EP3046416A1 - Active compound combinations - Google Patents

Active compound combinations

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Publication number
EP3046416A1
EP3046416A1 EP14766696.0A EP14766696A EP3046416A1 EP 3046416 A1 EP3046416 A1 EP 3046416A1 EP 14766696 A EP14766696 A EP 14766696A EP 3046416 A1 EP3046416 A1 EP 3046416A1
Authority
EP
European Patent Office
Prior art keywords
plant
active compound
increase
content
plants
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14766696.0A
Other languages
German (de)
French (fr)
Inventor
Lino Miguel Dias
Martin Vaupel
Andreas Goertz
Hilmar Wolf
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
Original Assignee
Bayer CropScience AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Priority to EP14766696.0A priority Critical patent/EP3046416A1/en
Publication of EP3046416A1 publication Critical patent/EP3046416A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A01N47/14—Di-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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • 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
    • 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
    • A01N59/14—Boron; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C05D9/02—Other inorganic fertilisers containing trace elements
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants

Definitions

  • the present invention primarily relates to active compound combinations comprising (A) propineb and a constituent (B) comprising (Bl) one or more salts containing boron (B), and (B2) one or more salts containing manganese (Mn). More specifically, the active compound combinations according to the invention are useful for improving plant quality. The present invention further relates to corresponding methods and uses of the active compound combinations according to the present invention.
  • Propineb of the formula (C53 ⁇ 4N2S4Zn) x is polymeric zinc propylenebis(dithiocarbamate) (CAS Reg No. 12071-83-9) and can be described by the following formula (I)
  • Propineb is known to have fungicidal properties and can be used for controlling various plant diseases (see e.g. GB 935,981).
  • WO 20 ⁇ /107443 Al teaches the use of propineb for the physiological preventive treatment and curative treatment under zinc deficiency. There, it is also reported that in addition to the physiological curative ef- feet propineb treatment resulted in higher yields.
  • propineb was applied to the respective plants through spray application.
  • WO 2012/089724 Al relates to a method for improving plant quality, which method comprises treating the crop plant and/or the locus where the crop plant is growing or is intended to grow and/or the plant propagules with a plant quality improving amount of a micronutrient containing active ingredient.
  • compositions providing an improving crop yield containing (1) certain dithio- carbamidates and (2) a manganese (Mn) salt of an inorganic or organic acid.
  • WO 2005/070204 reports the use of micronutrients in pesticide compositions for reducing phyto- toxicity.
  • the environmental and economic requirements imposed on modern-day crop protection compositions are continually increasing. This does not only relate to, for example, the spectrum of action, to toxicity, to selectivity, to application rate, and the like, but also to improved plant quality, in particular increased yield, and or to improved plant vigor. It has now surprisingly been found that the active compound combinations according to the present invention not only bring about an enhancement of the spectrum of action with respect to phytopathogens to be controlled, but moreover an improved plant quality, in particular increased yield, and/or to an improved plant vigor are achieved.
  • the active compound combinations according to the invention have properties which are synergistic, such as improved properties of the plant, for example better growth, increased harvest yields, a better developed root system, a larger leaf area, greener leaves, stronger shoots, in particular greener leaves.
  • the present invention relates to active compound combinations comprising:
  • constituent (Bl) are selected from the group consisting of boron oxides, and boric acids, and the salts thereof.
  • constituent (Bl) are selected from the group consisting of boron trioxide (B2O3), H3BO3, H2B4O7, sodium borates (preferably borax, also known as sodium borate, sodium tetraborate, or disodium tetraborate, preferably anhydrous borax borax pentahydrate or borax decahydrate lOEbO)), potassium borates (preferably K2B4O7, and the hydrates thereof, preferably the tetrahydrate thereof K2B4O7 4H2O), calcium borates (preferably CaB407, Ca3(B03)2, and the hydrates thereof), magnesium borates (preferably MgB/iOv, Mg3(B03)2, and the group consisting of constituent (Bl) are selected from the group consisting of boron trioxide (B2O3), H3BO3, H2B
  • constituent (B2) are selected from the group consisting of manganese (II) salts, preferably selected from the group consisting of manganese (II) acetate, manganese (II) sulfate, manganese (II) chloride, manganese (II) nitrate, and manganese (II) phosphate.
  • manganese (II) salts preferably selected from the group consisting of manganese (II) acetate, manganese (II) sulfate, manganese (II) chloride, manganese (II) nitrate, and manganese (II) phosphate.
  • constituent (Bl) comprises or consists of disodium tetraborate and/or disodium tetraborate hydrates, and/or
  • constituent (B2) comprises or consists of manganese (II) sulfate and/or manganese (II) chloride.
  • the synergistic effect is particularly pronounced.
  • the ratio by weight of constituent (A) to the total weight of boron and manganese of constituent (B) is in the range of 1250 : 1 to 25 : 1, preferably in the range of 1000 : 1 to 50 : 1, more preferably in the range of 500 : 1 to 75 : 1, and particularly preferably in the range of 350 : 1 to 100 : 1 , in each case based on the total weight of the active compound combination.
  • the ratio by weight of the total amount of boron [of constituent (Bl)] to the total amount of manganese [of constituent (B2)] is in the range of 3 : 1 to 1 : 3, preferably in the range of 2 : 1 to 1 : 2, more preferably in the range of 3 : 2 to 2 : 3, even more preferably in the range of 4 : 3 to 3 : 4, and most preferably in the range of 5 : 4 to 4 : 5, in each case based on the total weight of the active compound combination.
  • an active compound combination according to the present invention further comprises
  • micronutrients selected from the group consisting of zinc (Zn), copper (Cu), iron (Fe), molybdenum (Mo), selenium (Se), aluminum (Al), cobalt (Co) and nickel (Ni), and/or
  • an active compound combination according to the present invention further comprises
  • N nitrogen
  • P phosphorus
  • K potassium
  • micronutrients selected from the group consisting of zinc (Zn), copper (Cu), iron (Fe), molybdenum (Mo), selenium (Se), aluminum (Al), cobalt (Co) and nickel (Ni).
  • An active compound combination according to present invention preferably comprises one or more further components selected from the group consisting of zinc oxide, zinc acetate, zinc benzoate, zinc chloride, zinc citrate, zinc nitrate, zinc salicylate; cupric acetate, cupric butyrate, cupric chlorate, cupric chloride, cupric citrate, cupric gluconate, cupric glycinate, cupric nitrate, cupric salicylate, cuprous acetate, cuprous chloride; ferric chloride, ferric citrate, ferric fructose, ferric glycerophosphate, ferric nitrate, ferric oxide, saccharated ferric oxide, ferrous chloride, ferrous citrate, ferrous fumarate, ferrous gluconate, ferrous succinate; molybdic acid, calcium molybdate, potassium molybdate, sodium molybdate; sodium selenite, potassium selenite, sodium selenate, potassium selenate; aluminum phosphate, aluminum silicate; cobaltic
  • the expression “combination” stands for the various combinations of constituents (A) and (B), for example in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active compounds, such as a "tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other within a short period, preferably within less than two hours.
  • the present invention relates to the novel method for improving plant quality by applying the active compound combinations according to the present invention to the plants, plant part and/or their habitat.
  • plant quality quality of a plant
  • yield for example increased biomass, increased content of valuable ingredients and/or improved content or composition of certain ingredients
  • plant vigor for example improved plant growth and/or greener leaves
  • yield is to be understood as any plant part or product of economic value that is produced by the plant such as grains, leaves, roots, fruits in the proper sense, vegetables, nuts, seeds, wood (e.g. in the case of forestry) or even flowers (e.g. in the case of horticulture and ornamentals).
  • the plant products may in addition be further utilized and/or processed after harvesting.
  • "increased yield" of a crop plant means that the yield of a product of the respective crop plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the micronutrient containing active ingredient. Increased yield can be characterized inter alia by following improved properties of the crop plant:
  • vitamin content e.g. of Vitamin Bi, B2, C and E
  • the yield is increased by at least 5 % or more, preferably 10 % or more, more preferably 15 % or more, even more preferably 20 % or more, and even more preferably 25 % or more, in each case compared to the respective untreated control plant.
  • plant vigor Another indicator for the quality of a plant, in particular for the condition of the crop plant is the "plant vigor".
  • the plant vigor becomes manifest in several aspects such as the general visual appearance and growth.
  • Improved plant vigor can be characterized inter alia by following improved properties of the plant:
  • the plant vigor is increased by at least 5 % or more, preferably 10 % or more, more preferably 15 % or more, even more preferably 20 % or more, and even more preferably 25 % or more, in each case compared to the respective untreated control plant.
  • different quality parameters are more preferably increased than others. In the following some quality parameters are mentioned depending on the treated crop plant.
  • the following plants and plant parts are treated with an active compound combinations according to the present invention: cereals such as wheat, barley, rye, triticale, sorghum/millet and oats, maize, cotton, soy beans, rice, potatoes, sunflowers, beans, coffee, beets (for example sugar beet and fodder beet), peanuts, oilseed rape, fruits (such as apples, pears and citrus fruits), vegetables (such as tomatoes, cucumbers, onions and lettuce), turf and ornamentals (see also below).
  • cereals such as wheat, barley, rye, triticale, sorghum/millet and oats, maize, cotton, soy beans, rice, potatoes, sunflowers, beans, coffee, beets (for example sugar beet and fodder beet), peanuts, oilseed rape, fruits (such as apples, pears and citrus fruits), vegetables (such as tomatoes, cucumbers, onions and lettuce), turf and ornamentals (see also below).
  • plants and plant parts belonging to Solanaceae sp. e.g. tomatoes, potatoes, peppers, capsicum, aubergines, tobacco
  • Solanaceae sp. e.g. tomatoes, potatoes, peppers, capsicum, aubergines, tobacco
  • the preferred quality parameters for corn/maize are ⁇ increased carotenoid content (e.g. of Vitamin A),
  • the preferred quality parameters for tomatoes, cucumbers and peppers are
  • the preferred quality parameters for grapes/vine are ⁇ higher anthocyanin content
  • the present invention further relates to compositions comprising an effective and preferably non-phytotoxic amount of the active compound combinations according to the present invention. These compositions are also suitable for controlling unwanted microorganisms, especially unwanted fungi and bacteria. Said preferably fungicidal compositions comprise agriculturally suitable auxiliaries, solvents, carriers, surfactants and/or extenders.
  • control of harmful microorganisms means a reduction in infestation by harmful microorganisms, compared with the untreated plant measured as fungicidal efficacy, preferably a reduction by 25-50 %, compared with the untreated plant, more preferably a reduction by 40-79 %, compared with the untreated plant; even more preferably, the infection by harmful microorganisms is almost completely or entirely suppressed (by 80-100 %).
  • the control of harmful microorganisms may be curative, i.e. for treatment of already infected plants, or protective, i. e. for protection of plants which have not yet been infected.
  • an "effective but non-phytotoxic amount” means an amount which is sufficient to control the fungal disease of the plant in a satisfactory manner or to eradicate the fungal disease completely, and which, at the same time, does not cause any significant symptoms of phytotoxicity. In general, this application rate may vary within a relatively wide range. It depends on several factors, for example on the fungus to be con- trolled, the plant, the climatic conditions and the constituents of the active compound combinations according to the present invention.
  • the present invention relates to a composition
  • a composition comprising
  • adjuvants auxiliaries
  • adjuvants selected from the group consisting of organic solvents, surfactants, inorganic carriers, organic carriers, and other extenders.
  • composition according to the present invention comprises a total amount of
  • the active compound combination according to the present invention preferably as defined in one of the above-identified preferred embodiments, in the range of 0.05 to 0.5 wt.%, preferably in the range of 0.1 to 0.3 wt.%, and/or
  • composition according to the present invention comprises a total amount of
  • compositions according to the present invention may be preferably obtained by a method, characterized by the following steps:
  • Suitable organic solvents include all polar and non-polar organic solvents usually employed for formulation purposes.
  • the solvents are selected from ketones, e.g. methyl-isobutyl-ketone and cyclo- hexanone, amides, e.g. dimethyl formamide and alkanecarboxylic acid amides, e.g. N,N-dimethyl decane- amide and ⁇ , ⁇ -dimethyl octanamide, furthermore cyclic solvents, e.g.
  • a carrier is a natural or synthetic, organic or inorganic substance with which the active ingredients are mixed or combined for better applicability, in particular for application to plants or plant parts or seed.
  • the carrier which may be solid or liquid, is generally inert and should be suitable for use in agriculture.
  • Useful solid or liquid carriers include: for example ammonium salts and natural rock dusts, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock dusts, such as finely divided silica, alumina and natural or synthetic silicates, resins, waxes, solid fertilizers, water, alcohols, especially butanol, organic solvents, mineral and vegetable oils, and derivatives thereof. Mixtures of such carriers can likewise be used.
  • Suitable solid filler and carrier include inorganic particles, e.g.
  • Useful solid carriers for granules include: for example crushed and fractionated natural rocks such as cal- cite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic and organic meals, and also granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
  • Useful liquefied gaseous extenders or carriers are those liquids which are gaseous at standard temperature and under standard pressure, for example aerosol propellants such as halohydrocarbons, and also butane, propane, nitrogen and carbon dioxide.
  • tackifiers such as carboxymethylcellulose, and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids, such as cephalins and lecithins, and synthetic phospholip- ids.
  • Further additives may be mineral and vegetable oils.
  • Useful liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or dichloromethane, aliphatic hydrocarbons such as cyclohexane or paraffins, for example mineral oil fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl iso- butyl ketone or cyclohexanone, and/or strongly polar solvents such as dimethylformamide and dimethyl sulphoxide.
  • aromatics such as xylene, toluene or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or dichloromethane
  • the active compound combinations according to the present invention may additionally comprise further components, for example surfactants.
  • useful surfactants are emulsifiers and/or foam formers, dispersants or wetting agents having ionic or nonionic properties, or mixtures of these surfactants.
  • salts of poly- acrylic acid salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycon- densates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols, and derivatives of the compounds containing sulphates, sulphonates and phosphates, for example alkylaryl polyglycol ethers, alkylsulpho- nates, alkylsulphates, arylsulphonates, protein hydrolysates, lignosulphite waste liquors and methylcellulose.
  • the presence of a surfactant is necessary if one of the active ingredients and/or one of the inert carriers is insoluble in water and when application is effected in water.
  • the proportion of surfactants preferably is in the range of 5 and 40 % by weight of the composition according to the present invention.
  • Suitable surfactants include all common ionic and non-ionic substances, for example ethoxylated nonylphenols, polyalkylene glycolether of linear or branched alcohols, reaction products of alkyl phenols with ethylene oxide and/or propylene oxide, reaction products of fatty acid amines with ethylene oxide and/or propylene oxide, furthermore fattic acid esters, alkyl sulfonates, alkyl sulphates, alkyl ethersulphates, alkyl etherphosphates, arylsulphate, ethoxylated arylalkylphenols, e.g.
  • tristyryl-phenol-ethoxylates furthermore ethoxylated and propoxylated arylalkylphenols like sulphated or phosphated arylalkylphenol-ethoxylates and -ethoxy- and -propoxylates.
  • arylalkylphenols like sulphated or phosphated arylalkylphenol-ethoxylates and -ethoxy- and -propoxylates.
  • Further examples are natural and synthetic, water soluble polymers, e.g.
  • lignosulphonates gelatine, gum arabic, phospholipides, starch, hydrophobic modified starch and cellulose derivatives, in particular cellulose ester and cellulose ether, further polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrol- idone, polyacrylic acid, polymethacrylic acid and co-polymerisates of (meth)acrylic acid and (meth)acrylic acid esters, and further co-polymerisates of methacrylic acid and methacrylic acid esters which are neu- tralized with alkalimetal hydroxide and also condensation products of optionally substituted naphthalene sulfonic acid salts with formaldehyde.
  • dyes such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes.
  • Antifoams which may be present in the formulations include e.g. silicone emulsions, long chain alcohols, fatty acids and their salts as well as fluoroorganic substances and mixtures therof.
  • thickeners are polysaccharides, e.g. xanthan gum orveegum, silicates, e.g. attapulgite, bentonite as well as fine-particle silica.
  • additional components for example protective colloids, binders, adhesives, thickeners, thixotropic substances, penetrants, stabilizers, sequestrants, com- plexing agents.
  • the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes.
  • the active compound combinations or compositions according to the present invention can be used as such or, depending on their particular physical and/or chemical properties, in the form of their formulations or the use forms prepared therefrom, such as aerosols, capsule suspensions, cold-fogging concentrates, warm- fogging concentrates, encapsulated granules, fine granules, flowable concentrates for the treatment of seed, ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, macrogran- ules, microgranules, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, gas (under pressure), gas generating product, foams, pastes, pesticide coated seed, suspension concentrates, suspoemulsion concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, dusts and granules, water- soluble and water-disp
  • the active compound combinations according to the present invention include not only formulations which are already ready for use and can be applied with a suitable apparatus to the plant or the seed, but also commercial concentrates which have to be diluted with water prior to use. Customary applications are for example dilution in water and subsequent spraying of the resulting spray liquor, application after dilution in oil, direct application without dilution, seed treatment or soil application of granules.
  • the formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one customary extender, solvent or diluent, adjuvant, emulsifier, dispersant, and/or binder or fixative, wetting agent, water repellent, if appropriate desiccants and UV stabilizers and, if appropriate, dyes and pigments, antifoams, preservatives, inorganic and organic thickeners, adhesives, gibberellins and also further processing auxiliaries and also water.
  • further processing steps are necessary, e.g. wet grinding, dry grinding and granulation.
  • the active compound combinations according to the present invention may be present as such or in their (commercially available) formulations and in the use forms prepared from these formulations as a mixture with other (known) active ingredients, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners and/or semiochemicals.
  • active ingredients such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners and/or semiochemicals.
  • the inventive treatment of the plants and plant parts with the active ingredients or compositions is effected directly or by action on their surroundings, habitat or storage space by the customary treatment meth- ods, for example by dipping, spraying, atomizing, irrigating, evaporating, dusting, fogging, broadcasting, foaming, painting, spreading-on, watering (drenching), drip irrigating and, in the case of propagation material, especially in the case of seeds, also by dry seed treatment, wet seed treatment, slurry treatment, incrustation, coating with one or more coats, etc. It is also possible to deploy the active ingredients by the ultra-low volume method or to inject the active ingredient preparation or the active ingredient itself into the soil.
  • the active compound combinations or compositions according to the present invention exhibit potent microbicidal activity and can be used for control of unwanted microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.
  • the invention also relates to a method for controlling unwanted microorganisms, characterized in that an active ingredient combination or composition according to the present invention is applied to the phytopathogenic fungi, phytopathogenic bacteria and/or their habitat.
  • Fungicides can be used in crop protection for control of phytopathogenic fungi. They are characterized by an outstanding efficacy against a broad spectrum of phytopathogenic fungi, including soilborne pathogens, which are in particular members of the classes Plasmodiophoromycetes, Peronosporomycetes (Syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (Syn. Fungi imper- fecti). Some fungicides are systemically active and ca be used in plant protection as foliar, seed dressing or soil fungicide. Furthermore, they are suitable for combating fungi, which inter alia infest wood or roots of plant. Bactericides can be used in crop protection for control of Pseudomonadaceae, Rhizobiaceae, Enterobac- teriaceae, Corynebacteriaceae and Streptomycetaceae.
  • Non-limiting examples of pathogens of fungal diseases which can be treated in accordance with the invention include:
  • Blumeria species for example Blumeria graminis
  • Podosphaera species for example Podosphaera leucotricha
  • Sphaerotheca species for example Sphaerotheca fuliginea
  • Uncinula species for example Uncinula necator
  • rust disease pathogens for example Gymnosporangium species, for example Gymnospo- rangium sabinae
  • Hemileia species for example Hemileia vastatrix
  • Phakopsora species for example Phakopsora pachyrhizi and Phakopsora meibomiae
  • Puecinia species for example Puccinia recondite, P. trit- icina, P. graminis or P. striiformis
  • Uromyces species for example Uromyces appendiculatus
  • diseases caused by pathogens from the group of the Oomycetes for example Albugo species, for example Algubo Candida; Bremia species, for example Bremia lactucae; Peronospora species, for example Peronospora pisi or P. brassicae; Phytophthora species, for example Phytophthora infestans; Plasmo- para species, for example Plasmopara viticola; Pseudoperonospora species, for example Pseudoperono- spora humuli or Pseudoperonospora cubensis; Pythium species, for example Pythium ultimum;
  • Phaeosphaeria species for example Phaeosphaeria nodorum
  • Pyrenophora species for example Pyrenophora teres, Pyrenophora tritici repentis
  • Ramularia species for example Ramularia collo-cygni, Ramularia areola
  • Rhynchosporium species for example Rhynchosporium secalis
  • Septoria species for example Septoria apii, Septoria lycopersii
  • Typhula species for example Typhula incarnata
  • Venturia species for example Venturia inaequalis
  • Corticium species for example Corticium graminearum
  • Fusarium species for example Fusarium oxysporum
  • Gaeumannomyces species for example Gaeumannomy- ces graminis
  • Rhizoctonia species such as, for example Rhizoctonia solani
  • Sarocladium diseases caused for example by Sarocladium oryzae Sclerotium diseases caused for example by Sclerotium oryzae
  • Tapesia species for example Tapesia acuformis
  • Thielaviopsis species for example Thielaviopsis basicola
  • Thielaviopsis species for example Thielaviopsis basicola
  • ear and panicle diseases caused, for example, by Alternaria species, for example Alternaria spp.; Aspergillus species, for example Aspergillus flavus; Cladosporium species, for example Cladosporium cladosporioides; Claviceps species, for example Claviceps purpurea; Fusarium species, for example Fusarium culmorum; Gibberella species, for example Gibberella zeae; Monographella species, for example Monographella nivalis; Septoria species, for example Septoria nodorum;
  • Sphacelotheca species for example Sphacelotheca reiliana
  • Tilletia species for example Tilletia caries, T. controversa
  • Urocystis species for example Urocystis oc- culta
  • Ustilago species for example Ustilago nuda, U. nuda tritici
  • Nectria species for example Nectria galli- gena
  • wilt diseases caused, for example, by Monilinia species, for example Monilinia laxa;
  • leaf blister or leaf curl diseases caused, for example, by Exobasidium species, for example Exobasidium vexans;
  • Taphrina species for example Taphrina deformans
  • Botrytis species for example Botrytis cinerea
  • Rhizoctonia species for example Rhizoctonia solani
  • Helminthosporium species for example Helminthosporium solani;
  • Plasmodiophora species for example Plamodiophora brassicae
  • diseases caused by bacterial pathogens for example Xanthomonas species, for example Xanthomonas campestris pv. oryzae
  • Pseudomonas species for example Pseudomonas syringae pv. lachrymans
  • Er- winia species for example Erwinia amylovora.
  • phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregatd), pythium rot (Pythium aphanidermatum, Pythium irreg- ulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem decay, and damping-off (Rhizoctonia solani), sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotinia southern blight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).
  • the active compound combinations or compositions according to the present invention can be used for curative or protective/preventive control of phytopathogenic fungi.
  • the invention therefore also relates to curative and protective methods for controlling phytopathogenic fungi by the use of active compound combinations or compositions according to the present invention, which are applied to the seed, the plant or plant parts, the fruit or the soil in which the plants grow.
  • plants and plant parts can be treated.
  • plants are meant all plants and plant populations such as desirable and undesirable wild plants, cultivars and plant varieties (whether or not protectable by plant variety or plant breeder's rights).
  • Cultivars and plant varieties can be plants obtained by conventional propagation and breeding methods which can be assisted or supplemented by one or more biotechnological methods such as by use of double haploids, protoplast fusion, random and directed mutagenesis, molecular or genetic markers or by bioengineering and genetic engineering methods.
  • plant parts are meant all above ground and below ground parts and organs of plants such as shoot, leaf, blossom and root, whereby for example leaves, needles, stems, branches, blossoms, fruiting bodies, fruits and seed as well as roots, corms and rhizomes are listed.
  • Crops and vegetative and generative propagating material for example cuttings, corms, rhizomes, runners and seeds also belong to plant parts.
  • the active compound combinations or compositions according to the present invention have favourable home- otherm toxicity and are well tolerated by the environment, are suitable for protecting plants and plant or- gans, for enhancing harvest yields, for improving the quality of the harvested material. They can preferably be used as crop protection compositions. They are active against normally sensitive and resistant species and against all or some stages of development.
  • the active compound combinations according to the present invention are also suitable for protecting seed of any plant variety which is used in agriculture, in greenhouses, in forests or in horticulture and viticulture.
  • Plants which can be treated in accordance with the invention include the following main crop plants: maize, soy bean alfalfa, cotton, sunflower, Brassica oil seeds such as Brassica napus (e.g. canola, rapeseed), Brassica ra- pa, B. juncea (e.g. (field) mustard) and Brassica carinata, Arecaceae sp. (e.g.
  • pome fruits such as apples and pears, but also stone fruits such as apricots, cherries, almonds, plums and peaches, and berry fruits such as strawberries, raspberries, red and black currant and gooseberry), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Ana- cardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp. (e.g. olive tree), Actinidaceae sp., Lauraceae sp. (e.g. avocado, cinnamon camphor), Musaceae sp. (e.g.
  • Rubiaceae sp. e.g. coffee
  • Theaceae sp. e.g. tea
  • Sterculiceae sp. e.g. lemons, oranges, mandarins and grapefruit
  • Solanaceae sp. e.g. tomatoes, potatoes, peppers, capsicum, aubergines, tobacco
  • Liliaceae sp. Compositae sp. (e.g. lettuce, artichokes and chicory - including root chicory, endive or common chicory), Umbelliferae sp. (e.g.
  • Cucurbitaceae sp. e.g. cucumbers - including gherkins, pumpkins, watermelons, calabashes and melons
  • Alliaceae sp. e.g. leeks and onions
  • Cruciferae sp. e.g. white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes, horseradish, cress and Chinese cabbage
  • Leguminosae sp. e.g. peanuts, peas, lentils and beans - e.g. common beans and broad beans
  • Che- nopodiaceae sp. e.g.
  • the active compound combinations according to the invention also exhibit a potent strengthening effect in plants. Accordingly, they can be used for mobilizing the defences of the plant against attack by undesirable microorganisms.
  • Plant-strengthening (resistance-inducing) substances are to be understood as meaning, in the present context, those substances which are capable of stimulating the defence system of plants in such a way that the treated plants, when subsequently inoculated with undesirable microorganisms, develop a high degree of resistance to these microorganisms.
  • the active compound combinations according to the invention are suitable for increasing the yield of crops.
  • plant physiology effects comprise the following:
  • Abiotic stress tolerance comprising temperature tolerance, drought tolerance and recovery after drought stress, water use efficiency (correlating to reduced water consumption), flood tolerance, ozone stress and UV tolerance, tolerance towards chemicals like heavy metals, salts, pesticides (safener) etc.
  • Biotic stress tolerance comprising increased fungal resistance and increased resistance against nematodes, viruses and bacteria.
  • biotic stress tolerance preferably comprises increased fungal resistance and increased resistance against nematodes.
  • Increased plant vigor comprising plant health / plant quality and seed vigor, reduced stand failure, im- proved appearance, increased recovery, improved greening effect and improved photosynthetic efficiency.
  • growth regulators comprising earlier germination, better emergence, more developed root system and/or improved root growth, increased ability of tillering, more productive tillers, earlier flowering, increased plant height and/or biomass, shorting of stems, improvements in shoot growth, number of kernels/ear, number of ears/m 2 , number of stolons and/or number of flowers, enhanced harvest index, bigger leaves, less dead basal leaves, improved phyllotaxy, earlier maturation / earlier fruit finish, homogenous riping, increased duration of grain filling, better fruit finish, bigger fruit vegetable size, sprouting resistance and reduced lodging.
  • Increased yield referring to total biomass per hectare, yield per hectare, kernel/fruit weight, seed size and/or hectolitre weight as well as to increased product quality, comprising: improved processability relating to size distribution (kernel, fruit, etc.), homogenous riping, grain moisture, better milling, better vinification, better brewing, increased juice yield, harvestability, digestibility, sedimentation value, falling number, pod stability, storage stability, improved fiber length/strength/uniformity, increase of milk and/or meet quality of silage fed animals, adaption to cooking and frying; further comprising improved marketability relating to improved fruit/grain quality, size distribution (kernel, fruit, etc.), increased storage / shelf-life, firmness / softness, taste (aroma, texture, etc.), grade (size, shape, number of berries, etc.), number of berries/fruits per bunch, crispness, freshness, coverage with wax, frequency of physiological disorders, colour, etc.; further comprising increased desired ingredients such as e.g
  • protein content fatty acids, oil content, oil quality, aminoacid composition, sugar content, acid content (pH), sugar/acid ratio (Brix), polyphenols, starch content, nutritional quality, gluten content/index, energy content, taste, etc.; and further comprising decreased undesired ingredients such as e.g. less mycotoxines, less aflatoxines, ge- osmin level, phenolic aromas, laccase, polyphenol oxidases and peroxidases, nitrate content etc.
  • Sustainable agriculture comprising nutrient use efficiency, especially nitrogen (N)-use efficiency, phosphorus (P)-use efficiency, water use efficiency, improved transpiration, respiration and/or CO2 assimilation rate, better nodulation, improved Ca-metabolism etc.
  • Delayed senescence comprising improvement of plant physiology which is manifested, for example, in a longer grain filling phase, leading to higher yield, a longer duration of green leaf colouration of the plant and thus comprising colour (greening), water content, dryness etc..
  • the specific inventive application of the active compound combination makes it possible to prolong the green leaf area duration, which delays the maturation (senescence) of the plant.
  • the main advantage to the farmer is a longer grain filling phase leading to higher yield.
  • sedimentation value is a measure for protein quality and describes according to Zeleny (Zeleny value) the degree of sedimentation of flour suspended in a lactic acid solution during a standard time interval. This is taken as a measure of the baking quality. Swelling of the gluten fraction of flour in lactic acid solution affects the rate of sedimentation of a flour suspension. Both a higher gluten content and a better gluten quality give rise to slower sedimentation and higher Zeleny test values.
  • the sedimentation value of flour depends on the wheat protein composition and is mostly correlated to the protein content, the wheat hardness, and the volume of pan and hearth loaves. A stronger correlation between loaf volume and Zeleny sedimentation volume compared to SDS sedimentation volume could be due to the protein content influencing both the volume and Zeleny value ( Czech J. Food Sci. Vol. 21, No. 3: 91-96, 2000).
  • the falling number is a measure for the baking quality of cereals, especially of wheat.
  • the falling number test indicates that sprout damage may have occurred. It means that changes to the physical properties of the starch portion of the wheat kernel has already happened.
  • the falling number instrument analyzes viscosity by measuring the resistance of a flour and water paste to a fall- ing plunger. The time (in seconds) for this to happen is known as the falling number.
  • the falling number results are recorded as an index of enzyme activity in a wheat or flour sample and results are expressed in time as seconds.
  • a high falling number for example, above 300 seconds
  • a low falling number indicates substantial enzyme activity and sprout-damaged wheat or flour.
  • more developed root system / “improved root growth” refers to longer root system, deeper root growth, faster root growth, higher root dry/fresh weight, higher root volume, larger root surface area, bigger root diameter, higher root stability, more root branching, higher number of root hairs, and/or more root tips and can be measured by analyzing the root architecture with suitable methodologies and Image analysis programmes (e.g. WinRhizo).
  • crop water use efficiency refers technically to the mass of agriculture produce per unit water consumed and economically to the value of product(s) produced per unit water volume consumed and can e.g. be measured in terms of yield per ha, biomass of the plants, thousand-kernel mass, and the number of ears per m2.
  • nitrogen-use efficiency refers technically to the mass of agriculture produce per unit nitrogen consumed and economically to the value of product(s) produced per unit nitrogen consumed, reflecting uptake and utilization efficiency.
  • Fv/Fm is a parameter widely used to indicate the maximum quantum efficiency of photosystem II (PSII). This parameter is widely considered to be a selective indication of plant photosynthetic performance with healthy samples typically achieving a maximum Fv/Fm value of approx. 0.85. Values lower than this will be observed if a sample has been exposed to some type of biotic or abiotic stress factor which has reduced the capacity for photochemical quenching of energy within PSII.
  • Fv/Fm is presented as a ratio of variable fluorescence (Fv) over the maximum fluorescence value (Fm).
  • the Performance Index is essentially an indicator of sample vitality (see e.g. Advanced Techniques in Soil Microbiology, 2007, 11, 319-341 ; Applied Soil Ecology, 2000, 15, 169-182.)
  • the improvement in greening / improved colour and improved photosynthetic efficiency as well as the delay of senescence can also be assessed by measurement of the net photosynthetic rate (Pn), measurement of the chlorophyll content, e.g. by the pigment extraction method of Ziegler and Ehle, measurement of the photochemical efficiency (Fv/Fm ratio), determination of shoot growth and final root and/or canopy biomass, determination of tiller density as well as of root mortality.
  • Pn net photosynthetic rate
  • Fv/Fm ratio photochemical efficiency
  • determination of shoot growth and final root and/or canopy biomass determination of tiller density as well as of root mortality.
  • preference is given to improving plant physiology effects which are selected from the group comprising: enhanced root growth / more developed root system, improved greening, improved water use efficiency (correlating to reduced water consumption), improved nutrient use efficiency, comprising especially improved nitrogen (N)-use efficiency, delayed senescence and enhanced yield.
  • the novel use of the fungicidal compositions of the present invention relates to a combined use of a) preventively and/or curatively controlling pathogenic fungi and/or nematodes, with or without resistance management, and b) at least one of enhanced root growth, improved greening, improved water use efficiency, delayed senescence and enhanced yield. From group b) enhancement of root system, water use efficiency and N-use efficiency is particularly preferred.
  • the active compound combinations or compositions according to the present invention are also suitable for treating seeds.
  • a large part of the damage to crop plants caused by haimful organisms is triggered by the infection of the seed during storage or after sowing, and also during and after germination of the plant. This phase is particularly critical since the roots and shoots of the growing plant are particularly sensitive, and even minor damage may result in the death of the plant. There is therefore a great interest in protecting the seed and the germinating plant by using appropriate compositions.
  • the control of phytopathogenic fungi by treating the seed of plants has been known for a long time and is the subject of constant improvements. However, the treatment of seed entails a series of problems which cannot always be solved in a satisfactory manner.
  • the present invention therefore also relates to a method for protection of seed and germinating plants from attack by phytopathogenic fungi, by treating the seed with an active compound combination or composition according to the present invention.
  • the invention likewise relates to the use of the active compound combinations or compositions according to the present invention for treatment of seed to protect the seed and the ger- minating plant from phytopathogenic fungi.
  • the invention further relates to seed which has been treated with an active compound combination or composition according to the present invention for protection from phytopathogenic fungi.
  • One of the advantages of the present invention is that the particular systemic properties of the active compound combinations or compositions according to the present invention mean that treatment of the seed with said active ingredients and compositions not only protects the seed itself, but also the resulting plants after emergence, from phytopathogenic fungi. In this way, the immediate treatment of the crop at the time of sowing or shortly thereafter can be dispensed with.
  • an active compound combination or composition according to the present invention can especially also be used with transgenic plants and/or seeds, in which case the plant or the plant growing from this seed is capable of expressing a protein which acts against pests.
  • the active compound combinations or compositions according to the present invention merely the expression of the protein, for example an insecticidal protein, can control certain pests.
  • a further synergistic effect can be observed in this case, which additionally increases the effectiveness for protection against attack by pests.
  • the treatment of transgenic plants or seeds with an active compound combination or composition according to the present invention is of particular significance. This relates to the seed of plants containing at least one heterologous gene. Definition and examples of suitable heterologous genes are given below.
  • an active compound combination or composition according to the pre- sent invention is applied to the seed alone or in a suitable formulation.
  • the seed is treated in a state in which it is sufficiently stable for no damage to occur in the course of treatment.
  • the seed can be treated at any time between harvest and sowing. It is customary to use seed which has been separated from the plant and freed from cobs, shells, stalks, coats, hairs or the flesh of the fruits. For example, it is possible to use seed which has been harvested, cleaned and dried down to a moisture content of less than 15 % by weight. Alternatively, it is also possible to use seed which, after drying, for example, has been treated with water and then dried again.
  • the amount of the active compound combination or composition according to the present invention applied to the seed and/or the amount of further additives is selected such that the germination of the seed is not impaired, or that the resulting plant is not damaged.
  • the active compound combinations according to the present invention can be applied directly, i.e. without containing any other components and without having been diluted.
  • suitable formulations and methods for seed treatment are known to those skilled in the art and are described, for example, in the following documents: US 4,272,417, US 4,245,432, US 4,808,430, US 5,876,739, US 2003/0176428 Al, WO 2002/080675, WO 2002/028186.
  • the active ingredients usable in accordance with the invention can be converted to the customary seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other coating compositions for seed, and also ULV formulations.
  • formulations are prepared in a known manner, by mixing the active ingredients with customary additives, for example customary extenders and also solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins and also water.
  • customary additives for example customary extenders and also solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins and also water.
  • Useful dyes which may be present in the seed dressing formulations usable in accordance with the invention are all dyes which are customary for such purposes. It is possible to use either pigments, which are sparingly soluble in water, or dyes, which are soluble in water. Examples include the dyes known by the names Rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1.
  • Useful wetting agents which may be present in the seed dressing formulations usable in accordance with the invention are all substances which promote wetting and which are conventionally used for the formulation of active agrochemical ingredients. Preference is given to using alkyl naphthalenesulphonates, such as diisopropyl or diisobutyl naphthalenesulphonates.
  • Useiul dispersants and/or emulsifiers which may be present in the seed dressing formulations usable in accordance with the invention are all nonionic, anionic and cationic dispersants conventionally used for the formulation of active agrochemical ingredients. Usable with preference are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants.
  • Suitable nonionic dispersants include especially ethylene oxide/propylene oxide block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ether, and the phosphated or sul- phated derivatives thereof.
  • Suitable anionic dispersants are especially lignosulphonates, polyacrylic acid salts and arylsulphonate/formaldehyde condensates.
  • Antifoams which may be present in the seed dressing formulations usable in accordance with the invention are all foam-inhibiting substances conventionally used for the formulation of active agrochemical ingredients. Silicone antifoams and magnesium stearate can be used with preference.
  • Preservatives which may be present in the seed dressing formulations usable in accordance with the invention are all substances usable for such purposes in agrochemical compositions. Examples include dichlorophene and benzyl alcohol hemiformal.
  • Secondary thickeners which may be present in the seed dressing formulations usable in accordance with the invention are all substances usable for such purposes in agrochemical compositions.
  • Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica.
  • Adhesives which may be present in the seed dressing formulations usable in accordance with the invention are all customary binders usable in seed dressing products.
  • Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.
  • the seed dressing formulations usable in accordance with the invention can be used, either directly or after previously having been diluted with water, for the treatment of a wide range of different seed, including the seed of transgenic plants. In this case, additional synergistic effects may also occur in interaction with the substances formed by expression.
  • all mixing units usable customarily for the seed dressing are useful. Specifically, the procedure in the seed dressing is to place the seed into a mixer, to add the particular desired amount of seed dressing formulations, either as such or after prior dilution with water, and to mix everything until the formulation is distributed homogeneously on the seed. If appropriate, this is followed by a drying pro- cess.
  • the active compound combinations or compositions according to the present invention can also be used in the protection of materials, for protection of industrial materials against attack and destruction by unwanted microorganisms, for example fungi and insects.
  • active compound combinations according to the present invention can be used as antifouling compositions, alone or in combinations with other active ingredients.
  • Industrial materials in the present context are understood to mean inanimate materials which have been prepared for use in industry.
  • industrial materials which are to be protected by active compound combinations or compositions according to the present invention from microbial alteration or destruction may be adhe- sives, glues, paper, wallpaper and board/cardboard, textiles, carpets, leather, wood, fibers and tissues, paints and plastic articles, cooling lubricants and other materials which can be infected with or destroyed by microorganisms.
  • Parts of production plants and buildings for example cooling-water circuits, cooling and heating systems and ventilation and air-conditioning units, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected.
  • Industrial materials within the scope of the present invention preferably include adhesives, sizes, paper and card, leather, wood, paints, cooling lubri- cants and heat transfer fluids, more preferably wood.
  • the active compound combinations or compositions according to the present invention may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
  • the active compound combinations according to the invention may also be used against fungal diseases liable to grow on or inside timber.
  • the term "timber" means all types of species of wood, and all types of working of this wood intended for construction, for example solid wood, high-density wood, laminated wood, and plywood.
  • the method for treating timber according to the invention mainly consists in contacting one or more compounds according to the invention or a composition according to the invention; this includes for example direct application, spraying, dipping, injection or any other suitable means.
  • the active compound combinations according to the invention can be used to protect objects which come into contact with saltwater or brackish water, especially hulls, screens, nets, buildings, moorings and signalling systems, from fouling.
  • Storage goods are understood to mean natural substances of vegetable or animal origin or processed products thereof which are of natural origin, and for which long-term protection is desired.
  • Storage goods of vegetable origin for example plants or plant parts, such as stems, leaves, tubers, seeds, fruits, grains, can be protected freshly harvested or after processing by (pre)drying, moistening, comminuting, grinding, pressing or roasting.
  • Storage goods also include timber, both unprocessed, such as construction timber, electricity poles and barriers, or in the form of finished products, such as furniture.
  • Storage goods of ani- mal origin are, for example, hides, leather, furs and hairs.
  • the active compound combinations or compositions according to the present invention may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
  • Microorganisms capable of degrading or altering the industrial materials include, for example, bacteria, fungi, yeasts, algae and slime organisms.
  • the active compound combinations or compositions according to the present invention preferably act against fungi, especially moulds, wood-discoloring and wood-destroying fungi (Asco- mycetes, Basidiomycetes, Deuteromycetes and Zygomycetes), and against slime organisms and algae.
  • Exam- pies include microorganisms of the following genera: Alternaria, such as Alternaria tenuis; Aspergillus, such as Aspergillus niger; Chaetomium, such as Chaetomium globosum; Coniophora, such as Coniophora puetana; Lentinus, such as Lentinus tigrinus; Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans; Sclerophoma, such as Sclerophoma pityophila; Trichoderma, such as Trichoderma viride; Ophiostoma spp., Ceratocystis spp., Humicola spp., Petriella spp., Trichurus spp., Coriolus spp., Gloeophyllum spp., Pleurotus spp.
  • the active compound combinations or compositions according to the present invention also have very good antimycotic activity. They have a very broad antimycotic activity spectrum, especially against dermatophytes and yeasts, moulds and diphasic fungi (for example against Candida species, such as C. albicans, C. glabrata), and Epidermophyton floccosum, Aspergillus species, such as A. niger and A. fumigatus, Trichophyton species, such as T. mentagrophytes, Microsporon species such as M. canis and M. audouinii. The list of these fungi by no means constitutes a restriction of the mycotic spectrum covered, and is merely of illus- trative character.
  • the active compound combinations or compositions according to the present invention can therefore be used both in medical and in non-medical applications.
  • plants and their parts in accordance with the invention.
  • wild plant species and plant cultivars or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and also parts thereof, are treated.
  • transgenic plants and plant cultivars obtained by genetic engineering methods if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated.
  • the terms "parts” or “parts of plants” or “plant parts” have been explained above. More preferably, plants of the plant cultivars which are commercially available or are in use are treated in accordance with the invention.
  • Plant cultivars are understood to mean plants which have new properties ("traits”) and have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, bio- or genotypes.
  • the method of treatment according to the invention can be used in the treatment of genetically modified organisms (GMOs), e.g. plants or seeds.
  • GMOs genetically modified organisms
  • Genetically modified plants (or transgenic plants) are plants of which a heterologous gene has been stably integrated into genome.
  • heterologous gene essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mito- chondrial genome gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, cosuppression technology, RNA interference - RNAi - technology or microRNA - miRNA - technology).
  • a heterologous gene that is located in the genome is also called a transgene.
  • a transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
  • the treatment according to the invention may also result in superadditive ("synergistic") effects.
  • superadditive for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the active compounds and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, bigger fruits, larger plant height, greener leaf color, earlier flowering, higher quality and/or a higher nutritional value of the harvested products, higher sugar concentration within the fruits, better storage stability and/or pro- cessability of the harvested products are possible, which exceed the effects which were actually to be expected.
  • the active compound combinations according to the invention also have a strengthening effect in plants. Accordingly, they are also suitable for mobilizing the defense system of the plant against attack by unwanted microorganisms. This may, if appropriate, be one of the reasons of the enhanced activity of the active compound combinations according to the invention.
  • Plant-strengthening (resistance-inducing) substances are to be understood as meaning, in the present context, those substances or combinations of sub- stances which are capable of stimulating the defense system of plants in such a way that, when subsequently inoculated with unwanted microorganisms, the treated plants display a substantial degree of resistance to these microorganisms.
  • unwanted microorganisms are to be understood as meaning phytopathogenic fungi, bacteria and viruses.
  • the substances according to the invention can be employed for protecting plants against attack by the abovementioned pathogens within a certain period of time after the treatment.
  • the period of time within which protection is effected generally extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds.
  • Plants and plant cultivars which are preferably to be treated according to the invention include all plants which have genetic material which impart particularly advantageous, useful traits to these plants (whether obtained by breeding and/or biotechnological means). Plants and plant cultivars which are also preferably to be treated according to the invention are resistant against one or more biotic stresses, i.e. said plants show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.
  • nematode or insect resistant plants are for example those mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al.
  • Plants and plant cultivars which may also be treated according to the invention are those plants which are resistant to one or more abiotic stresses.
  • Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.
  • Plants and plant cultivars which may also be treated according to the invention are those plants characterized by enhanced yield characteristics. Increased yield in said plants can be the result of, for example, improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germi- nation efficiency and accelerated maturation.
  • Yield can furthermore be affected by improved plant architecture (under stress and non-stress conditions), including but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance.
  • Further yield traits include seed composition, such as carbohydrate content, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability.
  • Plants that may be treated according to the invention are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stresses). Such plants are typically made by crossing an inbred male-sterile par- ent line (the female parent) with another inbred male-fertile parent line (the male parent). Hybrid seed is typically harvested from the male sterile plants and sold to growers. Male sterile plants can sometimes (e.g. in corn) be produced by detasseling, i.e. the mechanical removal of the male reproductive organs (or males flowers) but, more typically, male sterility is the result of genetic determinants in the plant genome.
  • cytoplas- mic male sterility were for instance described in Brassica species (WO 92/05251, WO 95/09910, WO 98/27806, WO 2005/002324, WO 2006/021972 and US 6,229,072).
  • CMS cytoplas- mic male sterility
  • Male sterile plants can also be obtained by plant biotechnology methods such as genetic engineering.
  • a particularly useful means of obtaining male- sterile plants is described in WO 89/10396 in which, for example, a ribonuclease such as barnase is selectively expressed in the tapetum cells in the stamens. Fertility can then be restored by expression in the ta- petum cells of a ribonuclease inhibitor such as barstar (e.g. WO 91/02069).
  • Plants or plant cultivars obtained by plant biotechnology methods such as genetic engineering which may be treated according to the invention are herbicide-tolerant plants, i.e. plants made tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation, or by selection of plants containing a mutation imparting such herbicide tolerance.
  • Herbicide-resistant plants are for example glyphosate-tolerant plants, i.e. plants made tolerant to the herbicide glyphosate or salts thereof. Plants can be made tolerant to glyphosate through different means, for example those mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al . Other herbicide resistant plants are for example plants that are made tolerant to herbicides inhibiting the enzyme glutamine synthase, such as bialaphos, phosphinothricin or glufosinate. Such plants can be obtained for example by methods mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al.
  • HPPD hydroxyphenylpyruvatedioxygenase
  • HPPD is an enzyme that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is transformed into homogentisate.
  • Plants tolerant to HPPD- inhibitors can be transformed with a gene encoding a naturally-occurring resistant HPPD enzyme, or a gene encoding a mutated or chimeric HPPD enzyme, for example as mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al.
  • Still further herbicide resistant plants are plants that are made tolerant to aceto lactate synthase (ALS) inhibitors.
  • ALS -inhibitors include, for example, sulfonylurea, imidazolinone, triazolopyrimidines, piyimidinyoxy- (thio)benzoates, and/or sulfonylaminocarbonyltriazolinone herbicides.
  • Different mutations in the ALS enzyme also known as acetohydroxyacid synthase, AHAS
  • AHAS acetohydroxyacid synthase
  • Plants or plant cultivars obtained by plant biotechnology methods such as genetic engineering which may also be treated according to the invention are insect-resistant transgenic plants, i.e. plants made re- sistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance.
  • insect-resistant transgenic plant in particular relates to the insect-resistant transgenic plants mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al.
  • Plants or plant cultivars obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance. Particularly useful stress tolerance plants are those mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al.
  • Plants or plant cultivars obtained by plant biotechnology methods such as genetic engineering which may also be treated according to the invention show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product such those from transgenic plants mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al.
  • Plants or plant cultivars that can be obtained by plant biotechnology methods such as genetic engineering which may also be treated according to the invention are plants, such as oilseed rape or related Bras- sica plants, with altered oil profile characteristics.
  • Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered oil profile characteristics and include the oilseed rape plants mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al.
  • Particularly useful transgenic plants which may be treated according to the invention are plants containing transformation events, or combination of transformation events, that are the subject of petitions for non- regulated status, in the United States of America, to the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA) whether such petitions are granted or are still pending.
  • transgenic plants which may be treated according to the invention are plants containing transformation events, or a combination of transformation events, are those mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al.
  • the present invention relates to a method for achieving one, several or all of the following effects: control of phytopathogenic fungi in or on a plant, control of phytopathogenic fungi in crop protection, improve vitality of the plant and/or improve plant development (in particular improve plant growth, preferably increase the plant growth rate), enhance pigment content and/or enhance photosynthetic activity (preferably increase chlorophyll content, thereby preferably obtaining greener leaves ("greening") and/or larger leaves (particularly bigger leaf blade)), increase biomass, such as higher fresh weight (FW) and/or dry weight (DW), preferably increase plant weight (particularly higher fruit weight (per fruit) or higher grain weight (per grain) and/or higher overall fruit or higher overall grain yield), and/or increase plant height, - increase nutrient content, particularly increase micronutrient content (particularly
  • the application rates can be varied within a relatively wide range, depending on the kind of application.
  • the active compound combination according to the present invention or the composition according to the present invention is applied to seeds or leaves, wherein in the application the amount of the active compound combination on leaves is in the range of from 400 to 3000 g/ha (preferably of from 500 to 2500 g/ha, more preferably of from 600 to 2000 g/ha, and even more preferably of from 700 to 1700 g/ha), and in the treatment of seeds in the range of from 2 to 200 g per 100 kg of seeds, preferably of from 5 to 150 g per 100 kg of seeds, more preferably of from 10 to 100 g per 100 kg of seeds.
  • the active compound combinations according to the present invention or compositions according to the present invention can be used to protect plants from attack by the pathogens mentioned for a certain period of time after treatment.
  • the period for which protection is provided extends generally for 1 to 28 days, preferably for 1 to 14 days, more preferably for 1 to 10 days, most preferably for 1 to 7 days, after the treatment of the plants with the active ingredients, or for up to 200 days after a seed treatment.
  • the plants listed can particularly advantageously be treated in accordance with the invention with the active compound combinations according to the present invention and the compositions according to the present invention.
  • the active compound combinations according to the invention have an activity which exceeds a sim- pie addition of activities.
  • the improved activity of the active compound combinations according to the invention is evident from the examples below.
  • a synergistic effect is present when the activity of the active compound combinations exceeds the total of the activities of the active compounds when applied individually.
  • the expected activity for a given combination of two active compounds can be calculated as follows (cf. Colby, S.R., "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds 1967, 15, 20- 22):
  • X is the efficacy when active compound A is applied at an application rate of m ppm (or g/ha)
  • Y is the efficacy when active compound B is applied at an application rate of n ppm (or g/ha)
  • the degree of efficacy is expressed in %. 0 % means an efficacy which corresponds to that of the control.
  • the activity of the combination is superadditive, i.e. a synergistic effect exists.
  • the efficacy which was actually observed must be greater than the value for the expected efficacy (E) calculated from the abovementioned formula.
  • the present invention relates to the use of an active compound combination according to the present invention or a composition according to the present invention to control of phytopathogenic fungi in or on a plant, control of phytopathogenic fungi in crop protection, improve vitality of the plant and/or improve plant development (in particular improve plant growth, preferably increase the plant growth rate), enhance pigment content and/or enhance photosynthetic activity (preferably increase chlorophyll content, thereby preferably obtaining greener leaves ("greening") and/or larger leaves (particularly bigger leaf blade)), increase biomass, such as higher fresh weight (FW) and/or dry weight (DW), preferably increase plant weight (particularly higher fruit weight (per fruit) or higher grain weight (per grain) and/or higher overall fruit or higher overall grain yield), and/or increase plant height, increase nutrient content, particularly increase micronutrient content (particularly of , increase macronutrient content (particularly of N, P and/or K), increase protein content (particularly increase of water soluble proteins), increase vitamin content (particularly of vitamins A, Bi, B2, C and/or E
  • the present invention relates to the use of propineb to increase or improve the uptake of micronutrients (preferably one, two, three or more micronutrients selected from the group consisting of Mn, B, Zn, Cu, Fe, Mo, Se, Al, Co and Ni) and/or macronutrients (preferably one, two, or all macronutrients selected from the group consisting of N, P and ) in a plant or by a plant.
  • micronutrients preferably one, two, three or more micronutrients selected from the group consisting of Mn, B, Zn, Cu, Fe, Mo, Se, Al, Co and Ni
  • macronutrients preferably one, two, or all macronutrients selected from the group consisting of N, P and
  • the present invention relates to the use of an active compound combination according to the present invention or a composition according to the present invention for the foliar treatment of a plant or parts thereof, wherein said plant may be a transgenic plant.
  • the present invention relates to the use of an active compound combination according to the present invention or a composition according to the present invention for treating seed, seed of transgenic plants and transgenic plants.
  • the present invention relates to seed treated with an active compound combination according to the present invention or a composition according to the present invention.
  • the present invention relates to a kit of parts, comprising
  • (B2) one or more salts containing manganese (Mn), optionally further comprising instructions for applying constituents (A) and (B) in a manner to obtain an active compound combination according to the present invention or a composition according to the present invention.
  • propineb was used in the form of a wettable powder having a content of 70% by weight of propineb, referred to as Antracol 70WP.
  • Antracol 70WP is commercially available from Bayer CropScience.
  • T2 Antracol 70WP (1250 g / ha)
  • T3 Manganese (0.2%)
  • T7 Manganese (0.2%) + Boron (0.2%)
  • T8 Antracol 70WP (1250 g / ha) + Mn (0.2%) + B (0.2%)
  • T2 Antracol 70WP 79.00 26.80
  • T3 Manganese (Mn) 76.80 25.25
  • T4 Antracol 70WP + Manganese (Mn) 79.40 27.90
  • T6 Antracol 70WP + Boron (B) 78.50 25.10
  • T7 Manganese (Mn) + Boron (B) 77.10 25.20
  • T8 Antracol 70WP + Mn + B 81.20 27.85
  • T2 Antracol 70 WP 33.20 624.60 0.46
  • T3 Manganese (Mn) 29.25 544.92 0.40
  • T4 Antracol 70 WP + Mn 30.50 571.90 0.42
  • T6 Antracol 70 WP + B 29.90 566.47 0.42
  • T7 Manganese (Mn) + Boron (B) 29.55 555.45 0.41
  • T8 Antracol 70 WP + Mn + B 36.00 673.50 0.50
  • T2 Antracol 70 WP 1.27 0.34 1.14 0.020 0.030
  • T4 Antracol 70 WP + Mn 1.38 0.37 1.18 0.025 0.035
  • T6 Antracol 70 WP + B 1.42 0.41 1.17 0.022 0.040
  • T7 Manganese (Mn) + Boron (B) 1.40 0.40 1.06 0.028 0.044
  • T8 Antracol 70 WP + Mn + B 1.55 0.44 1.28 0.033 0.058
  • T8 (Antracol 70WP + Mn + B) recorded higher percentage of N (1.55 %) followed by T6 (Antracol + B: 1.42 %) and T7 (Mn + B: 1.40 %). Higher percentage of P content of 0.44 recorded in the treatment T8 (Antracol 70WP + Mn + B) next to T6 (Antracol 70WP + B: 0.41) which was on par with T7 (Mn + B: 0.40).
  • T8 (Antracol 70WP + Mn + B) recorded higher percentage of Mn (0.033 %) followed by T7 (Mn + B: 0.028 %) and T4 (Antracol 70WP + Mn: 0.025 %).
  • T8 (Antracol 70WP + Mn + B) recorded higher percentage of B (0.058 %) followed by T7 (Mn + B: 0.044 %) and T6 (Antracol 70WP + B: 0.040 %).
  • T2 Antracol 70WP 25.46 13.76
  • T3 Manganese (Mn) 25.88 12.00
  • T4 Antracol 70WP + Mn 26.69 12.60
  • T6 Antracol 70WP + B 26.69 12.48
  • T7 Manganese (Mn) + Boron (B) 26.52 12.24
  • T8 Antracol 70WP + Mn + B 27.35 14.84
  • Crop Growth Rate (g m "2 d "1 )
  • the crop growth rate was calculated during two stages; 60-90 and 90-120 days after planting (DAP) which was attained statistical significance at both stages of crop growth (Table 6).
  • the foliar spray of Antracol 70WP + Mn + B (T8) treated plants recorded higher growth rate of 27.35 and 14.84 g m "2 d "1 during 60-90 and 90-120 DAP respectively.
  • T8 was on par with the treatment Antracol 70 WP + Boron (T6: 26.69 g m 2 d 1 ) and Antracol 70WP + Manganese (T4: 26.69 g m 2 d 1 ) during 60-90 DAP.
  • Untreated control plants recorded a lower growth rate of 24.29 g m "2 d "1 at 60-90 DAP.
  • T2 Antracol 70 WP 27.15 28.23 5.40 25 232 46.46
  • T4 Antracol 70 WP + Mn 27.32 28.40 5.46 27 242 48.46
  • T6 Antracol 70 WP + B 27.46 28.58 5.47 28 245 49.03
  • T8 Antracol 70 WP + Mn + B 27.85 28.96 5.52 29 251 50.21
  • Antracol 70 WP + Mn + B The higher percent increase of 12.1 percent was recorded Antracol 70 WP + Mn + B followed by Antracol 70 WP + B (8.0) and Antracol 70WP + Mn (9.4) over unsprayed control. Again comparing Antracol treatments, Antracol 70WP + Mn + B recorded 8.2 percent fruit yield increment followed by Antracol 70WP + B (5.6) and Antracol 70WP + Mn (4.3) over unsprayed control.
  • T2 Antracol 70 WP 15.66 82.13
  • T4 Antracol 70 WP + Mn 13.42 84.69
  • T6 Antracol 70 WP + B 15.33 82.51
  • T8 Antracol 70 WP + Mn + B 13.22 84.92
  • TSS Total Soluble Solids
  • Foliar spray of Antracol 70WP combination with Mn and B on tomato plants performed well in terms of growth and development with reduced disease incidence tends to finally fruit yield.
  • - Foliar spray of Antracol 70 WP with Mn and B showed 13.4 percent increased root length than unsprayed control in tomato;

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Abstract

The present invention primarily relates to active compound combinations comprising (A) propineb and a constituent (B) comprising (B1) one or more salts containing boron (B), and (B2) one or more salts containing manganese (Mn). More specifically, the active compound combinations according to the invention are useful for improving plant quality. The present invention further relates to corresponding methods and uses of the active compound combinations according to the present invention.

Description

Active compound combinations
The present invention primarily relates to active compound combinations comprising (A) propineb and a constituent (B) comprising (Bl) one or more salts containing boron (B), and (B2) one or more salts containing manganese (Mn). More specifically, the active compound combinations according to the invention are useful for improving plant quality. The present invention further relates to corresponding methods and uses of the active compound combinations according to the present invention.
Propineb of the formula (C5¾N2S4Zn)x is polymeric zinc propylenebis(dithiocarbamate) (CAS Reg No. 12071-83-9) and can be described by the following formula (I)
Propineb is known to have fungicidal properties and can be used for controlling various plant diseases (see e.g. GB 935,981).
WO 20Π/107443 Al teaches the use of propineb for the physiological preventive treatment and curative treatment under zinc deficiency. There, it is also reported that in addition to the physiological curative ef- feet propineb treatment resulted in higher yields. For experimental purposes in the greenhouse, in WO 2011/107443 Al certain plants were sown and grown on rock wool which was fertilized with a Hoagland solution in drip application. Then, after certain time intervals, propineb was applied to the respective plants through spray application.
WO 2012/089724 Al relates to a method for improving plant quality, which method comprises treating the crop plant and/or the locus where the crop plant is growing or is intended to grow and/or the plant propagules with a plant quality improving amount of a micronutrient containing active ingredient.
A poster (http://www.zinccrops2011.org/presentations/2011_zinccrops201 l_goertz_abstract.pdf) with the title "Antracol® - A Fungicide Improving Zinc Nutrition in Plants" was presented at the 3rd International Zinc Symposium in Hyderabad, India in October 2011. Therein, it was concluded that beside its broad-spectrum fungicidal activity, Antracol® (active ingredient: propineb) applied at commercial rates has a pronounced positive influence on growth, development and quality of crops cultivated under Zn deficiency. Antracol® applications can avoid Zn deficiency in plants. The results demonstrate that under disease conditions, when farmers apply fungicides, Antracol® can also provide improved Zn nutrition for plants, reducing the need for Zn fertilization.
DE 25 58 385 Al relates to compositions providing an improving crop yield containing (1) certain dithio- carbamidates and (2) a manganese (Mn) salt of an inorganic or organic acid.
Further, WO 2005/070204 reports the use of micronutrients in pesticide compositions for reducing phyto- toxicity.
The environmental and economic requirements imposed on modern-day crop protection compositions are continually increasing. This does not only relate to, for example, the spectrum of action, to toxicity, to selectivity, to application rate, and the like, but also to improved plant quality, in particular increased yield, and or to improved plant vigor. It has now surprisingly been found that the active compound combinations according to the present invention not only bring about an enhancement of the spectrum of action with respect to phytopathogens to be controlled, but moreover an improved plant quality, in particular increased yield, and/or to an improved plant vigor are achieved. The active compound combinations according to the invention have properties which are synergistic, such as improved properties of the plant, for example better growth, increased harvest yields, a better developed root system, a larger leaf area, greener leaves, stronger shoots, in particular greener leaves.
Accordingly, the present invention relates to active compound combinations comprising:
(A) propineb,
and a constituent (B) comprising
(Bl) one or more salts containing boron (B), and
(B2) one or more salts containing manganese (Mn).
In an active compound combination according to the present invention preferably one, several or all components of constituent (Bl) are selected from the group consisting of boron oxides, and boric acids, and the salts thereof. In an active compound combination according to the present invention preferably one, several or all components of constituent (Bl) are selected from the group consisting of boron trioxide (B2O3), H3BO3, H2B4O7, sodium borates (preferably borax, also known as sodium borate, sodium tetraborate, or disodium tetraborate, preferably anhydrous borax borax pentahydrate or borax decahydrate lOEbO)), potassium borates (preferably K2B4O7, and the hydrates thereof, preferably the tetrahydrate thereof K2B4O7 4H2O), calcium borates (preferably CaB407, Ca3(B03)2, and the hydrates thereof), magnesium borates (preferably MgB/iOv, Mg3(B03)2, and the hydrates thereof), potassium borohydride, sodium borohydride, potassium borotartrate, and nickel (II) borate].
In a preferred active compound combination according to the present invention one, several or all components of constituent (B2) are selected from the group consisting of manganese (II) salts, preferably selected from the group consisting of manganese (II) acetate, manganese (II) sulfate, manganese (II) chloride, manganese (II) nitrate, and manganese (II) phosphate.
In a more preferred active compound combination according to the present invention
constituent (Bl) comprises or consists of disodium tetraborate and/or disodium tetraborate hydrates, and/or
constituent (B2) comprises or consists of manganese (II) sulfate and/or manganese (II) chloride.
If the active constituents in the active compound combinations according to the invention are present in certain weight ratios, the synergistic effect is particularly pronounced.
Thus, in a preferred active compound combination according to the present invention the ratio by weight of constituent (A) to the total weight of boron and manganese of constituent (B) is in the range of 1250 : 1 to 25 : 1, preferably in the range of 1000 : 1 to 50 : 1, more preferably in the range of 500 : 1 to 75 : 1, and particularly preferably in the range of 350 : 1 to 100 : 1 , in each case based on the total weight of the active compound combination.
In a preferred active compound combination according to the present invention the ratio by weight of the total amount of boron [of constituent (Bl)] to the total amount of manganese [of constituent (B2)] is in the range of 3 : 1 to 1 : 3, preferably in the range of 2 : 1 to 1 : 2, more preferably in the range of 3 : 2 to 2 : 3, even more preferably in the range of 4 : 3 to 3 : 4, and most preferably in the range of 5 : 4 to 4 : 5, in each case based on the total weight of the active compound combination.
In a preferred embodiment, an active compound combination according to the present invention further comprises
- one, several or all micronutrients selected from the group consisting of zinc (Zn), copper (Cu), iron (Fe), molybdenum (Mo), selenium (Se), aluminum (Al), cobalt (Co) and nickel (Ni), and/or
one, several or all macronutrients selected from the group consisting of nitrogen (N), phosphorus (P), and potassium (K). Preferably, an active compound combination according to the present invention further comprises
nitrogen (N), phosphorus (P), and potassium (K), and
at least one, preferably two or more, more preferably three or more micronutrients selected from the group consisting of zinc (Zn), copper (Cu), iron (Fe), molybdenum (Mo), selenium (Se), aluminum (Al), cobalt (Co) and nickel (Ni).
An active compound combination according to present invention preferably comprises one or more further components selected from the group consisting of zinc oxide, zinc acetate, zinc benzoate, zinc chloride, zinc citrate, zinc nitrate, zinc salicylate; cupric acetate, cupric butyrate, cupric chlorate, cupric chloride, cupric citrate, cupric gluconate, cupric glycinate, cupric nitrate, cupric salicylate, cuprous acetate, cuprous chloride; ferric chloride, ferric citrate, ferric fructose, ferric glycerophosphate, ferric nitrate, ferric oxide, saccharated ferric oxide, ferrous chloride, ferrous citrate, ferrous fumarate, ferrous gluconate, ferrous succinate; molybdic acid, calcium molybdate, potassium molybdate, sodium molybdate; sodium selenite, potassium selenite, sodium selenate, potassium selenate; aluminum phosphate, aluminum silicate; cobaltic acetate, cobaltous acetate, cobaltous chloride, cobaltous oxalate, cobaltous potassium sulfate, cobaltous sulfate; nickel (II) chloride, and nickel (II) sulfate.
According to the invention the expression "combination" stands for the various combinations of constituents (A) and (B), for example in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active compounds, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other within a short period, preferably within less than two hours.
The present invention relates to the novel method for improving plant quality by applying the active compound combinations according to the present invention to the plants, plant part and/or their habitat.
The term "plant quality" (quality of a plant) is defined as a condition of the crop plant and/or its products which is determined by several aspects alone or in combination with each other such as yield (for example increased biomass, increased content of valuable ingredients and/or improved content or composition of certain ingredients) and plant vigor (for example improved plant growth and/or greener leaves).
One indicator for the quality of a plant, in particular for the condition of the plant is its yield. "Yield" is to be understood as any plant part or product of economic value that is produced by the plant such as grains, leaves, roots, fruits in the proper sense, vegetables, nuts, seeds, wood (e.g. in the case of forestry) or even flowers (e.g. in the case of horticulture and ornamentals). The plant products may in addition be further utilized and/or processed after harvesting. According to the present invention "increased yield" of a crop plant means that the yield of a product of the respective crop plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the micronutrient containing active ingredient. Increased yield can be characterized inter alia by following improved properties of the crop plant:
• increased plant weight,
• increased plant height,
• increased zinc content,
• increased iron content,
• increased calcium content,
• increased biomass such as higher fresh weight (FW) and/or dry weight (DW),
• higher grain yield,
• higher acidity,
• higher anthocyanin content,
• more tillers,
• larger leaves,
• increased shoot growth,
• increased (e.g. of soluble proteins),
• increased oil content,
• increased starch content,
• increased pigment content,
• increased nutrient content,
• increased protein content,
• increased vitamin content (e.g. of Vitamin Bi, B2, C and E),
• increased content of fatty acids,
• increased metabolite content,
• increased carotenoid content (e.g. of Vitamin A),
• increased amount of essential amino acids,
• improved nutrient composition,
• improved protein composition,
• improved composition of fatty acids,
• improved metabolite composition,
• improved carotenoid composition,
• improved sugar composition, • improved amino acids composition,
• improved or optimal fruit color,
• improved leaf color,
• higher storage capacity,
· higher processability of the harvested products.
According to one embodiment of the present invention, depending on the type of improved property, the yield is increased by at least 5 % or more, preferably 10 % or more, more preferably 15 % or more, even more preferably 20 % or more, and even more preferably 25 % or more, in each case compared to the respective untreated control plant. Another indicator for the quality of a plant, in particular for the condition of the crop plant is the "plant vigor". The plant vigor becomes manifest in several aspects such as the general visual appearance and growth. Improved plant vigor can be characterized inter alia by following improved properties of the plant:
• improved vitality of the plant,
· improved plant growth,
• improved plant development,
• improved visual appearance,
• improved plant stand (less plant verse/lodging),
• improved emergence,
· enhanced root growth and/ or more developed root system,
• enhanced nodulation, in particular rhizobial nodulation,
• bigger leaf blade,
• bigger size,
• increased plant weight,
· increased fresh weight (FW),
• increased dry weight (DW),
• increased plant height,
• increased tiller number,
• increased shoot growth,
· increased root growth (extensive root system), increased yield when grown on poor soils or unfavorable climate,
• enhanced photosynthetic activity,
• enhanced pigment content (e.g. Chlorophyll content), • earlier flowering,
• earlier fruiting,
• earlier and improved germination,
• earlier grain maturity,
• better size distribution,
• higher grain hardness,
• improved self-defence mechanisms,
• improved stress tolerance and resistance of the plants against biotic and abiotic stress factors such as fungi, bacteria, viruses, insects, heat stress, cold stress, drought stress, UV stress and/or salt stress,
• less non-productive tillers,
• less dead basal leaves,
• less input needed (such as fertilizers or water),
• greener leaves,
• complete maturation under shortened vegetation periods,
• less fertilizers needed,
• less seeds needed,
• easier harvesting,
• faster and more uniform ripening,
• longer shelf-life,
• longer panicles,
• delay of senescence,
• stronger and/or more productive tillers,
• better extractability of ingredients,
• improved quality of seeds (for being seeded in the following seasons for seed production),
• reduced production of ethylene and/or the inhibition of its reception by the plant,
• higher luminosity,
• more intense color,
• improved texture,
• higher firmness,
• higher brix values.
According to one embodiment of the present invention, depending on the type of improved property, the plant vigor is increased by at least 5 % or more, preferably 10 % or more, more preferably 15 % or more, even more preferably 20 % or more, and even more preferably 25 % or more, in each case compared to the respective untreated control plant. Depending on the treated plant, different quality parameters are more preferably increased than others. In the following some quality parameters are mentioned depending on the treated crop plant.
Preferably, the following plants and plant parts are treated with an active compound combinations according to the present invention: cereals such as wheat, barley, rye, triticale, sorghum/millet and oats, maize, cotton, soy beans, rice, potatoes, sunflowers, beans, coffee, beets (for example sugar beet and fodder beet), peanuts, oilseed rape, fruits (such as apples, pears and citrus fruits), vegetables (such as tomatoes, cucumbers, onions and lettuce), turf and ornamentals (see also below).
The treatment of (seed of) cereals, preferably wheat, barley, rye, triticale and oats, maize and rice is of particularly preferred. Further, plants and plant parts belonging to Solanaceae sp. (e.g. tomatoes, potatoes, peppers, capsicum, aubergines, tobacco), are preferably treated in accordance with the present invention.
According to one embodiment of the invention the preferred quality parameters for potatoes are
• increased protein content (e.g. of soluble proteins),
• increased starch content,
• increased biomass such as higher fresh weight (FW) and/or dry weight (DW),
· increased zinc content,
• better size distribution.
According to one embodiment of the invention the preferred quality parameters for rice are
• increased carotenoid content (e.g. of Vitamin A),
• increased zinc content,
· increased iron content,
• increased protein content (e.g. of soluble proteins),
• improved grain hardness (lower breakability).
According to one embodiment of the invention the preferred quality parameters for wheat are
• increased carotenoid content (e.g. of Vitamin A),
· increased zinc content,
• increased iron content,
• increased protein content (e.g. of soluble proteins),
• improved grain hardness (lower breakability).
According to one embodiment of the invention the preferred quality parameters for corn/maize are · increased carotenoid content (e.g. of Vitamin A),
• increased zinc content, • increased iron content,
• increased protein content (e.g. of soluble proteins),
• increased oil content,
• increased starch content.
According to one embodiment of the invention the preferred quality parameters for apples are
increased zinc content,
increased calcium content,
more intense color,
improved texture,
· higher firmness,
higher brix values.
According to one embodiment of the invention the preferred quality parameters for citrus plants are
increased zinc content,
increased Vitamin C content,
· more intense color,
improved texture,
higher firmness,
higher brix values.
According to one embodiment of the invention the preferred quality parameters for tomatoes, cucumbers and peppers are
better size uniformity,
more intense color,
improved texture,
higher firmness,
· higher brix values,
enhanced root growth,
increased zinc content,
increased calcium content.
According to one embodiment of the invention the preferred quality parameters for grapes/vine are · higher anthocyanin content,
• higher acidity,
• higher zinc content, • higher brix values,
• higher firmness,
• more intense color,
• improved texture,
· better taste.
The present invention further relates to compositions comprising an effective and preferably non-phytotoxic amount of the active compound combinations according to the present invention. These compositions are also suitable for controlling unwanted microorganisms, especially unwanted fungi and bacteria. Said preferably fungicidal compositions comprise agriculturally suitable auxiliaries, solvents, carriers, surfactants and/or extenders. In the context of the present invention, "control of harmful microorganisms" means a reduction in infestation by harmful microorganisms, compared with the untreated plant measured as fungicidal efficacy, preferably a reduction by 25-50 %, compared with the untreated plant, more preferably a reduction by 40-79 %, compared with the untreated plant; even more preferably, the infection by harmful microorganisms is almost completely or entirely suppressed (by 80-100 %). The control of harmful microorganisms may be curative, i.e. for treatment of already infected plants, or protective, i. e. for protection of plants which have not yet been infected.
An "effective but non-phytotoxic amount" means an amount which is sufficient to control the fungal disease of the plant in a satisfactory manner or to eradicate the fungal disease completely, and which, at the same time, does not cause any significant symptoms of phytotoxicity. In general, this application rate may vary within a relatively wide range. It depends on several factors, for example on the fungus to be con- trolled, the plant, the climatic conditions and the constituents of the active compound combinations according to the present invention.
In another aspect, the present invention relates to a composition comprising
(i) an active compound combination according to the present invention, preferably as defined in one of the above-identified preferred embodiments,
(ii) water, and
(iii) one or more adjuvants (auxiliaries), preferably one or more adjuvants selected from the group consisting of organic solvents, surfactants, inorganic carriers, organic carriers, and other extenders.
Preferably, a composition according to the present invention comprises a total amount of
(i) the active compound combination according to the present invention, preferably as defined in one of the above-identified preferred embodiments, in the range of 0.05 to 0.5 wt.%, preferably in the range of 0.1 to 0.3 wt.%, and/or
(ii) water in the range of 70 to 99.9 wt.%, preferably in the range of 85 to 99.8 wt.%,
in each case based on the total weight of the composition.
More preferably, a composition according to the present invention comprises a total amount of
(i) the active compound combination according to the present invention, preferably as defined in one of the above-identified preferred embodiments, in the range of 0.1 to 0.3 wt.%,
and
(ii) water in the range of 70 to 99.9 wt.%, preferably in the range of 85 to 99.8 wt.%,
in each case based on the total weight of the composition. The compositions according to the present invention may be preferably obtained by a method, characterized by the following steps:
(i) providing (A) propineb, (Bl) one or more compounds containing boron (B), and (B2) one or more compounds containing manganese (Mn), or providing an active compound combination according to the present invention, preferably as defined in one of the preferred embodiments,
(ii) providing water,
(iii) providing one or more adjuvants (auxiliaries), preferably one or more adjuvants selected from the group consisting of organic solvents, surfactants, inorganic carriers, organic carriers, and other extenders, and mixing the constituents (i) to (iii), thereby obtaining a composition according to the present invention.
Suitable organic solvents include all polar and non-polar organic solvents usually employed for formulation purposes. Preferable the solvents are selected from ketones, e.g. methyl-isobutyl-ketone and cyclo- hexanone, amides, e.g. dimethyl formamide and alkanecarboxylic acid amides, e.g. N,N-dimethyl decane- amide and Ν,Ν-dimethyl octanamide, furthermore cyclic solvents, e.g. N-methyl-pyrrolidone, N-octyl- pyrrolidone, N-dodecyl-pyrrolidone, N-octyl-caprolactame, N-dodecyl-caprolactame and butyrolactone, furthermore strong polar solvents, e.g. dimethylsulfoxide, and aromatic hydrocarbons, e.g. xylol, Solvesso™, mineral oils, e.g. white spirit, petroleum, alkyl benzenes and spindle oil, also esters, e.g. pro- pyleneglycol-monomethylether acetate, adipic acid dibutylester, acetic acid hexylester, acetic acid hepty- lester, citric acid tri-n-butylester and phfhalic acid di-n-butylester, and also alkohols, e.g. benzyl alcohol and l-methoxy-2-propanol. According to the invention, a carrier is a natural or synthetic, organic or inorganic substance with which the active ingredients are mixed or combined for better applicability, in particular for application to plants or plant parts or seed. The carrier, which may be solid or liquid, is generally inert and should be suitable for use in agriculture. Useful solid or liquid carriers include: for example ammonium salts and natural rock dusts, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock dusts, such as finely divided silica, alumina and natural or synthetic silicates, resins, waxes, solid fertilizers, water, alcohols, especially butanol, organic solvents, mineral and vegetable oils, and derivatives thereof. Mixtures of such carriers can likewise be used. Suitable solid filler and carrier include inorganic particles, e.g. carbonates, silikates, sulphates and oxides with an average particle size of between 0.005 and 20 μηι, preferably of between 0.02 to 10 μηι, for example ammonium sulphate, ammonium phosphate, urea, calcium carbonate, calcium sulphate, magnesium sulphate, magnesium oxide, aluminium oxide, silicium dioxide, so-called fine-particle silica, silica gels, natural or synthetic silicates, and alumosilicates and plant products like cereal flour, wood powder/sawdust and cellulose powder.
Useful solid carriers for granules include: for example crushed and fractionated natural rocks such as cal- cite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic and organic meals, and also granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
Useful liquefied gaseous extenders or carriers are those liquids which are gaseous at standard temperature and under standard pressure, for example aerosol propellants such as halohydrocarbons, and also butane, propane, nitrogen and carbon dioxide.
In the formulations, it is possible to use tackifiers such as carboxymethylcellulose, and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids, such as cephalins and lecithins, and synthetic phospholip- ids. Further additives may be mineral and vegetable oils.
It is also possible to employ organic solvents as auxiliary solvents. Useful liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or dichloromethane, aliphatic hydrocarbons such as cyclohexane or paraffins, for example mineral oil fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl iso- butyl ketone or cyclohexanone, and/or strongly polar solvents such as dimethylformamide and dimethyl sulphoxide. The active compound combinations according to the present invention may additionally comprise further components, for example surfactants. Useful surfactants are emulsifiers and/or foam formers, dispersants or wetting agents having ionic or nonionic properties, or mixtures of these surfactants. Examples of these are salts of poly- acrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycon- densates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols, and derivatives of the compounds containing sulphates, sulphonates and phosphates, for example alkylaryl polyglycol ethers, alkylsulpho- nates, alkylsulphates, arylsulphonates, protein hydrolysates, lignosulphite waste liquors and methylcellulose. The presence of a surfactant is necessary if one of the active ingredients and/or one of the inert carriers is insoluble in water and when application is effected in water. The proportion of surfactants preferably is in the range of 5 and 40 % by weight of the composition according to the present invention.
Suitable surfactants (adjuvants, emulsifiers, dispersants, protective colloids, wetting agent and adhesive) include all common ionic and non-ionic substances, for example ethoxylated nonylphenols, polyalkylene glycolether of linear or branched alcohols, reaction products of alkyl phenols with ethylene oxide and/or propylene oxide, reaction products of fatty acid amines with ethylene oxide and/or propylene oxide, furthermore fattic acid esters, alkyl sulfonates, alkyl sulphates, alkyl ethersulphates, alkyl etherphosphates, arylsulphate, ethoxylated arylalkylphenols, e.g. tristyryl-phenol-ethoxylates, furthermore ethoxylated and propoxylated arylalkylphenols like sulphated or phosphated arylalkylphenol-ethoxylates and -ethoxy- and -propoxylates. Further examples are natural and synthetic, water soluble polymers, e.g. lignosulphonates, gelatine, gum arabic, phospholipides, starch, hydrophobic modified starch and cellulose derivatives, in particular cellulose ester and cellulose ether, further polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrol- idone, polyacrylic acid, polymethacrylic acid and co-polymerisates of (meth)acrylic acid and (meth)acrylic acid esters, and further co-polymerisates of methacrylic acid and methacrylic acid esters which are neu- tralized with alkalimetal hydroxide and also condensation products of optionally substituted naphthalene sulfonic acid salts with formaldehyde.
It is possible to use dyes such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes.
Antifoams which may be present in the formulations include e.g. silicone emulsions, long chain alcohols, fatty acids and their salts as well as fluoroorganic substances and mixtures therof.
Examples of thickeners are polysaccharides, e.g. xanthan gum orveegum, silicates, e.g. attapulgite, bentonite as well as fine-particle silica. If appropriate, it is also possible for other additional components to be present, for example protective colloids, binders, adhesives, thickeners, thixotropic substances, penetrants, stabilizers, sequestrants, com- plexing agents. In general, the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes. The active compound combinations or compositions according to the present invention can be used as such or, depending on their particular physical and/or chemical properties, in the form of their formulations or the use forms prepared therefrom, such as aerosols, capsule suspensions, cold-fogging concentrates, warm- fogging concentrates, encapsulated granules, fine granules, flowable concentrates for the treatment of seed, ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, macrogran- ules, microgranules, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, gas (under pressure), gas generating product, foams, pastes, pesticide coated seed, suspension concentrates, suspoemulsion concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, dusts and granules, water- soluble and water-dispersible granules or tablets, water-soluble and water-dispersible powders for the treatment of seed, wettable powders, natural products and synthetic substances impregnated with active ingredient, and also microencapsulations in polymeric substances and in coating materials for seed, and also ULV cold-fogging and warm- fogging formulations.
The active compound combinations according to the present invention include not only formulations which are already ready for use and can be applied with a suitable apparatus to the plant or the seed, but also commercial concentrates which have to be diluted with water prior to use. Customary applications are for example dilution in water and subsequent spraying of the resulting spray liquor, application after dilution in oil, direct application without dilution, seed treatment or soil application of granules.
The formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one customary extender, solvent or diluent, adjuvant, emulsifier, dispersant, and/or binder or fixative, wetting agent, water repellent, if appropriate desiccants and UV stabilizers and, if appropriate, dyes and pigments, antifoams, preservatives, inorganic and organic thickeners, adhesives, gibberellins and also further processing auxiliaries and also water. Depending on the formulation type to be prepared further processing steps are necessary, e.g. wet grinding, dry grinding and granulation.
The active compound combinations according to the present invention may be present as such or in their (commercially available) formulations and in the use forms prepared from these formulations as a mixture with other (known) active ingredients, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners and/or semiochemicals.
The inventive treatment of the plants and plant parts with the active ingredients or compositions is effected directly or by action on their surroundings, habitat or storage space by the customary treatment meth- ods, for example by dipping, spraying, atomizing, irrigating, evaporating, dusting, fogging, broadcasting, foaming, painting, spreading-on, watering (drenching), drip irrigating and, in the case of propagation material, especially in the case of seeds, also by dry seed treatment, wet seed treatment, slurry treatment, incrustation, coating with one or more coats, etc. It is also possible to deploy the active ingredients by the ultra-low volume method or to inject the active ingredient preparation or the active ingredient itself into the soil.
The active compound combinations or compositions according to the present invention exhibit potent microbicidal activity and can be used for control of unwanted microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials. The invention also relates to a method for controlling unwanted microorganisms, characterized in that an active ingredient combination or composition according to the present invention is applied to the phytopathogenic fungi, phytopathogenic bacteria and/or their habitat.
Fungicides can be used in crop protection for control of phytopathogenic fungi. They are characterized by an outstanding efficacy against a broad spectrum of phytopathogenic fungi, including soilborne pathogens, which are in particular members of the classes Plasmodiophoromycetes, Peronosporomycetes (Syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (Syn. Fungi imper- fecti). Some fungicides are systemically active and ca be used in plant protection as foliar, seed dressing or soil fungicide. Furthermore, they are suitable for combating fungi, which inter alia infest wood or roots of plant. Bactericides can be used in crop protection for control of Pseudomonadaceae, Rhizobiaceae, Enterobac- teriaceae, Corynebacteriaceae and Streptomycetaceae.
Non-limiting examples of pathogens of fungal diseases which can be treated in accordance with the invention include:
diseases caused by powdery mildew pathogens, for example Blumeria species, for example Blumeria graminis; Podosphaera species, for example Podosphaera leucotricha; Sphaerotheca species, for example Sphaerotheca fuliginea; Uncinula species, for example Uncinula necator;
diseases caused by rust disease pathogens, for example Gymnosporangium species, for example Gymnospo- rangium sabinae; Hemileia species, for example Hemileia vastatrix; Phakopsora species, for example Phakopsora pachyrhizi and Phakopsora meibomiae; Puecinia species, for example Puccinia recondite, P. trit- icina, P. graminis or P. striiformis; Uromyces species, for example Uromyces appendiculatus;
diseases caused by pathogens from the group of the Oomycetes, for example Albugo species, for example Algubo Candida; Bremia species, for example Bremia lactucae; Peronospora species, for example Peronospora pisi or P. brassicae; Phytophthora species, for example Phytophthora infestans; Plasmo- para species, for example Plasmopara viticola; Pseudoperonospora species, for example Pseudoperono- spora humuli or Pseudoperonospora cubensis; Pythium species, for example Pythium ultimum;
leaf blotch diseases and leaf wilt diseases caused, for example, by Alternaria species, for example Alternaria solani; Cercospora species, for example Cercospora beticola; Cladiosporium species, for example Cladio- sporium cucumerinum; Cochliobolus species, for example Cochliobolus sativus (conidia form: Drechslera, Syn: Helminthosporium), Cochliobolus miyabeanus; Colletotrichum species, for example Colletotrichum lin- demuthanium; Cycloconium species, for example Cycloconium oleaginum; Diaporthe species, for example Diaporthe citri; Elsinoe species, for example Elsinoe fawcettii; Gloeosporium species, for example Gloeo- sporium laeticolor; Glomerella species, for example Glomerella cingulata; Guignardia species, for example Guignardia bidwelli; Leptosphaeria species, for example Leptosphaeria maculans, Leptosphaeria nodorum; Magnaporthe species, for example Magnaporthe grisea; Microdochium species, for example Microdochium nivale; Mycosphaerella species, for example Mycosphaerella graminicola, M. arachidicola and M. fijiensis; Phaeosphaeria species, for example Phaeosphaeria nodorum; Pyrenophora species, for example Pyrenophora teres, Pyrenophora tritici repentis; Ramularia species, for example Ramularia collo-cygni, Ramularia areola; Rhynchosporium species, for example Rhynchosporium secalis; Septoria species, for example Septoria apii, Septoria lycopersii; Typhula species, for example Typhula incarnata; Venturia species, for example Venturia inaequalis;
root and stem diseases caused, for example, by Corticium species, for example Corticium graminearum; Fusarium species, for example Fusarium oxysporum; Gaeumannomyces species, for example Gaeumannomy- ces graminis; Rhizoctonia species, such as, for example Rhizoctonia solani; Sarocladium diseases caused for example by Sarocladium oryzae; Sclerotium diseases caused for example by Sclerotium oryzae; Tapesia species, for example Tapesia acuformis; Thielaviopsis species, for example Thielaviopsis basicola;
ear and panicle diseases (including com cobs) caused, for example, by Alternaria species, for example Alternaria spp.; Aspergillus species, for example Aspergillus flavus; Cladosporium species, for example Cladosporium cladosporioides; Claviceps species, for example Claviceps purpurea; Fusarium species, for example Fusarium culmorum; Gibberella species, for example Gibberella zeae; Monographella species, for example Monographella nivalis; Septoria species, for example Septoria nodorum;
diseases caused by smut fungi, for example Sphacelotheca species, for example Sphacelotheca reiliana; Tilletia species, for example Tilletia caries, T. controversa; Urocystis species, for example Urocystis oc- culta; Ustilago species, for example Ustilago nuda, U. nuda tritici;
fruit rot caused, for example, by Aspergillus species, for example Aspergillus flavus; Botrytis species, for example Botrytis cinerea; Penicillium species, for example Penicillium expansum and P. purpurogenum; Sclerotinia species, for example Sclerotinia sclerotiorum; Verticilium species, for example Verticilium alboatrum;
seed and soilborne decay, mould, wilt, rot and damping-off diseases caused, for example, by Alternaria species, caused for example by Alternaria brassicicola; Aphanomyces species, caused for example by Aphanomyces euteiches; Ascochyta species, caused for example by Ascochyta lentis; Aspergillus species, caused for example by Aspergillus flavus; Cladosporium species, caused for example by Cladosporium herbarum; Cochliobolus species, caused for example by Cochliobolus sativus; (Conidiaform: Drechslera, Bipolaris Syn: Helminthosporium); Colletotrichum species, caused for example by Colletotrichum coc- codes; Fusarium species, caused for example by Fusarium culmorum; Gibberella species, caused for example by Gibberella zeae; Macrophomina species, caused for example by Macrophomina phaseolina; Monographella species, caused for example by Monographella nivalis; Penicillium species, caused for example by Penicillium expansum; Phoma species, caused for example by Phoma lingam; Phomopsis species, caused for example by Phomopsis sojae; Phytophthora species, caused for example by Phy- tophthora cactorum; Pyrenophora species, caused for example by Pyrenophora graminea; Pyricularia species, caused for example by Pyricularia oryzae; Pythium species, caused for example by Pythium ul- timum; Rhizoctonia species, caused for example by Rhizoctonia solani; Rhizopus species, caused for example by Rhizopus oryzae; Sclerotium species, caused for example by Sclerotium rolfsii; Septoria species, caused for example by Septoria nodorum; Typhula species, caused for example by Typhula incar- nata; Verticillium species, caused for example by Verticillium dahliae;
cancers, galls and witches' broom caused, for example, by Nectria species, for example Nectria galli- gena;
wilt diseases caused, for example, by Monilinia species, for example Monilinia laxa;
leaf blister or leaf curl diseases caused, for example, by Exobasidium species, for example Exobasidium vexans;
Taphrina species, for example Taphrina deformans;
decline diseases of wooden plants caused, for example, by Esca disease, caused for example by Phaemoniella clamydospora, Phaeoacremonium aleophilum and Fomitiporia mediterranea; Eutypa dyeback, caused for example by Eutypa lata ; Ganoderma diseases caused for example by Ganoderma boninense; Rigidoporus dis- eases caused for example by Rigidoporus lignosus;
diseases of flowers and seeds caused, for example, by Botrytis species, for example Botrytis cinerea;
diseases of plant tubers caused, for example, by Rhizoctonia species, for example Rhizoctonia solani;
Helminthosporium species, for example Helminthosporium solani;
Club root caused, for example, by Plasmodiophora species, for example Plamodiophora brassicae; diseases caused by bacterial pathogens, for example Xanthomonas species, for example Xanthomonas campestris pv. oryzae; Pseudomonas species, for example Pseudomonas syringae pv. lachrymans; Er- winia species, for example Erwinia amylovora.
The following diseases of soy beans can be controlled with preference:
Fungal diseases on leaves, stems, pods and seeds caused, for example, by Alternaria leaf spot (Alternaria spec. atrans tenuissima), Anthracnose (Colletotrichum gloeosporoides dematium var. truncatum), brown spot [Sep- toria glycines), cercospora leaf spot and blight (Cercospora kikuchii), choanephora leaf blight (Choanephora infundibulifera trispora (Syn.)), dactuliophora leaf spot {Dactuliophora glycines), downy mildew (Peronospo- ra manshurica), drechslera blight (Drechslera glycini), frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot (Leptosphaerulina trifblii), p yllostica leaf spot (Phyllosticta sojaecola), pod and stem blight (Pho- mopsis sojae), powdery mildew (Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines), rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust (Phakopsora pachyrhizi, Phakopsora mei- bomiae), scab (Sphaceloma glycines), stemphylium leaf blight (Stemphylium botryosum), target spot (Corynespora cassiicola).
Fungal diseases on roots and the stem base caused, for example, by black root rot (Calonectria crotalariae), charcoal rot (Macrophomina phaseolina), fusarium blight or wilt, root rot, and pod and collar rot (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), mycoleptodiscus root rot (Myco- leptodiscus terrestris), neocosmospora (Neocosmospora vasinfecta), pod and stem blight (Diaporthe phaseolorum), stem canker (Diaporthe phaseolorum var. caulivora), phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregatd), pythium rot (Pythium aphanidermatum, Pythium irreg- ulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem decay, and damping-off (Rhizoctonia solani), sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotinia southern blight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).
The active compound combinations or compositions according to the present invention can be used for curative or protective/preventive control of phytopathogenic fungi. The invention therefore also relates to curative and protective methods for controlling phytopathogenic fungi by the use of active compound combinations or compositions according to the present invention, which are applied to the seed, the plant or plant parts, the fruit or the soil in which the plants grow.
The fact that the active ingredients are well tolerated by plants at the concentrations required for controlling plant diseases allows the treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.
According to the invention all plants and plant parts can be treated. By plants is meant all plants and plant populations such as desirable and undesirable wild plants, cultivars and plant varieties (whether or not protectable by plant variety or plant breeder's rights). Cultivars and plant varieties can be plants obtained by conventional propagation and breeding methods which can be assisted or supplemented by one or more biotechnological methods such as by use of double haploids, protoplast fusion, random and directed mutagenesis, molecular or genetic markers or by bioengineering and genetic engineering methods. By plant parts is meant all above ground and below ground parts and organs of plants such as shoot, leaf, blossom and root, whereby for example leaves, needles, stems, branches, blossoms, fruiting bodies, fruits and seed as well as roots, corms and rhizomes are listed. Crops and vegetative and generative propagating material, for example cuttings, corms, rhizomes, runners and seeds also belong to plant parts.
The active compound combinations or compositions according to the present invention have favourable home- otherm toxicity and are well tolerated by the environment, are suitable for protecting plants and plant or- gans, for enhancing harvest yields, for improving the quality of the harvested material. They can preferably be used as crop protection compositions. They are active against normally sensitive and resistant species and against all or some stages of development.
The active compound combinations according to the present invention are also suitable for protecting seed of any plant variety which is used in agriculture, in greenhouses, in forests or in horticulture and viticulture. Plants which can be treated in accordance with the invention include the following main crop plants: maize, soy bean alfalfa, cotton, sunflower, Brassica oil seeds such as Brassica napus (e.g. canola, rapeseed), Brassica ra- pa, B. juncea (e.g. (field) mustard) and Brassica carinata, Arecaceae sp. (e.g. oilpalm, coconut), rice, wheat, sugar beet, sugar cane, oats, rye, barley, millet and sorghum, triticale, flax, nuts, grapes and vine and various fruit and vegetables from various botanic taxa, e.g. Rosaceae sp. (e.g. pome fruits such as apples and pears, but also stone fruits such as apricots, cherries, almonds, plums and peaches, and berry fruits such as strawberries, raspberries, red and black currant and gooseberry), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Ana- cardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp. (e.g. olive tree), Actinidaceae sp., Lauraceae sp. (e.g. avocado, cinnamon camphor), Musaceae sp. (e.g. banana trees and plantations), Rubiaceae sp. (e.g. coffee), Theaceae sp. (e.g. tea), Sterculiceae sp., Rutaceae sp. (e.g. lemons, oranges, mandarins and grapefruit); Solanaceae sp. (e.g. tomatoes, potatoes, peppers, capsicum, aubergines, tobacco), Liliaceae sp., Compositae sp. (e.g. lettuce, artichokes and chicory - including root chicory, endive or common chicory), Umbelliferae sp. (e.g. carrots, parsley, celery and celeriac), Cucurbitaceae sp. (e.g. cucumbers - including gherkins, pumpkins, watermelons, calabashes and melons), Alliaceae sp. (e.g. leeks and onions), Cruciferae sp. (e.g. white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes, horseradish, cress and Chinese cabbage), Leguminosae sp. (e.g. peanuts, peas, lentils and beans - e.g. common beans and broad beans), Che- nopodiaceae sp. (e.g. Swiss chard, fodder beet, spinach, beetroot), Linaceae sp. (e.g. hemp), Cannabeacea sp. (e.g. cannabis), Malvaceae sp. (e.g. okra, cocoa), Papaveraceae (e.g. poppy), Asparagaceae (e.g. asparagus); useful plants and ornamental plants in the garden and woods including turf, lawn, grass and Stevia rebaudiana; and in each case genetically modified types of these plants. The active compound combinations according to the invention also exhibit a potent strengthening effect in plants. Accordingly, they can be used for mobilizing the defences of the plant against attack by undesirable microorganisms. Plant-strengthening (resistance-inducing) substances are to be understood as meaning, in the present context, those substances which are capable of stimulating the defence system of plants in such a way that the treated plants, when subsequently inoculated with undesirable microorganisms, develop a high degree of resistance to these microorganisms. The active compound combinations according to the invention are suitable for increasing the yield of crops.
Further, in context with the present invention plant physiology effects comprise the following:
Abiotic stress tolerance, comprising temperature tolerance, drought tolerance and recovery after drought stress, water use efficiency (correlating to reduced water consumption), flood tolerance, ozone stress and UV tolerance, tolerance towards chemicals like heavy metals, salts, pesticides (safener) etc..
Biotic stress tolerance, comprising increased fungal resistance and increased resistance against nematodes, viruses and bacteria. In context with the present invention, biotic stress tolerance preferably comprises increased fungal resistance and increased resistance against nematodes.
Increased plant vigor, comprising plant health / plant quality and seed vigor, reduced stand failure, im- proved appearance, increased recovery, improved greening effect and improved photosynthetic efficiency.
Effects on plant hormones and/or functional enzymes.
Effects on growth regulators (promoters), comprising earlier germination, better emergence, more developed root system and/or improved root growth, increased ability of tillering, more productive tillers, earlier flowering, increased plant height and/or biomass, shorting of stems, improvements in shoot growth, number of kernels/ear, number of ears/m2, number of stolons and/or number of flowers, enhanced harvest index, bigger leaves, less dead basal leaves, improved phyllotaxy, earlier maturation / earlier fruit finish, homogenous riping, increased duration of grain filling, better fruit finish, bigger fruit vegetable size, sprouting resistance and reduced lodging.
Increased yield, referring to total biomass per hectare, yield per hectare, kernel/fruit weight, seed size and/or hectolitre weight as well as to increased product quality, comprising: improved processability relating to size distribution (kernel, fruit, etc.), homogenous riping, grain moisture, better milling, better vinification, better brewing, increased juice yield, harvestability, digestibility, sedimentation value, falling number, pod stability, storage stability, improved fiber length/strength/uniformity, increase of milk and/or meet quality of silage fed animals, adaption to cooking and frying; further comprising improved marketability relating to improved fruit/grain quality, size distribution (kernel, fruit, etc.), increased storage / shelf-life, firmness / softness, taste (aroma, texture, etc.), grade (size, shape, number of berries, etc.), number of berries/fruits per bunch, crispness, freshness, coverage with wax, frequency of physiological disorders, colour, etc.; further comprising increased desired ingredients such as e.g. protein content, fatty acids, oil content, oil quality, aminoacid composition, sugar content, acid content (pH), sugar/acid ratio (Brix), polyphenols, starch content, nutritional quality, gluten content/index, energy content, taste, etc.; and further comprising decreased undesired ingredients such as e.g. less mycotoxines, less aflatoxines, ge- osmin level, phenolic aromas, laccase, polyphenol oxidases and peroxidases, nitrate content etc. Sustainable agriculture, comprising nutrient use efficiency, especially nitrogen (N)-use efficiency, phosphorus (P)-use efficiency, water use efficiency, improved transpiration, respiration and/or CO2 assimilation rate, better nodulation, improved Ca-metabolism etc..
Delayed senescence, comprising improvement of plant physiology which is manifested, for example, in a longer grain filling phase, leading to higher yield, a longer duration of green leaf colouration of the plant and thus comprising colour (greening), water content, dryness etc.. Accordingly, in the context of the present invention, it has been found that the specific inventive application of the active compound combination makes it possible to prolong the green leaf area duration, which delays the maturation (senescence) of the plant. The main advantage to the farmer is a longer grain filling phase leading to higher yield. There is also an advantage to the farmer on the basis of greater flexibility in the harvesting time. Therein "sedimentation value" is a measure for protein quality and describes according to Zeleny (Zeleny value) the degree of sedimentation of flour suspended in a lactic acid solution during a standard time interval. This is taken as a measure of the baking quality. Swelling of the gluten fraction of flour in lactic acid solution affects the rate of sedimentation of a flour suspension. Both a higher gluten content and a better gluten quality give rise to slower sedimentation and higher Zeleny test values. The sedimentation value of flour depends on the wheat protein composition and is mostly correlated to the protein content, the wheat hardness, and the volume of pan and hearth loaves. A stronger correlation between loaf volume and Zeleny sedimentation volume compared to SDS sedimentation volume could be due to the protein content influencing both the volume and Zeleny value ( Czech J. Food Sci. Vol. 21, No. 3: 91-96, 2000).
Further the "falling number" as mentioned herein is a measure for the baking quality of cereals, especially of wheat. The falling number test indicates that sprout damage may have occurred. It means that changes to the physical properties of the starch portion of the wheat kernel has already happened. Therein, the falling number instrument analyzes viscosity by measuring the resistance of a flour and water paste to a fall- ing plunger. The time (in seconds) for this to happen is known as the falling number. The falling number results are recorded as an index of enzyme activity in a wheat or flour sample and results are expressed in time as seconds. A high falling number (for example, above 300 seconds) indicates minimal enzyme activity and sound quality wheat or flour. A low falling number (for example, below 250 seconds) indicates substantial enzyme activity and sprout-damaged wheat or flour.
The term "more developed root system" / "improved root growth" refers to longer root system, deeper root growth, faster root growth, higher root dry/fresh weight, higher root volume, larger root surface area, bigger root diameter, higher root stability, more root branching, higher number of root hairs, and/or more root tips and can be measured by analyzing the root architecture with suitable methodologies and Image analysis programmes (e.g. WinRhizo).
The term "crop water use efficiency" refers technically to the mass of agriculture produce per unit water consumed and economically to the value of product(s) produced per unit water volume consumed and can e.g. be measured in terms of yield per ha, biomass of the plants, thousand-kernel mass, and the number of ears per m2. The term "nitrogen-use efficiency" refers technically to the mass of agriculture produce per unit nitrogen consumed and economically to the value of product(s) produced per unit nitrogen consumed, reflecting uptake and utilization efficiency.
Improvement in greening / improved colour and improved photo synthetic efficiency as well as the delay of senescence can be measured with well-known techniques such as a HandyPea system (Hansatech). Fv/Fm is a parameter widely used to indicate the maximum quantum efficiency of photosystem II (PSII). This parameter is widely considered to be a selective indication of plant photosynthetic performance with healthy samples typically achieving a maximum Fv/Fm value of approx. 0.85. Values lower than this will be observed if a sample has been exposed to some type of biotic or abiotic stress factor which has reduced the capacity for photochemical quenching of energy within PSII. Fv/Fm is presented as a ratio of variable fluorescence (Fv) over the maximum fluorescence value (Fm). The Performance Index is essentially an indicator of sample vitality (see e.g. Advanced Techniques in Soil Microbiology, 2007, 11, 319-341 ; Applied Soil Ecology, 2000, 15, 169-182.)
The improvement in greening / improved colour and improved photosynthetic efficiency as well as the delay of senescence can also be assessed by measurement of the net photosynthetic rate (Pn), measurement of the chlorophyll content, e.g. by the pigment extraction method of Ziegler and Ehle, measurement of the photochemical efficiency (Fv/Fm ratio), determination of shoot growth and final root and/or canopy biomass, determination of tiller density as well as of root mortality. Within the context of the present invention preference is given to improving plant physiology effects which are selected from the group comprising: enhanced root growth / more developed root system, improved greening, improved water use efficiency (correlating to reduced water consumption), improved nutrient use efficiency, comprising especially improved nitrogen (N)-use efficiency, delayed senescence and enhanced yield.
Within the enhancement of yield preference is given as to an improvement in the sedimentation value and the falling number as well as to the improvement of the protein and sugar content - especially with plants selected from the group of cereals (preferably wheat).
Preferably the novel use of the fungicidal compositions of the present invention relates to a combined use of a) preventively and/or curatively controlling pathogenic fungi and/or nematodes, with or without resistance management, and b) at least one of enhanced root growth, improved greening, improved water use efficiency, delayed senescence and enhanced yield. From group b) enhancement of root system, water use efficiency and N-use efficiency is particularly preferred.
The active compound combinations or compositions according to the present invention are also suitable for treating seeds. A large part of the damage to crop plants caused by haimful organisms is triggered by the infection of the seed during storage or after sowing, and also during and after germination of the plant. This phase is particularly critical since the roots and shoots of the growing plant are particularly sensitive, and even minor damage may result in the death of the plant. There is therefore a great interest in protecting the seed and the germinating plant by using appropriate compositions. The control of phytopathogenic fungi by treating the seed of plants has been known for a long time and is the subject of constant improvements. However, the treatment of seed entails a series of problems which cannot always be solved in a satisfactory manner. For instance, it is desirable to develop methods for protecting the seed and the gemrinating plant, which dispense with, or at least significantly reduce, the additional deployment of crop protection compositions after planting or after emergence of the plants. It is also desirable to optimize the amount of the active ingredient used so as to provide the best possible protection for the seed and the germinating plant from attack by phytopathogenic fungi, but without damaging the plant itself by the active ingredient employed. In particular, methods for the treatment of seed should also take account of the intrinsic fungicidal properties of transgenic plants in order to achieve optimal protection of the seed and the germinating plant with a minimum expenditure of crop protection compositions. The present invention therefore also relates to a method for protection of seed and germinating plants from attack by phytopathogenic fungi, by treating the seed with an active compound combination or composition according to the present invention. The invention likewise relates to the use of the active compound combinations or compositions according to the present invention for treatment of seed to protect the seed and the ger- minating plant from phytopathogenic fungi. The invention further relates to seed which has been treated with an active compound combination or composition according to the present invention for protection from phytopathogenic fungi.
The control of phytopathogenic fungi which damage plants post-emergence is effected primarily by treating the soil and the above-ground parts of plants with crop protection compositions. Owing to the concerns regarding a possible influence of the crop protection compositions on the environment and the health of humans and animals, there are efforts to reduce the amount of active ingredients deployed.
One of the advantages of the present invention is that the particular systemic properties of the active compound combinations or compositions according to the present invention mean that treatment of the seed with said active ingredients and compositions not only protects the seed itself, but also the resulting plants after emergence, from phytopathogenic fungi. In this way, the immediate treatment of the crop at the time of sowing or shortly thereafter can be dispensed with.
It is likewise considered to be advantageous that an active compound combination or composition according to the present invention can especially also be used with transgenic plants and/or seeds, in which case the plant or the plant growing from this seed is capable of expressing a protein which acts against pests. By virtue of the treatment of such seed with the active compound combinations or compositions according to the present invention, merely the expression of the protein, for example an insecticidal protein, can control certain pests. Surprisingly, a further synergistic effect can be observed in this case, which additionally increases the effectiveness for protection against attack by pests. As also described below, the treatment of transgenic plants or seeds with an active compound combination or composition according to the present invention is of particular significance. This relates to the seed of plants containing at least one heterologous gene. Definition and examples of suitable heterologous genes are given below.
In the context of the present invention, an active compound combination or composition according to the pre- sent invention is applied to the seed alone or in a suitable formulation. Preferably, the seed is treated in a state in which it is sufficiently stable for no damage to occur in the course of treatment. In general, the seed can be treated at any time between harvest and sowing. It is customary to use seed which has been separated from the plant and freed from cobs, shells, stalks, coats, hairs or the flesh of the fruits. For example, it is possible to use seed which has been harvested, cleaned and dried down to a moisture content of less than 15 % by weight. Alternatively, it is also possible to use seed which, after drying, for example, has been treated with water and then dried again. When treating the seed, care must generally be taken that the amount of the active compound combination or composition according to the present invention applied to the seed and/or the amount of further additives is selected such that the germination of the seed is not impaired, or that the resulting plant is not damaged. This has to be borne in mind in particular in the case of active ingredients which can have phytotoxic effects at certain application rates.
The active compound combinations according to the present invention can be applied directly, i.e. without containing any other components and without having been diluted. In general, it is preferable to apply the compositions to the seed in the form of a suitable formulation. Suitable formulations and methods for seed treatment are known to those skilled in the art and are described, for example, in the following documents: US 4,272,417, US 4,245,432, US 4,808,430, US 5,876,739, US 2003/0176428 Al, WO 2002/080675, WO 2002/028186.
The active ingredients usable in accordance with the invention can be converted to the customary seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other coating compositions for seed, and also ULV formulations.
These formulations are prepared in a known manner, by mixing the active ingredients with customary additives, for example customary extenders and also solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins and also water.
Useful dyes which may be present in the seed dressing formulations usable in accordance with the invention are all dyes which are customary for such purposes. It is possible to use either pigments, which are sparingly soluble in water, or dyes, which are soluble in water. Examples include the dyes known by the names Rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1.
Useful wetting agents which may be present in the seed dressing formulations usable in accordance with the invention are all substances which promote wetting and which are conventionally used for the formulation of active agrochemical ingredients. Preference is given to using alkyl naphthalenesulphonates, such as diisopropyl or diisobutyl naphthalenesulphonates. Useiul dispersants and/or emulsifiers which may be present in the seed dressing formulations usable in accordance with the invention are all nonionic, anionic and cationic dispersants conventionally used for the formulation of active agrochemical ingredients. Usable with preference are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants. Suitable nonionic dispersants include especially ethylene oxide/propylene oxide block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ether, and the phosphated or sul- phated derivatives thereof. Suitable anionic dispersants are especially lignosulphonates, polyacrylic acid salts and arylsulphonate/formaldehyde condensates. Antifoams which may be present in the seed dressing formulations usable in accordance with the invention are all foam-inhibiting substances conventionally used for the formulation of active agrochemical ingredients. Silicone antifoams and magnesium stearate can be used with preference.
Preservatives which may be present in the seed dressing formulations usable in accordance with the invention are all substances usable for such purposes in agrochemical compositions. Examples include dichlorophene and benzyl alcohol hemiformal.
Secondary thickeners which may be present in the seed dressing formulations usable in accordance with the invention are all substances usable for such purposes in agrochemical compositions. Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica. Adhesives which may be present in the seed dressing formulations usable in accordance with the invention are all customary binders usable in seed dressing products. Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.
The gibberellins which may be present in the seed dressing formulations usable in accordance with the invention may preferably be gibberellins Al, A3 (= gibberellic acid), A4 and A7; particular preference is given to using gibberellic acid.
The seed dressing formulations usable in accordance with the invention can be used, either directly or after previously having been diluted with water, for the treatment of a wide range of different seed, including the seed of transgenic plants. In this case, additional synergistic effects may also occur in interaction with the substances formed by expression. For treatment of seed with the seed dressing formulations usable in accordance with the invention, or the preparations prepared therefrom by adding water, all mixing units usable customarily for the seed dressing are useful. Specifically, the procedure in the seed dressing is to place the seed into a mixer, to add the particular desired amount of seed dressing formulations, either as such or after prior dilution with water, and to mix everything until the formulation is distributed homogeneously on the seed. If appropriate, this is followed by a drying pro- cess.
The active compound combinations or compositions according to the present invention can also be used in the protection of materials, for protection of industrial materials against attack and destruction by unwanted microorganisms, for example fungi and insects.
In addition, the active compound combinations according to the present invention can be used as antifouling compositions, alone or in combinations with other active ingredients. Industrial materials in the present context are understood to mean inanimate materials which have been prepared for use in industry. For example, industrial materials which are to be protected by active compound combinations or compositions according to the present invention from microbial alteration or destruction may be adhe- sives, glues, paper, wallpaper and board/cardboard, textiles, carpets, leather, wood, fibers and tissues, paints and plastic articles, cooling lubricants and other materials which can be infected with or destroyed by microorganisms. Parts of production plants and buildings, for example cooling-water circuits, cooling and heating systems and ventilation and air-conditioning units, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected. Industrial materials within the scope of the present invention preferably include adhesives, sizes, paper and card, leather, wood, paints, cooling lubri- cants and heat transfer fluids, more preferably wood.
The active compound combinations or compositions according to the present invention may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
In the case of treatment of wood the active compound combinations according to the invention may also be used against fungal diseases liable to grow on or inside timber. The term "timber" means all types of species of wood, and all types of working of this wood intended for construction, for example solid wood, high-density wood, laminated wood, and plywood. The method for treating timber according to the invention mainly consists in contacting one or more compounds according to the invention or a composition according to the invention; this includes for example direct application, spraying, dipping, injection or any other suitable means. In addition, the active compound combinations according to the invention can be used to protect objects which come into contact with saltwater or brackish water, especially hulls, screens, nets, buildings, moorings and signalling systems, from fouling.
The inventive method for controlling unwanted fungi can also be employed for protecting storage goods. Storage goods are understood to mean natural substances of vegetable or animal origin or processed products thereof which are of natural origin, and for which long-term protection is desired. Storage goods of vegetable origin, for example plants or plant parts, such as stems, leaves, tubers, seeds, fruits, grains, can be protected freshly harvested or after processing by (pre)drying, moistening, comminuting, grinding, pressing or roasting. Storage goods also include timber, both unprocessed, such as construction timber, electricity poles and barriers, or in the form of finished products, such as furniture. Storage goods of ani- mal origin are, for example, hides, leather, furs and hairs. The active compound combinations or compositions according to the present invention may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould. Microorganisms capable of degrading or altering the industrial materials include, for example, bacteria, fungi, yeasts, algae and slime organisms. The active compound combinations or compositions according to the present invention preferably act against fungi, especially moulds, wood-discoloring and wood-destroying fungi (Asco- mycetes, Basidiomycetes, Deuteromycetes and Zygomycetes), and against slime organisms and algae. Exam- pies include microorganisms of the following genera: Alternaria, such as Alternaria tenuis; Aspergillus, such as Aspergillus niger; Chaetomium, such as Chaetomium globosum; Coniophora, such as Coniophora puetana; Lentinus, such as Lentinus tigrinus; Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans; Sclerophoma, such as Sclerophoma pityophila; Trichoderma, such as Trichoderma viride; Ophiostoma spp., Ceratocystis spp., Humicola spp., Petriella spp., Trichurus spp., Coriolus spp., Gloeophyllum spp., Pleurotus spp., Porta spp., Serpula spp. and Tyromyces spp., Cladosporium spp., Paecilomyces spp. Mucor spp., Escherichia, such as Escherichia coli; Pseudomo- nas, such as Pseudomonas aeruginosa; Staphylococcus, such as Staphylococcus aureus, Candida spp. and Saccharomyces spp., such as Saccharomyces cerevisae.
In addition, the active compound combinations or compositions according to the present invention also have very good antimycotic activity. They have a very broad antimycotic activity spectrum, especially against dermatophytes and yeasts, moulds and diphasic fungi (for example against Candida species, such as C. albicans, C. glabrata), and Epidermophyton floccosum, Aspergillus species, such as A. niger and A. fumigatus, Trichophyton species, such as T. mentagrophytes, Microsporon species such as M. canis and M. audouinii. The list of these fungi by no means constitutes a restriction of the mycotic spectrum covered, and is merely of illus- trative character.
The active compound combinations or compositions according to the present invention can therefore be used both in medical and in non-medical applications.
As already mentioned above, it is possible to treat all plants and their parts in accordance with the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and also parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The terms "parts" or "parts of plants" or "plant parts" have been explained above. More preferably, plants of the plant cultivars which are commercially available or are in use are treated in accordance with the invention. Plant cultivars are understood to mean plants which have new properties ("traits") and have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, bio- or genotypes. The method of treatment according to the invention can be used in the treatment of genetically modified organisms (GMOs), e.g. plants or seeds. Genetically modified plants (or transgenic plants) are plants of which a heterologous gene has been stably integrated into genome. The expression "heterologous gene" essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mito- chondrial genome gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, cosuppression technology, RNA interference - RNAi - technology or microRNA - miRNA - technology). A heterologous gene that is located in the genome is also called a transgene. A transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive ("synergistic") effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the active compounds and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, bigger fruits, larger plant height, greener leaf color, earlier flowering, higher quality and/or a higher nutritional value of the harvested products, higher sugar concentration within the fruits, better storage stability and/or pro- cessability of the harvested products are possible, which exceed the effects which were actually to be expected. The active compound combinations according to the invention also have a strengthening effect in plants. Accordingly, they are also suitable for mobilizing the defense system of the plant against attack by unwanted microorganisms. This may, if appropriate, be one of the reasons of the enhanced activity of the active compound combinations according to the invention. Plant-strengthening (resistance-inducing) substances are to be understood as meaning, in the present context, those substances or combinations of sub- stances which are capable of stimulating the defense system of plants in such a way that, when subsequently inoculated with unwanted microorganisms, the treated plants display a substantial degree of resistance to these microorganisms. In the present case, unwanted microorganisms are to be understood as meaning phytopathogenic fungi, bacteria and viruses. Thus, the substances according to the invention can be employed for protecting plants against attack by the abovementioned pathogens within a certain period of time after the treatment. The period of time within which protection is effected generally extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds.
Plants and plant cultivars which are preferably to be treated according to the invention include all plants which have genetic material which impart particularly advantageous, useful traits to these plants (whether obtained by breeding and/or biotechnological means). Plants and plant cultivars which are also preferably to be treated according to the invention are resistant against one or more biotic stresses, i.e. said plants show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.
Examples of nematode or insect resistant plants are for example those mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al.
Plants and plant cultivars which may also be treated according to the invention are those plants which are resistant to one or more abiotic stresses. Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.
Plants and plant cultivars which may also be treated according to the invention, are those plants characterized by enhanced yield characteristics. Increased yield in said plants can be the result of, for example, improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germi- nation efficiency and accelerated maturation. Yield can furthermore be affected by improved plant architecture (under stress and non-stress conditions), including but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance. Further yield traits include seed composition, such as carbohydrate content, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability.
Plants that may be treated according to the invention are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stresses). Such plants are typically made by crossing an inbred male-sterile par- ent line (the female parent) with another inbred male-fertile parent line (the male parent). Hybrid seed is typically harvested from the male sterile plants and sold to growers. Male sterile plants can sometimes (e.g. in corn) be produced by detasseling, i.e. the mechanical removal of the male reproductive organs (or males flowers) but, more typically, male sterility is the result of genetic determinants in the plant genome. In that case, and especially when seed is the desired product to be harvested from the hybrid plants it is typically useful to ensure that male fertility in the hybrid plants is fully restored. This can be accomplished by ensuring that the male parents have appropriate fertility restorer genes which are capable of restoring the male fertility in hybrid plants that contain the genetic determinants responsible for male- sterility. Genetic determinants for male sterility may be located in the cytoplasm. Examples of cytoplas- mic male sterility (CMS) were for instance described in Brassica species (WO 92/05251, WO 95/09910, WO 98/27806, WO 2005/002324, WO 2006/021972 and US 6,229,072). However, genetic determinants for male sterility can also be located in the nuclear genome. Male sterile plants can also be obtained by plant biotechnology methods such as genetic engineering. A particularly useful means of obtaining male- sterile plants is described in WO 89/10396 in which, for example, a ribonuclease such as barnase is selectively expressed in the tapetum cells in the stamens. Fertility can then be restored by expression in the ta- petum cells of a ribonuclease inhibitor such as barstar (e.g. WO 91/02069).
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated according to the invention are herbicide-tolerant plants, i.e. plants made tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation, or by selection of plants containing a mutation imparting such herbicide tolerance.
Herbicide-resistant plants are for example glyphosate-tolerant plants, i.e. plants made tolerant to the herbicide glyphosate or salts thereof. Plants can be made tolerant to glyphosate through different means, for example those mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al . Other herbicide resistant plants are for example plants that are made tolerant to herbicides inhibiting the enzyme glutamine synthase, such as bialaphos, phosphinothricin or glufosinate. Such plants can be obtained for example by methods mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al.
Further herbicide-tolerant plants are also plants that are made tolerant to the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase (HPPD). HPPD is an enzyme that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is transformed into homogentisate. Plants tolerant to HPPD- inhibitors can be transformed with a gene encoding a naturally-occurring resistant HPPD enzyme, or a gene encoding a mutated or chimeric HPPD enzyme, for example as mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al.
Still further herbicide resistant plants are plants that are made tolerant to aceto lactate synthase (ALS) inhibitors. Known ALS -inhibitors include, for example, sulfonylurea, imidazolinone, triazolopyrimidines, piyimidinyoxy- (thio)benzoates, and/or sulfonylaminocarbonyltriazolinone herbicides. Different mutations in the ALS enzyme (also known as acetohydroxyacid synthase, AHAS) are known to confer tolerance to different herbicides and groups of herbicides (see the corresponding references mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al.
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are insect-resistant transgenic plants, i.e. plants made re- sistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance.
An "insect-resistant transgenic plant", as used herein, in particular relates to the insect-resistant transgenic plants mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al. Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance. Particularly useful stress tolerance plants are those mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al. Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product such those from transgenic plants mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al. Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Bras- sica plants, with altered oil profile characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered oil profile characteristics and include the oilseed rape plants mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al. Particularly useful transgenic plants which may be treated according to the invention are plants containing transformation events, or combination of transformation events, that are the subject of petitions for non- regulated status, in the United States of America, to the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA) whether such petitions are granted or are still pending.
Particularly useful transgenic plants which may be treated according to the invention are plants containing transformation events, or a combination of transformation events, are those mentioned in WO 2012/ 045798 Al and WO 2012/089757 Al. In a preferred embodiment, the present invention relates to a method for achieving one, several or all of the following effects: control of phytopathogenic fungi in or on a plant, control of phytopathogenic fungi in crop protection, improve vitality of the plant and/or improve plant development (in particular improve plant growth, preferably increase the plant growth rate), enhance pigment content and/or enhance photosynthetic activity (preferably increase chlorophyll content, thereby preferably obtaining greener leaves ("greening") and/or larger leaves (particularly bigger leaf blade)), increase biomass, such as higher fresh weight (FW) and/or dry weight (DW), preferably increase plant weight (particularly higher fruit weight (per fruit) or higher grain weight (per grain) and/or higher overall fruit or higher overall grain yield), and/or increase plant height, - increase nutrient content, particularly increase micronutrient content (particularly of , increase macronutrient content (particularly of N, P and/or K), increase protein content (particularly increase of water soluble proteins), increase vitamin content (particularly of vitamins A, Bi, B2, C and/or E), and/or increase amount of essential amino acids, characterized in that an active compound combination according to the present invention or a composition according to the present invention is applied to seeds, to plants, to plant parts (preferably fruits and/or leaves), or to the soil on which plants grow or are supposed to grow.
The effects observed in the context of the present invention were particularly observed in the foliar treatment of a plant or parts thereof with an active compound combination according to the present invention (as defined above, preferably in one of the preferred embodiments) or a composition according to the present in- vention (as defined above, preferably in one of the prefened embodiments).
When using the active compound combinations or compositions according to the present invention the application rates can be varied within a relatively wide range, depending on the kind of application. In a preferred method according to the present invention, the active compound combination according to the present invention or the composition according to the present invention is applied to seeds or leaves, wherein in the application the amount of the active compound combination on leaves is in the range of from 400 to 3000 g/ha (preferably of from 500 to 2500 g/ha, more preferably of from 600 to 2000 g/ha, and even more preferably of from 700 to 1700 g/ha), and in the treatment of seeds in the range of from 2 to 200 g per 100 kg of seeds, preferably of from 5 to 150 g per 100 kg of seeds, more preferably of from 10 to 100 g per 100 kg of seeds. The active compound combinations according to the present invention or compositions according to the present invention can be used to protect plants from attack by the pathogens mentioned for a certain period of time after treatment. The period for which protection is provided extends generally for 1 to 28 days, preferably for 1 to 14 days, more preferably for 1 to 10 days, most preferably for 1 to 7 days, after the treatment of the plants with the active ingredients, or for up to 200 days after a seed treatment.
The plants listed can particularly advantageously be treated in accordance with the invention with the active compound combinations according to the present invention and the compositions according to the present invention. The active compound combinations according to the invention have an activity which exceeds a sim- pie addition of activities. The improved activity of the active compound combinations according to the invention is evident from the examples below.
A synergistic effect is present when the activity of the active compound combinations exceeds the total of the activities of the active compounds when applied individually.
The expected activity for a given combination of two active compounds can be calculated as follows (cf. Colby, S.R., "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds 1967, 15, 20- 22):
If
X is the efficacy when active compound A is applied at an application rate of m ppm (or g/ha), Y is the efficacy when active compound B is applied at an application rate of n ppm (or g/ha), E is the efficacy when the active compounds A and B are applied at application rates of m and n ppm (or g/ha), respectively, and then E = X + Y - ^—?- 100 The degree of efficacy is expressed in %. 0 % means an efficacy which corresponds to that of the control.
If the observed activity exceeds the calculated value, then the activity of the combination is superadditive, i.e. a synergistic effect exists. In this case, the efficacy which was actually observed must be greater than the value for the expected efficacy (E) calculated from the abovementioned formula.
In another aspect, the present invention relates to the use of an active compound combination according to the present invention or a composition according to the present invention to control of phytopathogenic fungi in or on a plant, control of phytopathogenic fungi in crop protection, improve vitality of the plant and/or improve plant development (in particular improve plant growth, preferably increase the plant growth rate), enhance pigment content and/or enhance photosynthetic activity (preferably increase chlorophyll content, thereby preferably obtaining greener leaves ("greening") and/or larger leaves (particularly bigger leaf blade)), increase biomass, such as higher fresh weight (FW) and/or dry weight (DW), preferably increase plant weight (particularly higher fruit weight (per fruit) or higher grain weight (per grain) and/or higher overall fruit or higher overall grain yield), and/or increase plant height, increase nutrient content, particularly increase micronutrient content (particularly of , increase macronutrient content (particularly of N, P and/or K), increase protein content (particularly increase of water soluble proteins), increase vitamin content (particularly of vitamins A, Bi, B2, C and/or E), and/or increase amount of essential amino acids.
In another aspect, the present invention relates to the use of propineb to increase or improve the uptake of micronutrients (preferably one, two, three or more micronutrients selected from the group consisting of Mn, B, Zn, Cu, Fe, Mo, Se, Al, Co and Ni) and/or macronutrients (preferably one, two, or all macronutrients selected from the group consisting of N, P and ) in a plant or by a plant.
In another aspect, the present invention relates to the use of an active compound combination according to the present invention or a composition according to the present invention for the foliar treatment of a plant or parts thereof, wherein said plant may be a transgenic plant. In another aspect, the present invention relates to the use of an active compound combination according to the present invention or a composition according to the present invention for treating seed, seed of transgenic plants and transgenic plants.
In a further aspect the present invention relates to seed treated with an active compound combination according to the present invention or a composition according to the present invention. In another aspect the present invention relates to a kit of parts, comprising
(A) propineb,
and a constituent (B) comprising
(Bl) one or more salts containing boron (B), and
(B2) one or more salts containing manganese (Mn), optionally further comprising instructions for applying constituents (A) and (B) in a manner to obtain an active compound combination according to the present invention or a composition according to the present invention.
Examples:
The effect of propineb in combination with Mn and B was assessed on growth characteristics and physiological changes were assessed. Additionally the nutrio-physiological changes as well as the effects on disease management, yield and quality of the crop produce due to said treatment were assessed. In the following experiments propineb was used in the form of a wettable powder having a content of 70% by weight of propineb, referred to as Antracol 70WP. Antracol 70WP is commercially available from Bayer CropScience.
The experiments were conducted in a field in Tamil Nadu, Coimbatore District, India.
Crop : Tomato Plot area : 50 m2
Replications : Three
Spacing : 45 x 30 cm
Treatments : Eight
No. of sprays : Two sprays: 35 DAP (Days After Planting) and 45 DAP Treatment details:
Following treatments were employed in the experiments: Tl : Control
T2: Antracol 70WP (1250 g / ha) T3: Manganese (0.2%)
T4: Antracol 70WP (1250 g / ha) + Manganese (0.2%)
T5 Boron (0.2%)
T6: Antracol 70WP (1250 g / ha) + Boron (0.2%)
T7: Manganese (0.2%) + Boron (0.2%) T8: Antracol 70WP (1250 g / ha) + Mn (0.2%) + B (0.2%)
Good quality water was used for foliar spray (pH: 7.3)
The morphological observations in terms of plant height, root length, leaf number and leaf area as well as measurement of leaf chlorophyll index using SPAD meter were taken at 20 day after second spray. Be- sides, yield and its components were also recorded at the time of harvest. In addition, disease scoring (Early and late blight of tomato) and plant nutrient status also were recorded. The results of various parameters in different treatments are given in the respective tables.
The data collected were subjected to statistical analysis in the Randomized complete block design using ANOVA Package (AGRES version 7.01).
Field layout used
Table 1 : Initial soil parameters used in the experiments (before treatment)
Particulars values pH (1 : 2 of soil : water) 7.43
Electrical conductivity (dS m ) 0.51
N (kg ha 1) 278.20
P (kg ha ) 21.43
K kg ha 1) 280.57
Mn (g ha 1) 2.19
EKg ha4) 1.18
Table 2: Effect of Propineb, Mn and B on growth aspects of tomato Plant Height Root length
Treatment (cm)
(cm)
Tl : Control 77.50 24.55
T2: Antracol 70WP 79.00 26.80
T3: Manganese (Mn) 76.80 25.25
T4: Antracol 70WP + Manganese (Mn) 79.40 27.90
T5: Boron (B) 77.70 24.50
T6: Antracol 70WP + Boron (B) 78.50 25.10
T7: Manganese (Mn) + Boron (B) 77.10 25.20
T8: Antracol 70WP + Mn + B 81.20 27.85
Growth parameters
Regarding growth parameters, the plant height did not attained statistical significance (Table 2). The foliar spray of Antracol 70 WP with Mn and B showed taller plants (81.20 cm) followed by Antracol 70 WP + Mn (T4: 79.40 cm) and Antracol 70WP (T2: 79.00 cm). Comparatively smaller plants were observed in the foliar spray of Manganese alone (T3). In case of root length, significantly superior root length of 27.90 cm was recorded in the treatment T4 receiving Antracol 70WP + Mn which was on par with the treatment T8 (Antracol 70WP + Mn + B). The lowest value of 24.55 cm was recorded in the treatment unsprayed control.
Table 3: Effect of Propineb, Mn and B on tomato leafs
No. of leaves Leaf area
Treatment
plant"1 (cm2 plant"1)
Tl : Control 28.65 535.76 0.40
T2: Antracol 70 WP 33.20 624.60 0.46 T3 : Manganese (Mn) 29.25 544.92 0.40
T4: Antracol 70 WP + Mn 30.50 571.90 0.42
T5: Boron (B) 28.52 530.39 0.39
T6: Antracol 70 WP + B 29.90 566.47 0.42
T7: Manganese (Mn) + Boron (B) 29.55 555.45 0.41
T8: Antracol 70 WP + Mn + B 36.00 673.50 0.50
Leaf characteristics
All the leaf characteristics attained statistical significance (Table 3). Regarding leaf number, Antracol 70WP + Mn + B foliar spray showed higher number of leaves (36) which was significantly superior to the other treatments. With respect to leaf area and leaf area index (LAI), Antracol 70WP + Mn + B treated plants recorded higher leaf area of 673.50 cm2 plant"1 correspond to the LAI (T8: 0.50) followed by Antracol 70WP (624.60 cm2 plant4 and 0.46). The lesser leaf area of 530.39 cm2 plant 1 and LAI (0.39) were noticed in the treatment with foliar spray of boron alone (T5).
Table 4: Effect of Propineb, Mn and B on biochemical parameters of tomato
Water soluble IAA oxidase activity
Chlorophyll protein
Treatment
index ^g of unoxidised auxin
(mg g"1) g 1 h"1)
Tl : Control
38.6 9.1 15.85
T2: Antracol 70 WP
45.5 9.8 15.73
T3 : Manganese (Mn)
38.5 9.3 12.32
T4: Antracol 70 WP + Mn
45.7 10.2 13.24
T5: Boron (B)
39.2 9.7 14.78
T6: Antracol 70 WP + B
45.6 10.5 14.75
T7: Manganese (Mn) + Boron (B)
40.1 9.9 12.38
T8: Antracol 70 WP + Mn + B
47.7 11.3 12.42
Biochemical parameters
Respect to the biochemical parameters, all the parameters attained statistical significance (Table 4). Significantly higher chlorophyll index value recorded in the treatment Antracol 70WP + Mn + B (47.7) fol- lowed by Antracol 70WP + Manganese (45.7), Antracol 70WP + Boron (45.6) and Antracol 70WP (45.5). With regard to soluble protein, Antracol 70WP + Mn + B sprayed plants showed higher soluble protein content of 11.3 mg g4 followed by Antracol 70WP + B (10.5 mg g4) and Antracol 70WP + Mn (10.2 mg g4). Consider with IAA oxidase activity in terms of unoxidised auxin content, the control recorded higher unoxidised auxin content of 15.85 μg g4 h4 which was close to the treatment T2 receiving Antracol 70WP alone (15.73 μg g4 h4). The treatments with Mn showed higher IAA oxidase activity (Low unoxidised auxin content) in which Mn alone showed higher activity (12.32) followed by Mn + B (T7) and Antracol + Mn + B (T8).
Table 5: Effect of Propineb, Mn and B on plant nutrient content of tomato Potassium
Nitrogen Phosphorus Boron
Manganese
Treatment Content Content
Content Content Content
(%)
(%) (%) (%)
(%)
Tl : Control 1.20 0.32 0.93 0.018 0.028
T2: Antracol 70 WP 1.27 0.34 1.14 0.020 0.030
T3 : Manganese (Mn) 1.32 0.35 1.01 0.023 0.031
T4: Antracol 70 WP + Mn 1.38 0.37 1.18 0.025 0.035
T5: Boron (B) 1.33 0.39 1.03 0.020 0.036
T6: Antracol 70 WP + B 1.42 0.41 1.17 0.022 0.040
T7: Manganese (Mn) + Boron (B) 1.40 0.40 1.06 0.028 0.044
T8: Antracol 70 WP + Mn + B 1.55 0.44 1.28 0.033 0.058
In case of nutrient status, all the nutrients attained statistical significance (Table 5). Regarding nitrogen content, T8 (Antracol 70WP + Mn + B) recorded higher percentage of N (1.55 %) followed by T6 (Antracol + B: 1.42 %) and T7 (Mn + B: 1.40 %). Higher percentage of P content of 0.44 recorded in the treatment T8 (Antracol 70WP + Mn + B) next to T6 (Antracol 70WP + B: 0.41) which was on par with T7 (Mn + B: 0.40). In case of K, higher percentage of K recorded again in the treatment T8 (Antracol 70WP + Mn + B: 1.28) followed by the treatment T4 (Antracol 70WP + Mn: 1.18) which was on par with T6 (Antracol 70WP + B: 1.17) and T2 (Antracol 70WP: 1.14).
Regarding manganese content, T8 (Antracol 70WP + Mn + B) recorded higher percentage of Mn (0.033 %) followed by T7 (Mn + B: 0.028 %) and T4 (Antracol 70WP + Mn: 0.025 %). Respect to the Boron (B) content, T8 (Antracol 70WP + Mn + B) recorded higher percentage of B (0.058 %) followed by T7 (Mn + B: 0.044 %) and T6 (Antracol 70WP + B: 0.040 %). Overall performance, significantly higher content of N (1.55 %), P (0.44 %), K (1.28 %), Mn (0.033 %) and B (0.058 %) recorded in the treatment Antracol 70WP + Mn + B. The unsprayed control treatment (Tl) recorded lesser content of N (1.20 %), P (0.32 %), K (0.93 %), Mn (0.018 %) and B (0.028 %). Table 6: Effect of Propineb, Mn and B on Crop Growth Rate (CGR) (g m 2 d"1) of tomato
CGR (g m 2 d"1)
Treatment
60-90 DAP 90-120 DAP
Tl : Control 24.29 11.80
T2: Antracol 70WP 25.46 13.76
T3: Manganese (Mn) 25.88 12.00
T4: Antracol 70WP + Mn 26.69 12.60
T5: Boron (B) 26.05 11.68
T6: Antracol 70WP + B 26.69 12.48
T7: Manganese (Mn) + Boron (B) 26.52 12.24
T8: Antracol 70WP + Mn + B 27.35 14.84
Crop Growth Rate (g m"2 d"1)
The crop growth rate was calculated during two stages; 60-90 and 90-120 days after planting (DAP) which was attained statistical significance at both stages of crop growth (Table 6). The foliar spray of Antracol 70WP + Mn + B (T8) treated plants recorded higher growth rate of 27.35 and 14.84 g m"2 d"1 during 60-90 and 90-120 DAP respectively. T8 was on par with the treatment Antracol 70 WP + Boron (T6: 26.69 g m2 d 1) and Antracol 70WP + Manganese (T4: 26.69 g m2 d 1) during 60-90 DAP. Untreated control plants recorded a lower growth rate of 24.29 g m"2 d"1 at 60-90 DAP.
Table 7: Effect of Propineb, Mn and B on yield parameters and fruit yields of tomato Fruit di-
Average Fruit
Treatment Fruit alculated fruit ameter Fruit C
yield
volume number Fruit yield weight (kg plot"
(cc) (cm) plant"1 (tons ha"1) (g) ')
Tl : Control 26.13 26.59 5.36 23 224 44.82
T2: Antracol 70 WP 27.15 28.23 5.40 25 232 46.46
T3 : Manganese (Mn) 26.23 27.28 5.42 23 229 45.83
T4: Antracol 70 WP + Mn 27.32 28.40 5.46 27 242 48.46
T5: Boron (B) 26.30 27.31 5.43 24 230 46.04
T6: Antracol 70 WP + B 27.46 28.58 5.47 28 245 49.03
T7: Mn + B 26.68 27.84 5.46 26 238 47.67
T8: Antracol 70 WP + Mn + B 27.85 28.96 5.52 29 251 50.21
Yield parameters
Considering yield parameters all the yield parameters attained statistical significance except for the fruit diameter (Table 7). Regarding average fruit weight, Antracol 70WP + Mn + B (T8) treated fruits attained higher average weight of 27.85 g which was on par with the treatment Antracol 70WP + B (T6: 27.46), Antracol 70WP + Mn (T4: 27.32) and Antracol 70WP (T2: 27.15). However the fruit weight was 6.6 percent (T8) increase over unsprayed control (Tl : 26.13g). With respect to fruit volume, the volume of fruit was higher (28.96 cc) in case of Antracol 70WP + Mn + B sprayed fruits which was 8.9 percent increase over control (26.59 cc). Similar trend was followed as in the case of fruit weight. The fruit diame- ter did not attained statistical significance. The higher diameter of fruit was recorded in the treatment T8 and lesser fruit diameter attained in case of control (5.36).
With respect to the fruit number, higher number of 29 fruits per plant was recorded in Antracol 70WP + Mn + B treatment which was on par with Antracol 70WP + B (T6: 28). Lesser numbers of fruits were recorded in unsprayed control (Tl : 23). Comparing to T3 and Tl, T8 recorded 26.1 percent increased fruit number. Respect to the fruit yield, Antracol 70WP + Mn + B (T8) sprayed plots beard higher fruit yield of 251 kg plot"1 which was on par with the treatment T6 (Antracol 70WP + Boron) receiving fruit yield of 245 kg plot"1. The unsprayed control plants (Tl) recorded lower fruit yield (224 kg plot"1). The percent yield increase was calculated and the treatments compared. The higher percent increase of 12.1 percent was recorded Antracol 70 WP + Mn + B followed by Antracol 70 WP + B (8.0) and Antracol 70WP + Mn (9.4) over unsprayed control. Again comparing Antracol treatments, Antracol 70WP + Mn + B recorded 8.2 percent fruit yield increment followed by Antracol 70WP + B (5.6) and Antracol 70WP + Mn (4.3) over unsprayed control.
Table 8: Effect of Propineb, Mn and B on Percent disease index of tomato
Percent disease index Percent reduction over
Treatment
control
Tl : Control 87.64
T2: Antracol 70 WP 15.66 82.13
T3 : Manganese (Mn) 56.18 35.90
T4: Antracol 70 WP + Mn 13.42 84.69
T5: Boron (B) 51.34 41.42
T6: Antracol 70 WP + B 15.33 82.51
T7: Manganese (Mn) + Boron (B) 66.63 23.97
T8: Antracol 70 WP + Mn + B 13.22 84.92
In case of disease index values (Table 8), lesser percent disease index value was noticed in the Antracol sprayed treatments of foliar spray with Antracol 70WP + Mn + B (T8: 13.22), Antracol 70WP + B (T6: 15.33), Antracol 70WP + Mn (T4: 13.42) and Antracol 70WP (T2: 15.66). The higher percentage disease index values were observed in the unsprayed control plots (87.64). The higher percent reduction of 84.92 percent was recorded Antracol 70WP + Mn + B followed by Antracol 70WP + Mn (84.69), Antracol 70WP + B (82.51) and Antracol 70WP (82.13) over unsprayed control.
Table 9: Effect of Propineb, Mn and B on quality parameters of tomato Total Soluble
Lycopene (mg Percent weight loss
Treatment
100 g 1) after 5 days
Solids (°Brix)
Tl : Control
4.51 3.3 28.1
T2: Antracol 70 WP
4.52 3.8 27.9
T3 : Manganese (Mn)
4.55 3.6 27.8
T4: Antracol 70 WP + Mn
4.54 3.9 28.1
T5: Boron (B)
4.68 3.9 27.2
T6: Antracol 70 WP + B
4.60 4.1 27.6
T7: Manganese (Mn) + Boron (B)
4.75 4.2 27.2
T8: Antracol 70 WP + Mn + B
4.65 4.3 27.2
Quality parameters
Regarding quality parameters, the Total Soluble Solids (TSS) content attained statistical significant (Table 9). With regard to the lycopene content, higher content of 4.75 mg 100 g"1 fruit was recorded in the treatment Manganese + Boron followed by the treatment Boron alone (4.68). The lowest value was recorded in unsprayed control (Tl : 4.51). Considering TSS value, Antracol 70WP + Mn + B (T8) sprayed plants registered higher brix value of 4.3 which was on par with T7 (Manganese + Boron: 4.2) followed by T6 (4.1). The percent weight loss of fruits was calculated from first day of harvest to 5 days after harvest stored at room temperature. The highest percent was recorded in the control as well as T4 (Antracol 70WP + Manganese). Lesser percent of 27.2 was registered in the treatment T5 (Boron alone), T7 (Manganese + Boron) and T8 (Antracol 70WP + Mn + B).
Conclusion
Foliar spray of Antracol 70WP combination with Mn and B on tomato plants performed well in terms of growth and development with reduced disease incidence tends to finally fruit yield. - Foliar spray of Antracol 70 WP with Mn and B showed 13.4 percent increased root length than unsprayed control in tomato;
An increment of 23.6 percent in Chlorophyll index (SPAD value) and soluble protein (24.2%) was observed by the foliar spray of Antracol 70 WP with Mn and B; Improved nutrient status of tomato plants was registered by Antracol 70 WP with Mn and B with N (1.55%), P (0.44%), K (1.28%), Mn (0.033%) and B content (0.058%) over unsprayed control;
Increment of crop growth rate of 12.6 percent which produce 26.1 percent increased fruit number by Antracol with Mn and B;
- Foliar spray of Antracol 70 WP with Mn and B registered 12.1 percent increased fruit yield compared to unsprayed control.

Claims

Patent Claims
1. Active compound combination comprising
(A) propineb,
and a constituent (B) comprising
(Bl) one or more salts containing boron (B), and
(B2) one or more salts containing manganese (Mn).
2. Active compound combination according to claim 1, wherein one, several or all components of constituent (Bl) are selected from the group consisting of boron oxides, and boric acids, and the salts thereof.
3. Active compound combination according to claim 1 or claim 2, wherein one, several or all components of constituent (Bl) are selected from the group consisting of boron trioxide (B2O3), H3BO3, H2B4O7, sodium borates (preferably borax, also known as sodium borate, sodium tetraborate, or disodium tetraborate, preferably anhydrous borax (N 2B i07), borax pentahydrate ( a2B407-5H20) or borax decahydrate (Na2B4O7- 10H2O)), potassium borates (preferably K2B4O7, and the hydrates thereof, preferably the tetrahydrate thereof 2Β4θ7-4Η2θ), calcium borates (preferably CaB407, Ca3(BOs)2, and the hydrates thereof), magnesium borates (preferably MgB407, Mg3(B03)2, and the hydrates thereof), potassium borohydride, sodium borohydride, potassium borotartrate, and nickel (II) borate].
4. Active compound combination according to any one of claims 1 to 3, wherein one, several or all components of constituent (B2) are selected from the group consisting of manganese (II) salts, preferably selected from the group consisting of manganese (II) acetate, manganese (II) sulfate, manganese (II) chloride, manganese (II) nitrate, and manganese (II) phosphate.
5. Active compound combination according to any one of claims 1 to 4, wherein
constituent (Bl) comprises or consists of disodium tetraborate and/or disodium tetraborate hydrates,
and/or
constituent (B2) comprises or consists of manganese (II) sulfate and/or manganese (II) chloride.
6. Active compound combination according to any one of claims 1 to 5, wherein the ratio by weight of constituent (A) to the total weight of boron and manganese of constituent (B) is in the range of 1250 : 1 to 25 : 1 , preferably in the range of 1000 : 1 to 50 : 1, more preferably in the range of 500 : 1 to 75 : 1, and particularly preferably in the range of 350 : 1 to 100 : 1, in each case based on the total weight of the active compound combination.
7. Active compound combination according to any one of claims 1 to 6, wherein the ratio by weight of the total amount of boron [of constituent (Bl)] to the total amount of manganese [of constituent (B2)] is in the range of 3 : 1 to 1 : 3, preferably in the range of 2 : 1 to 1 : 2, more preferably in the range of 3 : 2 to 2 : 3, even more preferably in the range of 4 : 3 to 3 : 4, and most preferably in the range of 5 : 4 to 4 : 5, in each case based on the total weight of the active compound combination.
8. Active compound combination according to any one of claims 1 to 7, wherein said combination further comprises
one, several or all micronutrients selected from the group consisting of zinc (Zn), copper (Cu), iron (Fe), molybdenum (Mo), selenium (Se), aluminum (Al), cobalt (Co) and nickel (Ni), and/or
one, several or all macronutrients selected from the group consisting of nitrogen (N), phosphorus (P), and potassium (K).
9. Composition comprising
(i) an active compound combination according to any one of claims 1 to 8,
(ii) water, and
(iii) one or more adjuvants (auxiliaries), preferably one or more adjuvants selected from the group consisting of organic solvents, surfactants, inorganic carriers, organic carriers, and other extenders.
10. Composition according to claim 9, wherein the total amount of
(i) the active compound combination according to any one of claims 1 to 8 is in the range of 0.05 to 0.5 wt.%, preferably in the range of 0.1 to 0.3 wt.%,
and/or
(ii) water is in the range of 70 to 99.9 wt.%, preferably in the range of 85 to 99.8 wt.%, in each case based on the total weight of the composition.
11. Method for achieving one, several or all of the following effects: control of phytopathogenic fungi in or on a plant, control of phytopathogenic fungi in crop protection, improve vitality of the plant and/or improve plant development (in particular improve plant growth, preferably increase the plant growth rate), enhance pigment content and/or enhance photosynthetic activity (preferably increase chlorophyll content, thereby preferably obtaining greener leaves ("greening") and/or larger leaves (particularly bigger leaf blade)), increase biomass, such as higher fresh weight (FW) and/or dry weight (DW), preferably increase plant weight (particularly higher fruit weight (per fruit) or higher grain weight (per grain) and/or higher overall fruit or higher overall grain yield), and/or increase plant height, increase nutrient content, particularly increase micronutrient content (particularly of , increase macronutrient content (particularly of N, P and/or K), increase protein content (particularly increase of water soluble proteins), increase vitamin content (particularly of vitamins A, Bi, B2, C and/or E), and/or increase amount of essential amino acids, characterized in that an active compound combination according to any one of claims 1 to 8 or a composition according to claim 9 or 10 is applied to seeds, to plants, to plant parts (preferably fruits and/or leaves), or to the soil on which plants grow or are supposed to grow.
12. Method according to claim 11, characterized in that the active compound combination or the composition are applied to seeds or leaves, wherein in the application the amount of the active compound combination on leaves is in the range of from 400 to 3000 g/ha (preferably of from 500 to 2500 g/ha, more preferably of from 600 to 2000 g/ha, and even more preferably of from 700 to 1700 g/ha), and in the treatment of seeds in the range of from 2 to 200 g per 100 kg of seeds, preferably of from 5 to 150 g per 100 kg of seeds, more preferably of from 10 to 100 g per 100 kg of seeds.
13. Use of an active compound combination according to any one of claims 1 to 8 or a composition according to claim 9 or 10 to control of phytopathogenic fungi in or on a plant, control of phytopathogenic fungi in crop protection, improve vitality of the plant and/or improve plant development (in particular improve plant growth, preferably increase the plant growth rate), enhance pigment content and/or enhance photosynthetic activity (preferably increase chlorophyll content, thereby preferably obtaining greener leaves ("greening") and/or larger leaves (particularly bigger leaf blade)), increase biomass, such as higher fresh weight (FW) and/or dry weight (DW), preferably increase plant weight (particularly higher fruit weight (per fruit) or higher grain weight (per grain) and/or higher overall fruit or higher overall grain yield), and/or increase plant height, increase nutrient content, particularly increase micronutrient content (particularly of , increase macronutrient content (particularly of N, P and/or K), increase protein content (particularly increase of water soluble proteins), increase vitamin content (particularly of vitamins A, Bi, B2, C and/or E), and/or increase amount of essential amino acids.
Seed treated with an active compound combination according to any one of claims 1 to 8 or a composition according to claim 9 or 10.
Kit of parts, comprising
(A) propineb,
and a constituent (B) comprising
(Bl) one or more salts containing boron (B), and
(B2) one or more salts containing manganese (Mn), optionally further comprising instructions for applying constituents (A) and (B) in a manner to obtain an active compound combination according to any one of claims 1 to 8 or a composition according to claim 9 or 10.
EP14766696.0A 2013-09-20 2014-09-15 Active compound combinations Withdrawn EP3046416A1 (en)

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EP14766696.0A EP3046416A1 (en) 2013-09-20 2014-09-15 Active compound combinations
PCT/EP2014/069582 WO2015039983A1 (en) 2013-09-20 2014-09-15 Active compound combinations

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CN107316116B (en) * 2017-08-23 2020-11-10 吉林大学 Leaf vegetable yield prediction method
AR116016A1 (en) 2018-08-24 2021-03-25 Flagship Pioneering Innovations Vi Llc METHODS FOR MANUFACTURING VEGETABLE MESSENGER PACKAGES
JP2022542300A (en) * 2019-07-31 2022-09-30 ＥＦ Ｐｏｌｙｍｅｒ株式会社 Eco-friendly water-retentive natural polymer and method
CN110951746A (en) * 2019-10-30 2020-04-03 山东大学 Application of MtFRUITFULLc gene in regulation of leaf yield and protein content of legumes
CN111423274A (en) * 2020-04-16 2020-07-17 宜宾学院 A kind of foliar fertilizer and method for improving anthocyanin content of black rice
KR102667955B1 (en) * 2021-10-28 2024-05-21 김도현 Plant disease control composition and method for plant disease control thereof
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WO2015039983A1 (en) 2015-03-26
PH12016500523B1 (en) 2022-03-23
KR102334544B1 (en) 2021-12-02
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JP6600633B2 (en) 2019-10-30
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