WO2015062353A9/en
Priority to PH12016500798A priority Critical patent/PH12016500798A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper

Definitions

  • the present invention relates to an improved fungicidal composition which comprises pyraclostrobin.
  • the composition is particularly applicable for the prevention and control of phytopathogenic fungus and bacterium.
  • crops may be infected by various fungus or bacterium leading to different kinds of diseases, while they may also be infected by various pathogenic or saprotrophic fungus (for example, fythium, phytophthora, rhizoctonia solani, fusarium and botrytis cinerea etc.) and bacterium (Erwinia carotovora etc.) in soil, resulting in seed rot, root rot and seedling death.
  • pathogenic or saprotrophic fungus for example, fythium, phytophthora, rhizoctonia solani, fusarium and botrytis cinerea etc.
  • bacterium Erwinia carotovora etc.
  • a fungicide is a natural or synthetic compound, which is used to protect the plants from the infection of fungus.
  • the present agricultural methods rely heavily on the use of fungicides. In fact, certain crops cannot grow effectively without the use of fungicides. With the use of fungicides, farmers can increase the yield and the quality of crops, leading to an enhancement of the value of crops. In most situations, the added value of crops is at least three times of the expenditure of the use of fungicides.
  • a synergistic effect is present when the activity of two or more compounds is greater than the combined activity of the compounds applied individually.
  • the present invention aims to provide an agricultural method and a composition with good efficacy against harmful fungus and bacterium, which could reduce dosage rates and/or enhance activity spectra and/or solve the problem of the management of drug resistance.
  • Pyraclostrobin is a known fungicidally active compound, with its chemical name as methyl N- ⁇ 2-[1-(4-chlorophenyl)-1 H-pyrazol-3-yloxymethyl]phenyl ⁇ (N- methoxy)carbamate, and its structure as:
  • Pyraclostrobin is a mitochondrial respiration inhibitor, with the same mechanism as those of other synthetic strobin counterparts. It inhibits mitochondrial respiration by blocking electron transfer between cytochromes b and C1 , which in turn prevents mitochondrion not to generate and provide the energy required by the cells for normal metabolism (ATP), eventually resulting in the death of cells.
  • ATP normal metabolism
  • Pyraclostrobin possesses a higher ability in inhibition of spore germination of bacterium and mycelium growth in leaves. With potential curative activity, it has a longer validity period. The said compound is rather weak in transfer around leaf apex or leaf base on a leaf and fumigation, but its transfer activity within a plant body is relatively strong. Meanwhile, as a hormonal fungicide, it can help the crops to absorb more nitrogen which is useful for their growth. In summary, with a broad applicable scope, pyraclostrobin has a protective function, curative function and systemicity, and it is also resistant to rain wash.
  • Pyraclostrobin is mainly applicable for the prevention and control of diseases on wheat, paddy rice, peanuts, grapes, vegetables, bananas, lemons, coffees, fruit trees, walnuts, tea trees, tobaccos, ornamental plants, grasses and other field crops. It can effectively prevent and control several diseases such as leaf blight, rust, powdery mildew, downy mildew, phytophthora disease, anthracnose, black spot, leaf spot, scab, brown spot and rhizoctonia rot caused by ascomycetes, basidiomycetes, deuteromycetes and oomycetes.
  • pyraclostrobin Because of its broad-spectrum fungicidal activity for preventing and controlling diseases on cereal crops, pyraclostrobin demonstrates an outstanding efficacy on the prevention and control of diseases on leaves and grains of the cereal crops, as well as increases their yields significantly. Regarding crop safety, the said compound has low toxicity, and thus it is safe to non-target organisms, and furthermore, it is also safe to the users and environment. According to the results of most of the experiments, pyraclostrobin has no phytotoxicity on crops under the recommended dosages. However, there is phytotoxicity for a very few particular species of American grapes and plums in a certain stage of their growth stages.
  • Copper calcium sulphate with a commodity name as "duoning" (_£ ⁇ ), is a non-selective protective fungicide which comprises copper ions and with low toxicity. It is equivalent to the bordeaux powder from industrialized production, but does not produce any stain on the leaves after spraying. Copper calcium sulphate acts through binding the released copper ions with several biological groups in the pathogenic fungus or bacterium in order to form the substances such as copper complexes, which in turn causes protein denaturation that helps to hinder and inhibit metabolism, resulting in the death of bacterium. The unique copper calcium compound would release fungicidal copper ions slowly in water, simultaneously with the germination and infection of the bacterium. Bacteria killing and prevention of diseases would be carried out in time.
  • Copper calcium sulphate is different from the general bordeaux mixture. Copper calcium sulphate solution is mildly acidic and could be mixed with the non-alkaline formulations with no metal ions, and thus it is convenient to use. The particles of copper calcium sulphate are small with a villous structure, and they could be distributed evenly and adhered tightly on the leaf surface of the crop after spraying. They are very resistant to rain wash. Furthermore, copper calcium sulphate comprises 12% of calcium sulphate. Apart from the prevention and control of diseases, it also has a function of calcium supplementation.
  • the present invention provides a fungicidally active composition
  • a fungicidally active composition comprising pyraclostrobin and copper calcium sulphate.
  • the said fungicidal active compound combination has very good fungicidal property against fungus and bacterium.
  • the said combination comprises pyraclostrobin and copper calcium sulphate.
  • the fungicidal activity of the fungicidal active compound combination according to the present invention is substantially higher than the sum of the activities of the individual fungicidal active compounds.
  • a synergistic effect is particularly apparent when the fungicidal active compound combination is present in the fungicidal composition according to the present invention in certain weight ratios.
  • the weight ratios of the fungicidal active compound composition in the fungicidal composition can be varied within a wide range.
  • a fungicidal active compound combination according to the present invention is characterized in that it comprises pyraclostrobin and copper calcium sulphate, wherein the weight ratio between pyraclostrobin and copper calcium sulphate may be 1 : 100 to 100: 1 , preferably 1 :50 to 50: 1 , more preferably 1 :25 to 25: 1 , even more preferred 1 :15 to 15: 1 , most preferably 1 : 10 to 10: 1 or alternatively preferred 1 :5 to 5: 1.
  • a method of preparation of fungicidal composition is to mix the fungicidal active compound combination with a filling agent and/or a surfactant.
  • the types of formulation of the said fungicidal include suspension concentrate, seed coating formulation, wettable powder, water dispersible granule, microencapsulated suspension, coated granule, granule, emulsifiable concentrate, microemulsion, oil-in-water emulsion and effervescent tablet.
  • pyraclostrobin and copper calcium sulphate of the fungicidal active compound combination are present in an amount of 5 to 90%, preferably 10 to 90 %, more preferably 20 to 90 %, even more preferred 20 to 80 %, even more preferred 30 to 80 % by weight of the fungicidal composition.
  • a method for the prevention and control of phytopathogenic bacteria is to allow the fungicidal composition to act on a bacteria and/or a habitat thereof, or on a plant, plant part, seed, soil, area, material or space.
  • a method for the prevention and control of phytopathogenic bacteria is to apply pyraclostrobin and copper calcium sulphate simultaneously, separately or consecutively.
  • the said fungicidal composition is applicable for the prevention and control of fungus and bacterium.
  • the said fungicidal active compound combination is applicable for the prevention and control of fungus and bacterium.
  • the said fungicidal composition is applicable for the prevention and control of fungus and bacterium on crops, fruits, vegetables and cash crops.
  • the said fungicidal active compound combination is applicable for the prevention and control of fungus and bacterium on crops, fruits, vegetables and cash crops.
  • the fungicidal active compound combination according to the present invention has potent microbicidal activity and can be employed for the prevention and control of unwanted microorganisms, such as fungus and bacterium, in crop protection and in the protection of materials.
  • the fungicidal active compound combination according to the present invention has very good fungicidal property against fungus, and it can be employed for the prevention and control of phytopathogenic fungus, such as
  • plasmodiophoromycetes oomycetes, chytridiomycetes, zygomycetes, ascomycetes, basidiomycetes and deuteromycetes and the like.
  • the fungicidal active compound combination according to the present invention has very good fungicidal property against bacterium, and it can be employed for the prevention and control of phytopathogenic bacterium, such as pseudomonadaceae, rhizobiaceae, enterobacteriaceae, corynebacteriaceae and streptomycetaceae.
  • phytopathogenic bacterium such as pseudomonadaceae, rhizobiaceae, enterobacteriaceae, corynebacteriaceae and streptomycetaceae.
  • Seed- and soil-borne rot and wilts, and seedling diseases caused by, for example, Phytophthora species;
  • Cankers, galls and witches' broom diseases caused by, for example, Nectria species
  • Rhizoctonia species Diseases of the plant tubers, caused by, for example, Rhizoctonia species.
  • the fungicidal active compound combination according to the present invention also shows a strong stimulating effect in plants. Accordingly, they are suitable for mobilizing the internal defences of the plant against attack by harmful microorganisms.
  • plant-stimulating (resistance-inducing) compounds can be understood as substances which are capable of stimulating the defence system of plants such that, when the treated plants are subsequently inoculated with harmful microorganisms, they display substantial resistance to these microorganisms.
  • harmful microorganisms are to be understood as phytopathogenic fungus and bacterium.
  • the fungicidal active compound combination according to the present invention can thus be used to protect plants within a certain period of time after treatment against attack by the pathogens mentioned.
  • the period of time for which this protection is achieved generally extends for 1 to 10 days, preferably 1 to 7 days, from the treatment of the plants with the fungicidal active compound combination.
  • the fungicidal active compound combination according to the present invention is particularly suitable for the prevention and control of mildew, leaf blotch diseases, fruit and blossom rots, storage diseases and secondary infections by Aspergillus IPenicillium etc.
  • the fungicidal active compound combination according to the present invention is particularly suitable for use in viticulture, fruit cultivation, crop plantation, vegetable cultivation and leguminous plant plantation.
  • the fact that the fungicidal active compound combination is well tolerated by plants at the concentrations required for the prevention and control of plant diseases, thus permitting the treatment of above-ground plant parts, of propagation stock and seeds, and of the soil.
  • the fungicidal active compound combination according to the present invention can be used for foliar application or else as seed treatment.
  • Plants are to be understood here as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants can be plants which can be obtained by conventional breeding and optimization methods, or by biotechnological and genetic engineering methods, or combinations of these methods, including the transgenic plants and including plant cultivars which can or cannot be protected by plant breeders' right.
  • Plant parts are to be understood as meaning all above-ground and below-ground parts and organs of plants, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit-bodies, fruits, seeds, roots, tubers and rhizomes.
  • Plant parts also include harvested material, as well as vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.
  • the treatment of the plants and plant parts according to the present invention with the fungicidal active compound combination is carried out directly or by action on their environment, surroundings or storage area according to customary treatment methods, for example by immersing, spraying, evaporating, atomizing, scattering, painting on and, in the case of propagation material, in particular in the case of seeds, furthermore by one- or multilayer coating.
  • the fungicidal active compound combination according to the present invention can be converted into the customary formulations, such as a suspension concentrate, seed coating formulation, wettable powder, water dispersible granule, microencapsulated suspension, coated granule, granule, emulsifiable concentrate, microemulsion, oil-in-water emulsion and effervescent tablet.
  • customary formulations such as a suspension concentrate, seed coating formulation, wettable powder, water dispersible granule, microencapsulated suspension, coated granule, granule, emulsifiable concentrate, microemulsion, oil-in-water emulsion and effervescent tablet.
  • a fungicidal composition according to the present invention comprises the fungicidal active compounds pyraclostrobin and copper calcium sulphate combination.
  • the fungicidal active compounds pyraclostrobin and copper calcium sulphate are mixed with a filling agent and/or a surfactant.
  • the term "filling agent” means the natural or synthetic organic or inorganic compound which can be mixed with the fungicidal active compound combination or used together with the fungicidal active compound combination for the ease of application onto the targets (for example, plants, crops or grasses). Therefore, the preferred filling agent is inert, which is at least agriculturally acceptable.
  • the said filling agent can be in solid or liquid form.
  • the non-active carriers used in the present invention may be in solid or liquid form.
  • Suitable solid carriers include plant powders (such as soybean flour, starch, cereal powder, wood flour, bark powder, sawdust, walnut shell flour, bran, cellulose powder, coconut shell, corncob and tobacco stalk granule, and residues after the extraction of plant essences etc.), paper, sawdust, clays (such as kaolin, bentonite and acidic porcelain clay etc.), and talc.
  • silica such as diatomaceous earth, silica sand, mica, hydrous silicic acid and calcium silicate
  • activated carbon natural minerals (pumice, attapulgite and zeolite etc.), calcined diatomaceous earth, sand, plastic carriers (such as polyethylene, polypropylene, and poly(vinylidene chloride) etc.), inorganic mineral powders (such as potassium chloride, calcium carbonate and calcium phosphate etc.), chemical fertilizers (such as ammonium sulphate, ammonium phosphate, urea and ammonium chloride etc.) , and soil fertilizers.
  • silica such as diatomaceous earth, silica sand, mica, hydrous silicic acid and calcium silicate
  • activated carbon natural minerals (pumice, attapulgite and zeolite etc.)
  • calcined diatomaceous earth sand
  • plastic carriers such as polyethylene, polypropylene, and poly(vinylidene chlor
  • Suitable liquid carriers include water, alcohols (such as methanol, ethanol, isopropanol, butanol and ethylene glycol etc.), ketones (such as acetone, methyl ethyl ketone, diisobutyl ketone, and cyclohexanone etc.), ethers (such as ethyl ether, dioxane, methyl cellulose and tetrahydrofuran etc.), aliphatic hydrocarbon (such as kerosene and mineral oil etc.), aromatic hydrocarbon (such as benzene, toluene, xylene, solvent naphtha, alkyl naphthalene, aryl chloride, chlorinated aliphatic hydrocarbon and chlorobenzene etc.), halogenated hydrocarbons, amides, sulfones, dimethyl sulfoxide, minerals and vegetable oil and animal oil etc.
  • alcohols such as methanol, ethanol, isopropanol, but
  • the following surfactants can be used: fatty alcohol- polyoxyethylene ether, polyoxyethylene alkyl aryl ether, polyoxyethylene aliphatate, phosphate of polyoxyethylated alcohol or phenol, fatty acid ester of polyol, alkylaryl sodium sulfonate, naphthalene sulfonic acid polymer, sodium ligninsulfonate, comb- shaped graft copolymer, butyl naphthalenesulfonate, alkylaryl sulfonate, sodium alkyl sulfosuccinate, lipid, fatty alcohol /ethylene oxide condensate, polyacrylate such as alkylbenzene sulfonate, and protein hydrolysate.
  • Suitable oligosaccharide material or polymers include, for example, single ethylene monomer, acrylic acid, ethylene oxide and/or prop
  • the following adjuvants could be used: xanthan gum, magnesium aluminum silicate, gelatin, starch, methyl cellulose, polyvinyl alcohol, polyvinyl acetate), natural phospholipids (such as cephalin and lecithin) and synthetic phospholipids, bentonite, and sodium ligninsulfonate, and the like.
  • Anti-freezing agents may include ethylene glycol, propanediol, glycerol and sorbitol.
  • Deflocculation agents of suspension products may include adjuvants such as naphthalene sulfonic acid polymer and polyphosphate.
  • the defoamer may include an organic silicon defoamer.
  • colorants such as inorganic pigments, for example iron oxide, titanium oxide and prussian blue; and organic pigments/dyestuffs such as alizarin dyestuffs, azo dyes and metal phthalocyanine dyes; and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • colorants such as inorganic pigments, for example iron oxide, titanium oxide and prussian blue
  • organic pigments/dyestuffs such as alizarin dyestuffs, azo dyes and metal phthalocyanine dyes
  • trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • additive components for example, protective colloids, adhesive agents, thickeners, thixotropic agents, penetrating agents, stabilizers and masking agents.
  • the said formulations according to the present invention are produced in a known manner by mixing the fungicidal active compound combination with other conventional additives.
  • the said conventional additives include conventional extenders and solvents or diluents, emulsifiers, dispersants, and/ or adhesive agents or fixing agents, wetting agents, water-proofing agents. They may also include dryers and colorants, stabilizers, pigments, defoamers, preservatives, thickener, water and other formulation adjuvants, if necessary.
  • the fungicidal composition not only includes those which are immediately available for the targets to be treated with the help of proper equipment such as spraying or dusting equipment, as well as the concentrated commercial compositions which are required to be diluted before applying to the targets.
  • the fungicidal active compound combination comprising pyraclostrobin and copper calcium sulphate according to the present invention can also be used in a mixture with other active compounds, for example, to broaden the activity spectrum or to prevent development of resistance.
  • the said other active compounds include fungicides, bactericides, attractants, insecticides, acaricides, nematicides, growth regulators, herbicides, safeners, fertilizers, or chemical components, and the like.
  • the said fungicidal composition shall be used for the prevention and control of fungal and bacterial diseases on crops.
  • the fungicidally active compounds can be applied simultaneously, or separately, or consecutively. In the case of separate application, the sequence in which the two components are applied generally has no consequence for the control outcome.
  • the fungicidally active compound combination according to the present invention can be used as such, in the form of their formulations or the use forms prepared therefrom. Application is carried out in a customary manner, for example by watering, spraying, atomizing, scattering, dusting, as well as in the form of powder, dry dressing powder, moistened dressing, wet dressing or slurry dressing for treating dry seeds, solution or soluble powder for treating seeds, soluble powder for treating soil, or by encrusting.
  • the following application rates may be applied:
  • the application rates of the active compounds are generally between 0.1 and 10000 g/ha, preferably between 10 and 1000 g/ha;
  • the application rates of the active compounds are generally between 0.001 and 50 g/kg of seed, preferably between 0.01 and 10 g/kg of seed;
  • the application rates of the active compounds are generally between 0.1 and 10000 g/ha, preferably between 1 and 5000 g/ha.
  • the above dosages are merely general exemplary dosages.
  • the personnel skilled in the art shall adjust the application rates according to the actual conditions and needs, particularly according to the nature of the plants or crops to be treated and the severity of the bacterium.
  • the fungicidally active compound combination of the present invention comprising pyraclostrobin and copper calcium sulphate, possesses a synergistic effect.
  • the fungicidal activity of the fungicidally active compound combination according to the present invention is substantially higher than the sum of the activities of the individual active compounds. In other words there is an
  • synergistic effect is particularly apparent when the active compounds are present in the fungicidal active compound combination according to the present invention in certain weight ratios, as noted above.
  • the good fungicidal activity of the fungicidal active compound combination according to the present invention is demonstrated by the examples below. Whereas the individual fungicidal active compound exhibits weaknesses in fungicidal activity, the fungicidal active compound combination displays an activity which goes beyond a simple summation of activities.
  • Example 1 A 2% Pyraclostrobin + 10% Copper calcium sulphate wettable powder was prepared from the following components:
  • the fungicidal active compounds, adjuvants and fillers were mixed according to the indicated ratios of the components and ground with an ultrafine milling machine. A 2% pyraclostrobin + 10% copper calcium sulphate wettable powder was obtained.
  • a 1 % Pyraclostrobin + 50% Copper calcium sulphate wettable powder prepared from the following components:
  • the fungicidal active compounds, adjuvants and fillers were mixed according to the indicated ratios of the components and ground with an ultrafine milling machine. A 1 % pyraclostrobin + 50% copper calcium sulphate wettable powder was obtained.
  • a 1 % Pyraclostrobin + 4% Copper calcium sulphate emulsifiable concentrate was prepared from the following components:
  • Dimethyl sulfoxide Balance 100% The above ingredients were prepared according to the indicated ratios of the components, and stirred well to form a uniform phase.
  • a 5% Pyraclostrobin + 50% Copper calcium sulphate wettable powder prepared from the following components:
  • the above ingredients were mixed according to the indicated ratios of the components, crushed and ground, and then prepared into the wettable powder.
  • a 2% Pyraclostrobin + 50% Copper calcium sulphate water dispersible granule was prepared from the following components:
  • Pyraclostrobin, dispersants, wetting agents, disintegrants and fillers were mixed well according to the indicated ratios of the components and formed into a wettable powder after airflow grinding. Copper calcium sulphate was then added and mixed well. Water was added and the resulting mixture extruded to produce a material. A 2% pyraclostrobin + 50% copper calcium sulphate water dispersible granule was obtained after dry sieving.
  • Pyraclostrobin was dissolved in methyl oleate, and polyoxyethylene castor oil was added to form an oil phase.
  • a liquid phase copper calcium sulphate suspension concentrate was obtained after grinding and high-speed shearing of copper calcium sulphate, sodium salt of naphthalene sulfonated formaldehyde condensates and water according.
  • a suspoemulsion was obtained by adding the oil phase into the liquid phase under stirring.
  • a 10% Pyraclostrobin + 10% Copper calcium sulphate wettable powder was prepared from the following components:
  • the above ingredients were mixed according to the indicated ratios of the components, crushed and ground, and prepared into the wettable powder.
  • a 40% Pyraclostrobin + 50% Copper calcium sulphate coated granule was prepared from the following components:
  • a 50% Pyraclostrobin + 10% Copper calcium sulphate wettable powder was prepared from the following components:
  • the above ingredients were mixed according to the indicated ratios, crushed and ground, and prepared into the wettable powder.
  • the active ingredients and adjuvants were mixed and ground, wetted with water, and then extruded and dried in an airflow drier.
  • a 50% Pyraclostrobin + 2% Copper calcium sulphate seed coating formulation was prepared from the following components:
  • the above ingredients were mixed according to the indicated ratios and the seed coating formulation was obtained after the grinding and/or high-speed shearing.
  • a 50% Pyraclostrobin + 5% Copper calcium sulphate microencapsulated suspension was prepared from the following components:
  • AtloxTM4913 dispersant LFH, defoamer, urea, copper calcium sulphate and water were combined, and a suspension concentrate was obtained after high-speed shearing.
  • the obtained pyraclostrobin capsule suspension was combined with the copper calcium sulphate suspension concentrate, and stirred well to obtain 50% pyraclostrobin + 5% copper calcium sulphate ZC.
  • Example 13 A 50% Pyraclostrobin + 1 % Copper calcium sulphate suspoemulsion was prepared from the following components:
  • Pyraclostrobin was dissolved in Solvesso 200, and polyoxyethylene castor oil was added to form the pyraclostrobin oil phase.
  • the suspoemulsion was obtained by adding the oil phase with pyraclostrobin to the suspension concentrate with copper calcium sulphate with stirring.
  • a 50% Pyraclostrobin + 0.5% Copper calcium sulphate emulsifiable concentrate was prepared from the following components:
  • Example 15 A 20% Pyraclostrobin + 30% Copper calcium sulphate water dispersible granule was prepared from the following components:
  • a 5% Pyraclostrobin + 30% Copper calcium sulphate wettable powder was prepared from the following components:
  • the above ingredients were mixed, crushed and ground, and prepared into the wettable powder.
  • Example 18 A 20% Pyraclostrobin + 80% Copper calcium sulphate mixture was prepared from the following components:
  • the toxicity index of each of the formulations and the co-toxicity coefficient (CTC value) of the mixed formulation were calculated according to Sun Yunpei's method.
  • CTC ⁇ 80 the composition exhibits an antagonistic effect.
  • 80 ⁇ CTC ⁇ 120 the composition exhibits an additive effect.
  • CTC ⁇ 120 the composition exhibits a synergistic effect.
  • TTI (toxicity index of formulation A * percentage of A in the mixed formulation) + (toxicity index of formulation B * percentage of B in the mixed formulation)
  • Test 1 Toxicity test of cucumber downy mildew
  • the samples were selected from cucumber seedlings in the same growing period.
  • the pots were sprayed with a potter spray tower at the pressure of 50PSI. 5ml per each pot.
  • a concentration gradient of 12 levels was prepared for each formulation. Inoculation was carried out 24 hours after the treatment of the formulations.
  • the conidiums from the leaves with cucumber downy mildew collected from a field was spread evenly on the cucumber seedlings, and then the cucumber seedlings were put in the green house for culturing.
  • CTC co-toxicity coefficient
  • Test 2 Toxicity test of banana black spot
  • the natural inoculation method of bacterium of banana black spot in the orchard was employed.
  • the samples were selected from the bananas with their buds just being cut off, and being smooth in surface and with no black spots.
  • Testing formulations and comparison formulations were prepared in liquid form according to a range of concentrations and sprayed evenly on the surfaces of the bananas.
  • the disease condition of the bananas was studied 25 days after the treatment.
  • the disease index was studied according to the pathological grading standard of banana, the prevention and control efficacy was determined, and the generalized least square method was applied to calculate the half maximal effective
  • Test 3 Toxicity test of potato early blight
  • the samples were selected from the potato seedlings in the same growing period. 3 pots of testing seedlings were used for each treatment. The pots were sprayed with a potter spray tower at the pressure of 50PSI. 5ml per each pot. A concentration gradient of 12 levels was prepared for each formulation. Inoculation was carried out 24 hours after the treatment of the formulations. The conidiums from the leaves with potato early blight (collected from the field) was spread evenly on the potato seedlings, and the potato seedlings were then put in the green house for culturing.
  • the expected activity for a given combination of two active compounds can be calculated in accordance with Colby's formula (refer to S.R. Colby,
  • X denotes the activity when using active compound A at an application rate of m g/ha or in a concentration of m ppm;
  • Y denotes the activity when using active compound B at an application rate of n g/ha or in a concentration of n ppm;
  • E denotes the activity when using active compounds A and B at application rates of m and n g/ha or in concentration of m and n ppm;
  • the present invention is illustrated by the following biological testing examples.
  • the present invention is not, however, limited to the following examples.
  • the leaves of the cucumber seedlings in pots were sprayed with the suspension concentrate in a range of concentrations of the active compounds, as indicated in Table 4.
  • the next day, the treated plants were inoculated with a spore suspension of cucumber downy mildew.
  • the pots were then allowed to stand for 24 hours in a room at 20-22°C and with high humidity (90-95%). During this period, the spores
  • Treatments were replicated four times.
  • the pots were arranged in groups randomly with 3 banana trees in a small group.
  • the application time was from September to
  • the spray volume was about 100kg/667m 2 .
  • the whole fruit trees were

Abstract

A fungicidal composition comprising pyraclostrobin and copper calcium sulphate exhibits synergy and is useful in the control of fungus and bacterium at a locus. The combination is particularly applicable for the prevention and control of phytopathogenic fungus and bacterium.

Description

FUNGICIDAL COMPOSITION AND THE USE THEREOF
The present invention relates to an improved fungicidal composition which comprises pyraclostrobin. The composition is particularly applicable for the prevention and control of phytopathogenic fungus and bacterium.
In the production of horticultural crops and dry farming, crops may be infected by various fungus or bacterium leading to different kinds of diseases, while they may also be infected by various pathogenic or saprotrophic fungus (for example, fythium, phytophthora, rhizoctonia solani, fusarium and botrytis cinerea etc.) and bacterium (Erwinia carotovora etc.) in soil, resulting in seed rot, root rot and seedling death.
A fungicide is a natural or synthetic compound, which is used to protect the plants from the infection of fungus. The present agricultural methods rely heavily on the use of fungicides. In fact, certain crops cannot grow effectively without the use of fungicides. With the use of fungicides, farmers can increase the yield and the quality of crops, leading to an enhancement of the value of crops. In most situations, the added value of crops is at least three times of the expenditure of the use of fungicides.
However, there is no fungicide which can be applied in all situations. Also, repeated usage of a single fungicide generates resistance to that kind of fungicide or any other related types. Therefore, research has been carried out to produce safer fungicides and fungicidal compositions with higher performance, lower cost, less required dosage and easy to be used.
A synergistic effect is present when the activity of two or more compounds is greater than the combined activity of the compounds applied individually.
The present invention aims to provide an agricultural method and a composition with good efficacy against harmful fungus and bacterium, which could reduce dosage rates and/or enhance activity spectra and/or solve the problem of the management of drug resistance.
Pyraclostrobin is a known fungicidally active compound, with its chemical name as methyl N-{2-[1-(4-chlorophenyl)-1 H-pyrazol-3-yloxymethyl]phenyl}(N- methoxy)carbamate, and its structure as:
Figure imgf000003_0001
Pyraclostrobin is a mitochondrial respiration inhibitor, with the same mechanism as those of other synthetic strobin counterparts. It inhibits mitochondrial respiration by blocking electron transfer between cytochromes b and C1 , which in turn prevents mitochondrion not to generate and provide the energy required by the cells for normal metabolism (ATP), eventually resulting in the death of cells.
Pyraclostrobin possesses a higher ability in inhibition of spore germination of bacterium and mycelium growth in leaves. With potential curative activity, it has a longer validity period. The said compound is rather weak in transfer around leaf apex or leaf base on a leaf and fumigation, but its transfer activity within a plant body is relatively strong. Meanwhile, as a hormonal fungicide, it can help the crops to absorb more nitrogen which is useful for their growth. In summary, with a broad applicable scope, pyraclostrobin has a protective function, curative function and systemicity, and it is also resistant to rain wash.
Pyraclostrobin is mainly applicable for the prevention and control of diseases on wheat, paddy rice, peanuts, grapes, vegetables, bananas, lemons, coffees, fruit trees, walnuts, tea trees, tobaccos, ornamental plants, grasses and other field crops. It can effectively prevent and control several diseases such as leaf blight, rust, powdery mildew, downy mildew, phytophthora disease, anthracnose, black spot, leaf spot, scab, brown spot and rhizoctonia rot caused by ascomycetes, basidiomycetes, deuteromycetes and oomycetes. Because of its broad-spectrum fungicidal activity for preventing and controlling diseases on cereal crops, pyraclostrobin demonstrates an outstanding efficacy on the prevention and control of diseases on leaves and grains of the cereal crops, as well as increases their yields significantly. Regarding crop safety, the said compound has low toxicity, and thus it is safe to non-target organisms, and furthermore, it is also safe to the users and environment. According to the results of most of the experiments, pyraclostrobin has no phytotoxicity on crops under the recommended dosages. However, there is phytotoxicity for a very few particular species of American grapes and plums in a certain stage of their growth stages. Since the environmental and economic requirements imposed on modern-day fungicides are continuously increasing, with regard, for example, to the activity spectra, toxicity, selectivity, application rate, formation of residues, and feasibility of the production of beneficial formulations, and since, furthermore, there may be problems, for example, with resistances, a constant task is to develop new fungicides which in some areas at least have advantages over their known counterparts.
Accordingly, there is a need for an improved composition comprising pyraclostrobin.
Copper calcium sulphate, with a commodity name as "duoning" (_£τ), is a non-selective protective fungicide which comprises copper ions and with low toxicity. It is equivalent to the bordeaux powder from industrialized production, but does not produce any stain on the leaves after spraying. Copper calcium sulphate acts through binding the released copper ions with several biological groups in the pathogenic fungus or bacterium in order to form the substances such as copper complexes, which in turn causes protein denaturation that helps to hinder and inhibit metabolism, resulting in the death of bacterium. The unique copper calcium compound would release fungicidal copper ions slowly in water, simultaneously with the germination and infection of the bacterium. Bacteria killing and prevention of diseases would be carried out in time. The said compound is effective in the prevention and control of both fungal and bacterial diseases. Copper calcium sulphate is different from the general bordeaux mixture. Copper calcium sulphate solution is mildly acidic and could be mixed with the non-alkaline formulations with no metal ions, and thus it is convenient to use. The particles of copper calcium sulphate are small with a villous structure, and they could be distributed evenly and adhered tightly on the leaf surface of the crop after spraying. They are very resistant to rain wash. Furthermore, copper calcium sulphate comprises 12% of calcium sulphate. Apart from the prevention and control of diseases, it also has a function of calcium supplementation.
Due to its broad spectrum, copper calcium sulphate fungicide, copper calcium sulphate would not easily induce resistance on pathogenic fungus. It demonstrates good efficacy on all fungal and bacterial diseases. It can be widely applied on the prevention and control of various fungal and bacterial diseases on several fruit trees, vegetables and cash crops which are not sensitive to copper ions, for example, stem diseases on several deciduous fruit trees; marssonina leaf spot of apple; canker, scab and anthracnose of citrus; tobacco wildfire disease; downy mildew, anthracnose, marssonina leaf spot and anthracnose of grape; rust, ring spot, anthracnose and marssonina leaf spot of jujube; black spot and marssonina leaf spot of pear tree; stem rot (fythium stem base rot) and ginger blast of ginger; root rot and soft rot of garlic; late blight disease of potato, as well as phytophthora disease, damping-off, rhizoctonia rot, downy mildew, late blight disease, fungal leaf spot and bacterial leaf spot and the like.
Surprisingly, it has been found that a combination of pyraclostrobin and copper calcium sulphate exhibits a very high activity towards fungi and bacteria. In particular, it has been found that the combination of pyraclostrobin and copper calcium sulphate exhibits a syntergistic activity.
Accordingly, the present invention provides a fungicidally active composition comprising pyraclostrobin and copper calcium sulphate.
It is found that the said fungicidal active compound combination has very good fungicidal property against fungus and bacterium. The said combination comprises pyraclostrobin and copper calcium sulphate.
Surprisingly, the fungicidal activity of the fungicidal active compound combination according to the present invention is substantially higher than the sum of the activities of the individual fungicidal active compounds.
A synergistic effect is particularly apparent when the fungicidal active compound combination is present in the fungicidal composition according to the present invention in certain weight ratios. However, the weight ratios of the fungicidal active compound composition in the fungicidal composition can be varied within a wide range.
A fungicidal active compound combination according to the present invention is characterized in that it comprises pyraclostrobin and copper calcium sulphate, wherein the weight ratio between pyraclostrobin and copper calcium sulphate may be 1 : 100 to 100: 1 , preferably 1 :50 to 50: 1 , more preferably 1 :25 to 25: 1 , even more preferred 1 :15 to 15: 1 , most preferably 1 : 10 to 10: 1 or alternatively preferred 1 :5 to 5: 1.
A method of preparation of fungicidal composition is to mix the fungicidal active compound combination with a filling agent and/or a surfactant.
The types of formulation of the said fungicidal include suspension concentrate, seed coating formulation, wettable powder, water dispersible granule, microencapsulated suspension, coated granule, granule, emulsifiable concentrate, microemulsion, oil-in-water emulsion and effervescent tablet.
In the said fungicidal composition, pyraclostrobin and copper calcium sulphate of the fungicidal active compound combination are present in an amount of 5 to 90%, preferably 10 to 90 %, more preferably 20 to 90 %, even more preferred 20 to 80 %, even more preferred 30 to 80 % by weight of the fungicidal composition.
A method for the prevention and control of phytopathogenic bacteria is to allow the fungicidal composition to act on a bacteria and/or a habitat thereof, or on a plant, plant part, seed, soil, area, material or space.
A method for the prevention and control of phytopathogenic bacteria is to apply pyraclostrobin and copper calcium sulphate simultaneously, separately or consecutively.
The said fungicidal composition is applicable for the prevention and control of fungus and bacterium. The said fungicidal active compound combination is applicable for the prevention and control of fungus and bacterium.
The said fungicidal composition is applicable for the prevention and control of fungus and bacterium on crops, fruits, vegetables and cash crops. The said fungicidal active compound combination is applicable for the prevention and control of fungus and bacterium on crops, fruits, vegetables and cash crops.
The fungicidal active compound combination according to the present invention has potent microbicidal activity and can be employed for the prevention and control of unwanted microorganisms, such as fungus and bacterium, in crop protection and in the protection of materials.
The fungicidal active compound combination according to the present invention has very good fungicidal property against fungus, and it can be employed for the prevention and control of phytopathogenic fungus, such as
plasmodiophoromycetes, oomycetes, chytridiomycetes, zygomycetes, ascomycetes, basidiomycetes and deuteromycetes and the like.
The fungicidal active compound combination according to the present invention has very good fungicidal property against bacterium, and it can be employed for the prevention and control of phytopathogenic bacterium, such as pseudomonadaceae, rhizobiaceae, enterobacteriaceae, corynebacteriaceae and streptomycetaceae. Some pathogens causing fungal and bacterial diseases which come under the generic names listed above may be mentioned as examples, but not by way of limitation:
Diseases caused by powdery mildew pathogens, such as, Blumeria species; Diseases caused by rust pathogens, such as, Gymnosporangium species;
Diseases caused by pathogens from Oomycetes such as, peronospora species;
Diseases caused by leaf spot and leaf wilt pathogens, such as, Alternaria species;
Root and stem diseases caused by, for example, Fusarium species;
Spadix and panicle diseases, caused by, for example, Alternaria species;
Diseases caused by smut pathogens, such as, Ustilago species;
Fruit rots caused by, for example, Penicillium species;
Seed- and soil-borne rot and wilts, and seedling diseases, caused by, for example, Phytophthora species;
Wilts caused by, for example, Monilinia species;
Deformations of leaves, flowers and fruits, caused by, for example, Taphrina species;
Cankers, galls and witches' broom diseases, caused by, for example, Nectria species;
Degenerative diseases of woody species, caused by, for example, esca species;
Diseases of inflorescences and seeds, caused by, for example, botrytis species;
Diseases of the plant tubers, caused by, for example, Rhizoctonia species.
The fungicidal active compound combination according to the present invention also shows a strong stimulating effect in plants. Accordingly, they are suitable for mobilizing the internal defences of the plant against attack by harmful microorganisms.
In the present context, plant-stimulating (resistance-inducing) compounds can be understood as substances which are capable of stimulating the defence system of plants such that, when the treated plants are subsequently inoculated with harmful microorganisms, they display substantial resistance to these microorganisms. In the present invention, harmful microorganisms are to be understood as phytopathogenic fungus and bacterium. The fungicidal active compound combination according to the present invention can thus be used to protect plants within a certain period of time after treatment against attack by the pathogens mentioned. The period of time for which this protection is achieved generally extends for 1 to 10 days, preferably 1 to 7 days, from the treatment of the plants with the fungicidal active compound combination.
The fungicidal active compound combination according to the present invention is particularly suitable for the prevention and control of mildew, leaf blotch diseases, fruit and blossom rots, storage diseases and secondary infections by Aspergillus IPenicillium etc.
The fungicidal active compound combination according to the present invention is particularly suitable for use in viticulture, fruit cultivation, crop plantation, vegetable cultivation and leguminous plant plantation.
The fact that the fungicidal active compound combination is well tolerated by plants at the concentrations required for the prevention and control of plant diseases, thus permitting the treatment of above-ground plant parts, of propagation stock and seeds, and of the soil. The fungicidal active compound combination according to the present invention can be used for foliar application or else as seed treatment.
According to the present invention, it is possible to treat all plants and plant parts. Plants are to be understood here as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods, or by biotechnological and genetic engineering methods, or combinations of these methods, including the transgenic plants and including plant cultivars which can or cannot be protected by plant breeders' right. Plant parts are to be understood as meaning all above-ground and below-ground parts and organs of plants, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit-bodies, fruits, seeds, roots, tubers and rhizomes. Plant parts also include harvested material, as well as vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.
The treatment of the plants and plant parts according to the present invention with the fungicidal active compound combination is carried out directly or by action on their environment, surroundings or storage area according to customary treatment methods, for example by immersing, spraying, evaporating, atomizing, scattering, painting on and, in the case of propagation material, in particular in the case of seeds, furthermore by one- or multilayer coating.
The fungicidal active compound combination according to the present invention can be converted into the customary formulations, such as a suspension concentrate, seed coating formulation, wettable powder, water dispersible granule, microencapsulated suspension, coated granule, granule, emulsifiable concentrate, microemulsion, oil-in-water emulsion and effervescent tablet.
A fungicidal composition according to the present invention comprises the fungicidal active compounds pyraclostrobin and copper calcium sulphate combination. In the said fungicidal composition, the fungicidal active compounds pyraclostrobin and copper calcium sulphate are mixed with a filling agent and/or a surfactant.
According to the present invention, the term "filling agent" means the natural or synthetic organic or inorganic compound which can be mixed with the fungicidal active compound combination or used together with the fungicidal active compound combination for the ease of application onto the targets (for example, plants, crops or grasses). Therefore, the preferred filling agent is inert, which is at least agriculturally acceptable. The said filling agent can be in solid or liquid form.
The non-active carriers used in the present invention may be in solid or liquid form. Suitable solid carriers include plant powders (such as soybean flour, starch, cereal powder, wood flour, bark powder, sawdust, walnut shell flour, bran, cellulose powder, coconut shell, corncob and tobacco stalk granule, and residues after the extraction of plant essences etc.), paper, sawdust, clays (such as kaolin, bentonite and acidic porcelain clay etc.), and talc. The following substances can be used separately or used in mixture: silica (such as diatomaceous earth, silica sand, mica, hydrous silicic acid and calcium silicate), activated carbon, natural minerals (pumice, attapulgite and zeolite etc.), calcined diatomaceous earth, sand, plastic carriers (such as polyethylene, polypropylene, and poly(vinylidene chloride) etc.), inorganic mineral powders (such as potassium chloride, calcium carbonate and calcium phosphate etc.), chemical fertilizers (such as ammonium sulphate, ammonium phosphate, urea and ammonium chloride etc.) , and soil fertilizers.
Suitable liquid carriers include water, alcohols (such as methanol, ethanol, isopropanol, butanol and ethylene glycol etc.), ketones (such as acetone, methyl ethyl ketone, diisobutyl ketone, and cyclohexanone etc.), ethers (such as ethyl ether, dioxane, methyl cellulose and tetrahydrofuran etc.), aliphatic hydrocarbon (such as kerosene and mineral oil etc.), aromatic hydrocarbon (such as benzene, toluene, xylene, solvent naphtha, alkyl naphthalene, aryl chloride, chlorinated aliphatic hydrocarbon and chlorobenzene etc.), halogenated hydrocarbons, amides, sulfones, dimethyl sulfoxide, minerals and vegetable oil and animal oil etc.
For the purpose of emulsification, dispersion, dissolving and/ or wetting of the active compounds, the following surfactants can be used: fatty alcohol- polyoxyethylene ether, polyoxyethylene alkyl aryl ether, polyoxyethylene aliphatate, phosphate of polyoxyethylated alcohol or phenol, fatty acid ester of polyol, alkylaryl sodium sulfonate, naphthalene sulfonic acid polymer, sodium ligninsulfonate, comb- shaped graft copolymer, butyl naphthalenesulfonate, alkylaryl sulfonate, sodium alkyl sulfosuccinate, lipid, fatty alcohol /ethylene oxide condensate, polyacrylate such as alkylbenzene sulfonate, and protein hydrolysate. Suitable oligosaccharide material or polymers include, for example, single ethylene monomer, acrylic acid, ethylene oxide and/or propylene oxide (EO and/or PO), or their combination with polyol or polyamine.
For the purpose of stabilizing the dispersion of active compounds, and/or adhesion and/or combination of active compounds, the following adjuvants could be used: xanthan gum, magnesium aluminum silicate, gelatin, starch, methyl cellulose, polyvinyl alcohol, polyvinyl acetate), natural phospholipids (such as cephalin and lecithin) and synthetic phospholipids, bentonite, and sodium ligninsulfonate, and the like.
Anti-freezing agents may include ethylene glycol, propanediol, glycerol and sorbitol.
Deflocculation agents of suspension products may include adjuvants such as naphthalene sulfonic acid polymer and polyphosphate.
The defoamer may include an organic silicon defoamer.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and prussian blue; and organic pigments/dyestuffs such as alizarin dyestuffs, azo dyes and metal phthalocyanine dyes; and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. Optionally, it may also include other additive components, for example, protective colloids, adhesive agents, thickeners, thixotropic agents, penetrating agents, stabilizers and masking agents.
The said formulations according to the present invention are produced in a known manner by mixing the fungicidal active compound combination with other conventional additives. The said conventional additives include conventional extenders and solvents or diluents, emulsifiers, dispersants, and/ or adhesive agents or fixing agents, wetting agents, water-proofing agents. They may also include dryers and colorants, stabilizers, pigments, defoamers, preservatives, thickener, water and other formulation adjuvants, if necessary.
The fungicidal composition not only includes those which are immediately available for the targets to be treated with the help of proper equipment such as spraying or dusting equipment, as well as the concentrated commercial compositions which are required to be diluted before applying to the targets.
The fungicidal active compound combination comprising pyraclostrobin and copper calcium sulphate according to the present invention can also be used in a mixture with other active compounds, for example, to broaden the activity spectrum or to prevent development of resistance. The said other active compounds include fungicides, bactericides, attractants, insecticides, acaricides, nematicides, growth regulators, herbicides, safeners, fertilizers, or chemical components, and the like.
As a further aspect of the present invention, the said fungicidal composition shall be used for the prevention and control of fungal and bacterial diseases on crops.
The fungicidally active compounds, pyraclostrobin and copper calcium sulphate, can be applied simultaneously, or separately, or consecutively. In the case of separate application, the sequence in which the two components are applied generally has no consequence for the control outcome.
The fungicidally active compound combination according to the present invention can be used as such, in the form of their formulations or the use forms prepared therefrom. Application is carried out in a customary manner, for example by watering, spraying, atomizing, scattering, dusting, as well as in the form of powder, dry dressing powder, moistened dressing, wet dressing or slurry dressing for treating dry seeds, solution or soluble powder for treating seeds, soluble powder for treating soil, or by encrusting. When using the fungicidally active compound combination according to the present invention or the fungicide composition according to the present invention the following application rates may be applied:
For the treatment of plant parts, the application rates of the active compounds are generally between 0.1 and 10000 g/ha, preferably between 10 and 1000 g/ha;
For seed treatment, the application rates of the active compounds are generally between 0.001 and 50 g/kg of seed, preferably between 0.01 and 10 g/kg of seed;
For the treatment of the soil, the application rates of the active compounds are generally between 0.1 and 10000 g/ha, preferably between 1 and 5000 g/ha.
The above dosages are merely general exemplary dosages. The personnel skilled in the art shall adjust the application rates according to the actual conditions and needs, particularly according to the nature of the plants or crops to be treated and the severity of the bacterium.
The fungicidally active compound combination of the present invention, comprising pyraclostrobin and copper calcium sulphate, possesses a synergistic effect. The fungicidal activity of the fungicidally active compound combination according to the present invention is substantially higher than the sum of the activities of the individual active compounds. In other words there is an
unforeseeable, true synergistic effect and not merely a supplementation of activities. A synergistic effect is particularly apparent when the active compounds are present in the fungicidal active compound combination according to the present invention in certain weight ratios, as noted above.
The good fungicidal activity of the fungicidal active compound combination according to the present invention is demonstrated by the examples below. Whereas the individual fungicidal active compound exhibits weaknesses in fungicidal activity, the fungicidal active compound combination displays an activity which goes beyond a simple summation of activities.
The following examples are presented for illustration purposes only.
Percentages indicated in the examples are weight %, unless otherwise indicated.
EXAMPLES
Example 1 A 2% Pyraclostrobin + 10% Copper calcium sulphate wettable powder was prepared from the following components:
Pyraclostrobin 2%
Copper calcium sulphate 10%
Sodium dodecyl sulfate 10%
Sodium ligninsulfonate 5%
White carbon black 10%
Kaolin Balance to 100%
The fungicidal active compounds, adjuvants and fillers were mixed according to the indicated ratios of the components and ground with an ultrafine milling machine. A 2% pyraclostrobin + 10% copper calcium sulphate wettable powder was obtained.
Example 2
A 1 % Pyraclostrobin + 50% Copper calcium sulphate wettable powder prepared from the following components:
Pyraclostrobin 1 %
Copper calcium sulphate 50%
Calcium dodecybenzene sulfonate 1 %
Sodium ligninsulfonate 2%
Sucrose Balance to 100%
The fungicidal active compounds, adjuvants and fillers were mixed according to the indicated ratios of the components and ground with an ultrafine milling machine. A 1 % pyraclostrobin + 50% copper calcium sulphate wettable powder was obtained.
Example 3
A 1 % Pyraclostrobin + 4% Copper calcium sulphate emulsifiable concentrate was prepared from the following components:
Pyraclostrobin 1 %
Copper calcium sulphate 4%
Polyoxyethylene castor oil 5%
Calcium dodecybenzene sulfonate 3%
Dimethyl sulfoxide Balance to 100% The above ingredients were prepared according to the indicated ratios of the components, and stirred well to form a uniform phase.
Example 4
A 5% Pyraclostrobin + 50% Copper calcium sulphate wettable powder prepared from the following components:
Pyraclostrobin 5%
Copper calcium sulphate 50%
Sodium dodecyl sulfate 10%
Sodium ligninsulfonate 5%
White carbon black 10%
Kaolin Balance to 100%
The above ingredients were mixed according to the indicated ratios of the components, crushed and ground, and then prepared into the wettable powder.
Example 5
A 2% Pyraclostrobin + 50% Copper calcium sulphate water dispersible granule was prepared from the following components:
Pyraclostrobin 2%
Copper calcium sulphate 50%
Modified calcium lignosulphonate 5%
Sodium dodecyl sulfate 5%
Urea 5%
Kaolin Balance to 100%
Pyraclostrobin, dispersants, wetting agents, disintegrants and fillers were mixed well according to the indicated ratios of the components and formed into a wettable powder after airflow grinding. Copper calcium sulphate was then added and mixed well. Water was added and the resulting mixture extruded to produce a material. A 2% pyraclostrobin + 50% copper calcium sulphate water dispersible granule was obtained after dry sieving.
Example 6
A 0.5% Pyraclostrobin + 50% Copper calcium sulphate suspoemulsion was prepared from the following components: Oil phase:
Pyraclostrobin 0.5% Methyl oleate 10% Polyoxyethylene castor oil 5% Liquid phase:
Copper calcium sulphate 50% Sodium salt of naphthalene sulfonated formaldehyde condensates 1 % Water Balance to 100%
Pyraclostrobin was dissolved in methyl oleate, and polyoxyethylene castor oil was added to form an oil phase. A liquid phase copper calcium sulphate suspension concentrate was obtained after grinding and high-speed shearing of copper calcium sulphate, sodium salt of naphthalene sulfonated formaldehyde condensates and water according. A suspoemulsion was obtained by adding the oil phase into the liquid phase under stirring.
Example 7
A 10% Pyraclostrobin + 10% Copper calcium sulphate wettable powder was prepared from the following components:
Pyraclostrobin 10%
Copper calcium sulphate 10%
Sodium ligninsulfonate 1 %
Sodium lauryl sulfate 2%
Highly dispersed silicic acid 1 %
Kaolin Balance to 100%
The above ingredients were mixed according to the indicated ratios of the components, crushed and ground, and prepared into the wettable powder.
Example 8
A 40% Pyraclostrobin + 50% Copper calcium sulphate coated granule was prepared from the following components:
Pyraclostrobin 40%
Copper calcium sulphate 50%
Polyethylene glycol 3%
Highly dispersed silicic acid 1 % Calcium carbonate Balance to 100%
In a mixer, the ground fungicidal active compounds were coated evenly on the carrier wetted by polyethylene glycol to obtain the dust-free coated granule. Example 9
A 50% Pyraclostrobin + 10% Copper calcium sulphate wettable powder was prepared from the following components:
Pyraclostrobin 50%
Copper calcium sulphate 10%
Sodium dodecyl sulfate 1 %
Sodium ligninsulfonate 1 %
Kaolin Balance to 100%
The above ingredients were mixed according to the indicated ratios, crushed and ground, and prepared into the wettable powder.
Example 10
A 20% Pyraclostrobin + 60% Copper calcium sulphate granule was prepared from the following components:
Pyraclostrobin 20%
Copper calcium sulphate 60%
Sodium ligninsulfonate 4%
Carboxymethyl cellulose 2%
Kaolin Balance to 100%
The active ingredients and adjuvants were mixed and ground, wetted with water, and then extruded and dried in an airflow drier.
Example 11
A 50% Pyraclostrobin + 2% Copper calcium sulphate seed coating formulation was prepared from the following components:
Pyraclostrobin 50%
Copper calcium sulphate 2%
Disodium alkyl polyoxyethylene sulfosuccinate 10%
Modified calcium lignosulphonate 5%
Xanthan gum 1 % Bentonite 1 %
Glycerol 5%
PVP-K30 1 %
Water Balance to 100%
The above ingredients were mixed according to the indicated ratios and the seed coating formulation was obtained after the grinding and/or high-speed shearing.
Example 12
A 50% Pyraclostrobin + 5% Copper calcium sulphate microencapsulated suspension was prepared from the following components:
Atlox™4913 4%
Citric acid 0.05%
Catalyst 0.1 %
Water 13%
Copper calcium sulphate 5%
PAPI™ 1.35%
Solvesso™200 10%
Atlox™4913 16%
Dispersant LFH 0.3%
Defoamer 0.16%
Urea 8.4%
Pyraclostrobin 50%
Water Balance to 100%
An oil phase formed by PAPI , pyraclostrobin and Solvesso 200 was added to the liquid solution having Atlox™4913 with stirring to form an emulsion. The mixture was heated and kept with the addition of the catalyst at 50°C for 2 hours. A pyraclostrobin capsule suspension was obtained after the cooling of the mixture.
Atlox™4913, dispersant LFH, defoamer, urea, copper calcium sulphate and water were combined, and a suspension concentrate was obtained after high-speed shearing.
The obtained pyraclostrobin capsule suspension was combined with the copper calcium sulphate suspension concentrate, and stirred well to obtain 50% pyraclostrobin + 5% copper calcium sulphate ZC.
Example 13 A 50% Pyraclostrobin + 1 % Copper calcium sulphate suspoemulsion was prepared from the following components:
Pyraclostrobin 50%
Copper calcium sulphate 1 %
SOLVESSO™200 10%
Polyoxyethylene castor oil 4%
Disodium alkyl polyoxyethylene sulfosuccinate 5%
Modified calcium lignosulphonate 5%
Xanthan gum 1 %
Bentonite 1 %
Glycerol 5%
Water Balance to 100%
Pyraclostrobin was dissolved in Solvesso 200, and polyoxyethylene castor oil was added to form the pyraclostrobin oil phase.
Disodium alkyl polyoxyethylene sulfosuccinate, modified calcium
lignosulphonate, copper calcium sulphate and water were mixed, and a copper calcium sulphate suspension concentrate was obtained after grinding and high-speed shearing.
The suspoemulsion was obtained by adding the oil phase with pyraclostrobin to the suspension concentrate with copper calcium sulphate with stirring.
Example 14
A 50% Pyraclostrobin + 0.5% Copper calcium sulphate emulsifiable concentrate was prepared from the following components:
Pyraclostrobin 50%
Copper calcium sulphate 0.5%
Polyoxyethylene castor oil 5%
Calcium dodecybenzene sulfonate 3%
Solvesso™ 100 Balance to 100%
The above ingredients were mixed and stirred until a transparent uniform phase was formed.
Example 15 A 20% Pyraclostrobin + 30% Copper calcium sulphate water dispersible granule was prepared from the following components:
Pyraclostrobin 20%
Copper calcium sulphate 30%
Modified calcium lignosulphonate 5%
Sodium dodecyl sulfate 5%
Urea 5%
Kaolin Balance to 100%
Pyraclostrobin, copper calcium sulphate, dispersants, wetting agents, disintegrants and fillers were mixed well. A wettable powder was formed after airflow grinding. The wettable powder was then mixed with water and extruded to produce an extrudate. A 20% pyraclostrobin + 30% copper calcium sulphate water dispersible granule was obtained after dry sieving. Example 16
A 5% Pyraclostrobin + 30% Copper calcium sulphate wettable powder was prepared from the following components:
Pyraclostrobin 5%
Copper calcium sulphate 30%
Sodium dodecyl sulfate 1 %
Sodium ligninsulfonate 1 %
Kaolin Balance to 100%
The above ingredients were mixed, crushed and ground, and prepared into the wettable powder.
Example 17
A 10% Pyraclostrobin + 90% Copper calcium sulphate mixture was prepared from the following components:
Pyraclostrobin 10%
Copper calcium sulphate 90%
Pyraclostrobin and copper calcium sulphate were mixed well according to the indicated ratio.
Example 18 A 20% Pyraclostrobin + 80% Copper calcium sulphate mixture was prepared from the following components:
Pyraclostrobin 20%
Copper calcium sulphate 80%
Pyraclostrobin and copper calcium sulphate were mixed well according to the indicated ratio.
Biological Testing Examples
The toxicity index of each of the formulations and the co-toxicity coefficient (CTC value) of the mixed formulation were calculated according to Sun Yunpei's method. When CTC≤80, the composition exhibits an antagonistic effect. When 80<CTC<120, the composition exhibits an additive effect. When CTC≥120, the composition exhibits a synergistic effect.
Actual toxicity index (ATI) = (standard formulation EC50/ testing formulation EC50)*100
Theoretical toxicity Index (TTI) = (toxicity index of formulation A * percentage of A in the mixed formulation) + (toxicity index of formulation B * percentage of B in the mixed formulation)
Co-toxicity coefficient (CTC) = [actual toxicity index (ATI) of the mixed formulation / theoretical toxicity index (TTI) of the mixed formulation] *100
Test 1 : Toxicity test of cucumber downy mildew
The samples were selected from cucumber seedlings in the same growing period. The pots were sprayed with a potter spray tower at the pressure of 50PSI. 5ml per each pot. A concentration gradient of 12 levels was prepared for each formulation. Inoculation was carried out 24 hours after the treatment of the formulations. The conidiums from the leaves with cucumber downy mildew (collected from a field) was spread evenly on the cucumber seedlings, and then the cucumber seedlings were put in the green house for culturing.
Seven days later, the disease index for the whole plant was studied according to the pathological grading standard of cucumber downy mildew, the prevention and control efficacy was determined, and the generalized least square method was applied to calculate the half maximal effective concentration EC50. The Sun Yunpei's method was applied to calculate the co-toxicity coefficient (CTC). The results are set out in Table 1 below.
Table 1 : Toxicity Test Result on the Prevention and Control of Cucumber Downy mildew
Figure imgf000021_0001
From Table 1 , it can be seen that while the ratio of pyraclostrobin to copper calcium sulphate on the prevention and control of cucumber downy mildew was in the range of 1 : 100 to 100: 1 , all CTC values were larger than 120. This indicates that the mixing of these two components in the said range displayed a synergistic effect. A synergistic effect was particularly apparent when the components were present in the ratio of 1 :5.
Test 2: Toxicity test of banana black spot
The natural inoculation method of bacterium of banana black spot in the orchard was employed. The samples were selected from the bananas with their buds just being cut off, and being smooth in surface and with no black spots. Testing formulations and comparison formulations were prepared in liquid form according to a range of concentrations and sprayed evenly on the surfaces of the bananas.
Treatments were replicated four times. The disease condition of the bananas was studied 25 days after the treatment. The disease index was studied according to the pathological grading standard of banana, the prevention and control efficacy was determined, and the generalized least square method was applied to calculate the half maximal effective
concentration EC50 . The Sun Yunpei's method was applied to calculate the co- toxicity coefficient (CTC). The results are set out in Table 2 below.
Table 2: Toxicity Test Result on the Prevention and Control of Banana Black Spot
Figure imgf000022_0001
From Table 2, it can be seen that while the ratio of pyraclostrobin to copper calcium sulphate on the prevention and control of banana black spot was in the range of 1 : 100 to 100: 1 , all CTC values were larger than 120. This indicates that the mixing of these two components in the said range displayed a synergistic effect. A synergistic effect was particularly apparent when the components were present in the ratio of 1 :5.
Test 3: Toxicity test of potato early blight
The samples were selected from the potato seedlings in the same growing period. 3 pots of testing seedlings were used for each treatment. The pots were sprayed with a potter spray tower at the pressure of 50PSI. 5ml per each pot. A concentration gradient of 12 levels was prepared for each formulation. Inoculation was carried out 24 hours after the treatment of the formulations. The conidiums from the leaves with potato early blight (collected from the field) was spread evenly on the potato seedlings, and the potato seedlings were then put in the green house for culturing.
Seven days later, the disease index for the whole plant was studied according to the pathological grading standard of potato early blight, the prevention and control efficacy was determined, and the generalized least square method was then applied to calculate the half maximal effective concentration EC50 . The Sun Yunpei's method was applied to calculate the co-toxicity coefficient (CTC). The results are set out in Table 3 below.
Table 3: Toxicity Test Result on the Prevention and Control of Potato Early Blight
Figure imgf000023_0001
Testing Formulation Ratio TTI ATI CTC
(PPM)
Pyraclostrobin — 158.4 100 / /
327.2
Copper calcium sulphate — 48.4 / /
7
214.1
Pyraclostrobin : Copper calcium sulphate 1 :100 73.95 48.91 151.2
9
195.3
Pyraclostrobin : Copper calcium sulphate 1 :50 81.08 49.41 164.1
5
152.0
Pyraclostrobin : Copper calcium sulphate 1 : 25 104.16 50.86 204.8
8
140.5
Pyraclostrobin : Copper calcium sulphate 1 :10 112.71 53.09 212.3
4
108.4
Pyraclostrobin : Copper calcium sulphate 1 :5 146.03 57.00 243.8
7
Pyraclostrobin : Copper calcium sulphate 1 :1 78.69 201.30 74.20 256.2
Pyraclostrobin : Copper calcium sulphate 5:1 63.88 247.97 91.40 271.3
Pyraclostrobin : Copper calcium sulphate 10: 1 70.10 225.98 95.31 237.1
Pyraclostrobin : Copper calcium sulphate 25: 1 82.81 191.28 97.54 196.1
Pyraclostrobin : Copper calcium sulphate 50: 1 98.66 160.56 98.99 162.2
Pyraclostrobin : Copper calcium sulphate 100: 1 118.7 133.41 99.49 134.1
Figure imgf000024_0001
From Table 3, it can be seen that while the ratio of pyraclostrobin to copper calcium sulphate on the prevention and control of potato early blight was in the range of 1 : 100 to 100: 1 , the CTC is larger than 120. This indicates that the mixing of these two components in the said range displayed a synergistic effect. A synergistic effect was particularly apparent when the components were present in the ratio of 5:1.
Prevention and Control Testing
A synergistic effect exists when the fungicidal activity of the active compound composition is greater than the sum of the activities of the active compounds applied individually. The expected activity for a given combination of two active compounds can be calculated in accordance with Colby's formula (refer to S.R. Colby,
"Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds 1967, 15, 20-22) as follows:
If X denotes the activity when using active compound A at an application rate of m g/ha or in a concentration of m ppm;
Y denotes the activity when using active compound B at an application rate of n g/ha or in a concentration of n ppm;
E denotes the activity when using active compounds A and B at application rates of m and n g/ha or in concentration of m and n ppm;
Then:
If the actual fungicidal activity (O) is greater than the expected activity (E), then the activity of the composition is superadditive: in other words, synergism is present.
The present invention is illustrated by the following biological testing examples. The present invention is not, however, limited to the following examples.
Test 4 Prevention and control efficacy of cucumber downy mildew
The leaves of the cucumber seedlings in pots were sprayed with the suspension concentrate in a range of concentrations of the active compounds, as indicated in Table 4. The next day, the treated plants were inoculated with a spore suspension of cucumber downy mildew. The pots were then allowed to stand for 24 hours in a room at 20-22°C and with high humidity (90-95%). During this period, the spores
germinated and the germ tubes penetrated into the leaf tissues. The day after, the testing plants were put back to the greenhouse at 20-22°C at a relative humidity of 65-70% for culturing for another seven days. Later, the development of downy
mildew on the leaves was determined by visual observation. The results are set out in Table 4 below.
Table 4: Prevention and control efficacy of cucumber downy mildew
Figure imgf000025_0001
Test 5 Prevention and control efficacy of potato early blight
The leaves of the potato seedlings in pots were sprayed with suspension concentrates with a range of concentrations of the active compounds, as indicated in Table 5.
The next day, the treated plants were inoculated with a spore suspension of potato early blight. The pots were then allowed to stand for 24 hours in a room at 20- 22°C and with high humidity (90-95%). During this period, the spores germinated and the germ tubes penetrated into the leaf tissues. The day after, the testing plants were put back to the greenhouse at 20-22°C at a relative humidity of 65-70% for culturing for another seven days. Later, the development of early blight on the leaves was determined by visual observation. The results are set out in Table 5 below.
Table 5: Prevention and control efficacy of potato early blight
Active compound/ Concentration Ratio Observed Activity Synergistic Active compound (ppm) activity (%) according to effect combination Colby's
calculation
(%)
Pyraclostrobin 80 - 57 - -
Copper calcium
16 - 3 - - sulphate
Pyraclostrobin
+Copper calcium 80+16 5:1 79.3 58.29 Yes sulphate
Test 6 Prevention and control efficacy of banana black spot
In the following tests, spraying stated at the initial stage of the disease.
Treatments were replicated four times. The pots were arranged in groups randomly with 3 banana trees in a small group. The application time was from September to
October. The spray volume was about 100kg/667m2. The whole fruit trees were
sprayed. The surface of the fruits, together with the front and back of the leaves were sprayed evenly until there was a dripping of liquid. The development of banana black spot was determined by visual observation. The results are set out in Table 6 below.
Table 6: Prevention and control efficacy of banana black spot
Activity
Active compound/ Observed according to
Concentration Synergistic Active compound Ratio activity Colby's
(ppm) effect combination (%) calculation
(%)
Pyraclostrobin 60 - 61.3 - -
Copper calcium
300 - 1 1 - - sulphate
Pyraclostrobin + Copper
60+300 1 :5 90.4 65.5 Yes calcium sulphate

Claims

1. A fungicidal active compound combination, comprising pyraclostrobin and copper calcium sulphate.
2. The combination according to claim 1 , wherein the pyraclostrobin and copper calcium sulphate are present in a weight ratio of from 1 : 100 to 100: 1.
3. The fungicidal active compound combination according to claim 2, wherein the weight ratio of pyraclostrobin and copper calcium sulphate is 1 :50 to 50:1.
4. The fungicidal active compound composition according to claim 3, wherein the weight ratio of pyraclostrobin and copper calcium sulphate is 1 :25 to 25:1.
5. A method for the prevention and control of phytopathogenic bacterium, comprising applying the fungicidal active compound combination according to any of claims 1 to 4 on a bacterium or a habitat thereof, on a plant, plant part, seed, soil, area, material or locus.
6. The method according to claim 5, wherein pyraclostrobin and copper calcium sulphate are applied simultaneously, separately or consecutively.
7. A method of preparing a fungicidal composition, wherein pyraclostrobin and copper calcium sulphate are combined with a filling agent and/ or a surfactant.
8. A fungicidal composition, comprising pyraclostrobin and copper calcium sulphate.
9. The fungicidal composition according to claim 8, wherein the said fungicidal composition is in the form of a suspension concentrate, seed coating formulation, wettable powder, water dispersible granule, microencapsulated suspension, a mixed formulation of microencapsulated suspension and suspension concentrate (ZC), coated granule, granule, emulsifiable concentrate, microemulsion, oil-in-water emulsion and effervescent tablet.
10. The fungicidal composition according to either of claims 8 or 9, wherein pyraclostrobin and copper calcium sulphate are present in an amount of 5 to 90% of the fungicidal composition.
11. The fungicidal composition according to claim 10, wherein pyraclostrobin and copper calcium sulphate are present in an amount of 20 to 80% of the fungicidal composition.
12. Use of a fungicidal active compound combination according to any of claims 1 to 4 for the prevention and control of fungus and bacterium.
13. Use of fungicidal composition according to any of claims 8 to 11 for the prevention and control of fungus and bacterium.
14. The use of either of claims 12 or 13, for the prevention and control of fungus and bacterium on crops, fruits, vegetables and cash crops.
15. A method of controlling fungus and bacterium growth at a locus, comprising applying to the locus pyraclostrobin and copper calcium sulphate.
16. A fungicidally active combination of pyraclostrobin and copper calcium sulphate substantially as hereinbefore described.
17. A fungicidal composition substantially as hereinbefore described.
18. A method of controlling fungicidal and/or bacterial infections substantially as hereinbefore described.
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