CA2179181A1 - Fungicide - Google Patents
FungicideInfo
- Publication number
- CA2179181A1 CA2179181A1 CA002179181A CA2179181A CA2179181A1 CA 2179181 A1 CA2179181 A1 CA 2179181A1 CA 002179181 A CA002179181 A CA 002179181A CA 2179181 A CA2179181 A CA 2179181A CA 2179181 A1 CA2179181 A1 CA 2179181A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- active compound
- acid
- active
- composition
- 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.)
- Abandoned
Links
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
- 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
- A01N25/12—Powders or granules
-
- 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
- A01N25/26—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 in coated particulate form
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Agronomy & Crop Science (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Feed For Specific Animals (AREA)
- Medicines Containing Plant Substances (AREA)
- Pretreatment Of Seeds And Plants (AREA)
- Fertilizers (AREA)
- Medicinal Preparation (AREA)
- Materials For Medical Uses (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention concerns an agent, suitable for use as a fungicide, which contains, in a slow-release formation, a fungicidally effective quantity of a) 4-(2-methyl-3-[4-tert-butylphenyl]-propyl)-2,6-dimethylmorpholine (fenpropimorph) and/or tridemorph and/or fenpropidine and b) another fungicidal plant-protection substance. The invention also concerns a method of controlling fungi with this agent.
Description
;` 2179181 Funglcidal composLtions The present invention relates to fungicidal compositions having 5 synergistic fungicidal action in a formulation having delayed release of active compound and methods of controlling fungi using these compositions.
It is known to use a mixture of a) 2-(1,2,4-triazol-1-ylmethyl)-2-(4-fluorophenyl)-3-(2-chloro-phenyl ) oxirane ( ~p~Yi c^n~
and b ) 4- ( 2-methyl-3- [ 4-tert-butylphenyl ] propyl ) -2, 6-dimethylmorpho-line (fenpropimorph) or tridemorph or fenpropidine as a fungicide (EP--A 425 857).
It is further known to use a mixture of a) prochloraz 25 and b) tridemorph or fenpropimorph as a fungicide (EP--A 72 156).
According to the known methods, the application of the active ~ J~ (a) and (b) for controlling fungi is carried out in the customary manner, eg. by spray application. In this case, as a rule several applications to the growing crop are necessary, 80 35 these applications are associated with appreciable expenditure of labor. In the case of application to the plant and foliar appli-cation, the problem further arises that the active ~ u--ds can come into contact with the surrounding air on account of the application method, 90 that they become partly lost for applica-40 tion as a fungicide and at the same time can pollute the environ-ment .
A fungicidal composition has now been found which contains, in a formulation having delayed release of active compound, a fungi-45 cidally active amount of .
It is known to use a mixture of a) 2-(1,2,4-triazol-1-ylmethyl)-2-(4-fluorophenyl)-3-(2-chloro-phenyl ) oxirane ( ~p~Yi c^n~
and b ) 4- ( 2-methyl-3- [ 4-tert-butylphenyl ] propyl ) -2, 6-dimethylmorpho-line (fenpropimorph) or tridemorph or fenpropidine as a fungicide (EP--A 425 857).
It is further known to use a mixture of a) prochloraz 25 and b) tridemorph or fenpropimorph as a fungicide (EP--A 72 156).
According to the known methods, the application of the active ~ J~ (a) and (b) for controlling fungi is carried out in the customary manner, eg. by spray application. In this case, as a rule several applications to the growing crop are necessary, 80 35 these applications are associated with appreciable expenditure of labor. In the case of application to the plant and foliar appli-cation, the problem further arises that the active ~ u--ds can come into contact with the surrounding air on account of the application method, 90 that they become partly lost for applica-40 tion as a fungicide and at the same time can pollute the environ-ment .
A fungicidal composition has now been found which contains, in a formulation having delayed release of active compound, a fungi-45 cidally active amount of .
a ) 4- ( 2-methyl-3- [ 4-tert-butylphenyl ] propyl ) -2, 6-dimethylmorpho-line ( ~enpropimorph ) and/or the active compound tridemorph and/or the active compound fenpropidine 5 and b ) a f urther f ungicidal crop protection active compound in a formulation having delayed release of active compound [sic], 10 [lacuna] is advantageously suitable for controlling fungi.
~hese fllnr~ compositions arQ preferably formulated in the form of granules or pellets having delayed release of active com-pound. The control of fungi using the f~lnr; r~ ~Al composition3 in 15 a formulation having delayed release of active compound is expe-diently carried out by allowing a fllnriri~7l ly active amount of the ~llnriri~l composition to act in or on the soil on the seed planted in the soil or on the plants developing therefrom or on seedlings .
Owing to the delayed release of the active ~ ~, the release rates of the active _ in the soil can be controlled such that an effective protection frora fungal diseases can be main-tained over the whole vegetation period. Absorption of the active 25 compound takes place continuously via the roots to the extent of the controlled release of the active ~ '- from the active compounds formulated according to the invention, and the active compounds are then distributed in the plants systemically via the roots .
::ompared with the spray application of the active ~ (a) and (b) customary hitherto for fungal control, the process ac-cording to the invention for fungal control offers the following advantages:
- Effective protection of the plants against fungal diseases can be achieved over the whole vegetation period by a single application of the active ~Q formulated according to the invention to soil, which advantageously is carried out together with the seed or with the planting of g~e~ll in~8.
- ~he hitherto customary use of several spray applications to the growing crop hereby becomes llnn~r~Qs~ry~ whereby a sig-nif Lcant expenditure of labor can be saved.
. 3 2179181 - The contact of a part of the active _ ' with the sur-rounding air taking place during foliar application according to the prior processes and the loss of active compound associated therewith and a pollution of the environment which may be associated therewith do not apply.
- The process according to the invention makes possible a more specific application of active compound to a smaller area.
10 - ~ower amounts of the active _ .1~ to be applied thereby result .
-- When using the process according to the invention, the seed dressing necessary according to the conventional process does not apply.
Tridemorph is 2, 6-dimethyl-4-tridecylmorpholine .
Fenpropidine is N- [ 3- ( 4-tert-butylphenyl ) -2-methylpropyl-20 piperidine [sic].
The component fenpropimorph can be present in two stereoisomericforms (morpholine ring), the cis isomer being preferred. The in-vention includes mixtures which contain the pure isomers of the 25 compound fenpropimorph, in particular the Ci8 isomer, and mix-tures which contain mixtures of the isomers.
The following is [sic] suitable, for example, as further fungi-cidal crop protection active compound ( b ):
( + ) -cis--1- ( 4-chlorophenyl ) -2- ( lH-1, 2, 4--triazol--1--yl ) cyclohepta-nol, metsulfovax, cyprodinil, methyl (E)-2--{2--[6--(2--cyano-phenoxy ) pyrimidin- 4--yloxy ] phenyl } - 3--methoxyacryl ate and, i n particular, the azole active _ N-propyl-N- [ 2, 4, 6-tri-35 chlorophenoxy)ethyl]imida2ole-l- ~-~rh~Y~rn;de (prochloraz), (Z)-2-(1,2,4-triazol-1-ylmethyl)-2-(4-fluorophenyl)-3-(2-chloro-phenyl)oxirane (~rnY;~ n~7ol~) of the formula N
! ~ ~J
- 4 2~79l8i 1-butyl-1-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)ethanol (h~Y:Ir~nA7nl,0), 1-[(2-chlorophenyl)methyl]-1-(1,1-dimethyl)-2-(1,2,4-triazol-1-ylethanol [sic], 1-(4-fluorophenyl)-1-(2-fluorophenyl)-2-(1,2,4-triazol-l-yl)ethanol (flutriafol), 5 (RS)-4-(4-chlorophenyl)-2-phenyl-2-(lH-1,2,4-triazol-l-yl-methyl)butyronitrile, 1-[(2 RS, 4 RS; 2 RS, 4 SR)-4-bromo-2-(2,4-dichlorophenyl)tetrahy.lLuruL~uLyl]-lH-1,2,4-triazole, 3-(2,4-dichlorophenyl)-2-(lH-1,2,4-triazol-l-yl)q~l;n~7nl;n_ 4- ( 3H ) -one, ( RS ) -2, 2-dimethyl-3- ( 2-chlorobenzyl ) -4- ( lH-1, 2, 4-tri-10 azol-1-yl)-butan-3-ol, bitertanol, triadimefon, tr; ;-.1; nnl ~
I~L- ~7nl~ cyproconazole, dichlobutrazole, difl~nn~nnA7c~l e, ~l;n;rnns~7nl~ et~rnn~701P, fluqll;nr~ 7nl-~, ;m;hc~nrnn~7n~
prnp; c~nn~7nl ~ flllQ; 1 :l7nl F~, tl~hurnnsl7c~ imazalil, p~.nrnn;l7nl F., tetraconazole, triflumizole, metconazole, fluqll;nrnnsl7nl~ [8ic]~
15 fc~nhllrnn~7ol~-~ triticonazole.
The following are preferred as azole active compound (b): pro-chloraz, ~pnY;cnn~7n1~, h~yArnn~7r~le~ cyprornn~7nlF~ difenocona--zole, pro~;cnn:~7nl~ fl~lQ;l5l7ol~ ;n;rnn:~7ole~ triticonazole and 20 teb~rnn~7nl-~, epoxiconazole being used with particular advantage.
The active ~ (a) and (b) can also be present in the form of their salt3 or metal complexes. These mixtures are also in-cluded by the invention.
The salts are prepared by reaction with acids, eg. hydrohalic acids such as hydrofluoric acid, hydrochloric acid, ~ydLublu.,ic acid or hydriodic acid, or sulfuric acid, phosphoric acid, nitric acid or organic acids such as acetic acid, trifluoroacetic acid, 30 tri--chloroacetic acid, propionic acid, glycolic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, bc~n7~npslll fonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p_~m; nns~l; rylic acid or 1,2-naphth~ n~-l;Qulfonic acid.
By choice, metal 1~Y-~Q can contain only one component (a) or one component (b) or alternatively several components (a) or (b).
Metal complexes can also be prepared which contain both compo-nents ( a ) and ( b ) together in a mixed complex .
Metal ~ yl~q are prepared from the organic molecule on which they are based and an inorganic or organic metal salt, for exam-ple the halides, nitrates, sulfates, phosphates, acetates, tri-fluoroacetates, trichloroacetates, propionates, tartrates, sulfo-45 nates, salicylates or benzoates of the metals of the second maingroup, such as calcium and r-~n~; , and of the third and fourth main group, such as aluminum, tin or lead, and of the first to 5 2179l81 eighth subgroup, such as chromium, manganese, iron, cobalt, nick-el, copper or zinc. The subgroup elements of the 4th period and in particular copper are preferred. The metals can in this case be present in the various valencies befitting them. The metal 5 complexes can contain one or more organic molecule components as ligands .
It is an essential feature of the present invention that the com-ponents (a) and the components (b) are present in a formulation 10 having delayed release of active compound. By means of such a controlled release of active compound, it is possible to maintain an effective protection of the crop plants against fungal attack over the entire vegetation period using one application of the ~llnqi ~ composition8 according to the invention to the soil.
Preferably, the fungicides according to the invention are formu-lated as granules or pellets having delayed release of active compound .
20 Suitable granules are prepared, for eYample, as coated granules by first applying the active . to solid granule-shaped carriers. The active substance-containing granules obtained are then coated with suitable coating substances which cause a delayed, controlled release of active compound.
Suitable solid carriers for the coated granules are, for example, mineral earths such as silica gel, silicic acids, silica gels [sic], silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diat~ earth, calcium sulfate and 30 magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammo--nium nitrate and ureas, eg. crotonylidenediurea or isobutylidene-diurea, and vegetable products such as grain flour, corn flour, tree bark, wood and nutshell meal, corn meal and cellulose 35 powder. Fertilizers are advantageously used as carriers. Ferti-lizer granules or pellets are preferred as carriers, in particu-lar those containing phosphate.
The granules in general have a grain size range of from 0.1 to 40 10 mm, preferably from 0.5 to 8 mm, in particular from 1 to 6 mm.
The active ~1~ are as a rule applied to the carriers by spraying them on in the form of oil--in-water emulsions, emulsion concentrates, ~uaL - 1 ~ions, suspension concentrates or in or-45 ganic solvents, or preferably dissolved in water.
- ` ~ 6 217918~
In the case of the active ~ ( a ), the use of oil-in-water 1 q;onc~ emulsion concentrates or the solutions mentioned is pref erred .
5 The spraying--on i8 carried out eg. in fluidized bed apparatuses or in drums or rotary disks in which the carrier granules are rolled, in perforated vessels with controlled conduct of the dry-ing medium, expediently air, or in air suspension processes. In general, temperatures of from 10 C to 110 C are used for the 10 spraying-on and the drying.
~he carrier containing the applied active compound is then coated with suitable coating substances. Suitable coating substances for the controlled release of active compound from the coated gran-15 ules are eg. polymers and copolymers of acrylic acid and/ormethacrylic acid and/or their esters, preferably copolymers based on Cl-C6-alkyl acrylates and Cl-C6-alkyl methacrylates, for exam-ple based on butyl acrylate and methyl methacrylate; copolymers of acrylic and methacrylic acid esters with a low content of 20 ammonium groups (eg. Eudragit~9 RS), copolymers of acrylic and methacrylic acid esters and trimethylammonium methacrylate; poly-vinyl acetate; hydroxypropylmethylcellulose phthalate or acetate succinate; cellulose acetate phthalate, starch acetate phthalate and polyvinyl acetate phthalate; carboxymethylcellulose; methyl-25 cellulose phthalate, succinate, phthalate succinate and hemi-phthalate, ethyl~ se and ethylcellulose succinate; shellac;
ethylcarboxyethylcellulose; methacrylate/maleic anhydride copoly-mer; maleic anhydride/vinyl methyl ether copolymer; styrene/
maleic acid copolymer3; 2-ethylhexyl acrylate/maleic anhydride, 30 crotonic acidtvinyl acetate copolymer; carboxymethylethylcellu-lose glycerol monooctanoate; r~ 11 ose acetate succinate; poly-ethylene, polypropylene and copolymers of ethylene or propylene with acrylates and methacrylates and also acrylic acid and meth-acrylic acid.
Aqueous wax dispersions are advantageously employed as coating ~ubstances, containing, based on the aqueous wax dispersion, from 5 to 40& by weight of an ethylene copolymer wax, consisting of from 10 to 25% by weight of an -olefinically unsaturated mono-40 or dicarboxylic acid having 3 to 8 C atoms and from 90 to 75t byweight of ethylene having an MFI value, measured at 190 C and~a loading of 2.16 kp, of from 1 to 600, preferably from 5 to 500, in particular from 15 to 300, or an MFI value, measured at 160 C
and 325 p, of from 1 to 600, from 0.1 to 5& by weight of alkali 45 metal hydroxide, ammonia, an ~lkAnolAmino or a ~l;AlkAnolAm;n~ and their mixtures and, as the .. -; nr3rr~ water to 100% .
___ _ __ _ 7 2~7918 The copolymers of ethylene to be used for the wax dispersions contain from 10 to 25, preferably from 15 to 24, ~ by weight of C-ol~f;n;cAl1y unsaturated mono-- or dicarboxylic acids having 3 to 8 C atoms, of which, for example, acrylic acid, methacrylic 5 acid, crotonic acid, maleic acid, fumaric acid and itaconic acid may be mentioned. Of these, methacrylic acid and, in particular, acrylic acid and their mixtures are preferred.
The ethylene copolymer waxes are characterized according to the 10 invention by a specific MFI (melt flow index) or melt index. The MFI indicates the amount of the polymer melt in grams which can be forced at a specific t- .ILuLe through a nozzle of specific dimensions with a specific expenditure of force (loading~. The determination of the melt indices (MFI units) is carried out 15 according to the following standard ~Lu~:dur~s, ASTM D 1238-65 T, ISo R 1133-1696 (E) or DIN 53 735 (1970), which are identical with one another.
The wax dispersions furthermore contain mostly bases, namely, as 20 a rule, from 0.1 to 5, preferably from 1 to 3, ~ by weight of alkali metal hydroxide, preferably potassium hydroxide or sodium hydroxide, ammonia, a mono-, di- or tr;AlkAnr~1Am;n~ in each case having from 2 to 18 C atoms in the hydroxyalkyl radical, prefer-ably from 2 to 6 C atoms, or mixtures of the AlkAn~-lAm;n~Q men-25 tioned or a dialky1n~n~A1kAnolamine in each case having from 2 to8 C atoms in the alkyl or hydroxyalkyl radical, or their mix-tures. Amines which may be mentioned are, for example, diethanol-amine, triethAn~l ;n~ 2-amino--2-methylpropanol or dimethyl-ethanolamine. Ammonia is preferably used.
t~wing to the base content in the wax dispersions, the carboxylic acid groups in the copolymer waxes are at least partly present in the salt form. Preferably, these groups are neutralized to 50 to 90 and, especially, to 60 to 859~.
One or more of the coating substances mentioned can be used for the coating layer. The coating layer can additionally contain substances for controlling the release of the active ~Q.
These are eg. water-soluble substances such as polyethylene gly-40 cols, polyvinylpyrrolidone, or copolymers of polyvinylpyrrolidoneand polyvinyl acetate. The amount thereof iB, for example, from 0.1 to 5% by weight, preferably from 0.1 to 396 by weight, based on the coating 3ubstance.
45 The application of the coating layer is expediently carried out by spraying on solutions, dispersions or dispersion [sic] of the coating substances mentioned in organic solvents or ~ater. An 2 ~ 79 1 8 t a~ueous suspension or an emulsion of the coating substance is preferably used which ha~, in particular, a content of polymer substance of from 0.1 to 50 and especially of from 1 to 35~ by weight. Further auxiliaries can be added in this case to optimize 5 the processability, eg. surface-active substances and solids such as talc and/or magnesium stearate.
A wax dispersion is particularly preferred which contains from 5 to 40~ by weight of an ethylene copolymer wax, from 0.1 to 596 by 10 weight of ammonia and from 55 to 94.9% by weight of water or con-sists of the8e components, thQ ethylene copolymer wax being com-posed of from 75 to 90~ by weight of ethylene units and of from 10 to 251; by weight of units of an ~ f~n;c~lly unsaturated mono-- or dicarboxylic acid having 3 to 8 carbon atoms.
Spraying-on is carried out, for example, in fluidized bed appara-tuses or in drums or rotating disks in which the carrier granules are rolled, in perforated vessels with controlled conduct of the drying medium or in air suspension processes. In general, the 20 process is carried out at from 10 C to 110 C.
The fungicidal compositions thus obtained and provided with the coating layer can be used as such for the control of fungi according to the invention with controlled release of active 25 compound.
However, it can also be advantageous additionally to apply active compound from outside to these compositions. The flln~ Al com-positions thus obtained enable a further graduation of the con-30 trolled release of active compound, the active _ ` appliedto the coating layer on the outside being important for a more specific initial action. It may :~A~l;t;~ lly be advantageous also to use a second coating layer, by means of which a further possi-bility of control for the delayed release of the active 35 results.
In addition to th~ coating technique described above, there is a further advantageous technique for the production of the fungi-cidal compositions according to the invention in a formulation 40 having delayed release of active compound in which the active c _ .iq are incorporated into suitable matrix substances from which the active ~ _ ~- are relQased in a delayed and con-' trolled manner. The matrix used in this case can be, for example, the material employed for the coating. Preparation is expediently 45 carried out here by dissolving or dispersing the active ~
in the solution or dispersion of the coating material and then applying this preparation, as described above for the coating _ _ _ _ _ _ .
g substances, to the carrier material. It is ensured by this means that the active flC are dispersed uniformly in the coating layer. As a rule, release from these formulations i8 diffusion-controlled .
The fungicidal compositions in general contain from 0.01 to gS, preferably from 0.05 to 90, 96 by weight of active compound (a) and (b).
10 D~rF~n~;n~ on the effect desired, the application rates are from 0.02 to 5 kg, preferably from 0.05 to 3 kg, of active ~ '-( a ) and ( b ) per ha . The ratio of active compound ( a ) to active compound (b) in the flln~ l mixture in this case is in general from 50:1 to 1:10, preferably from 20:1 to 1:5, in particular 15 from 10:1 to 1:2.
The mixtures are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the Ascomycetes and R~q; ~ es classes .
They are of particular importance for the control of a multiplic-ity of fungi on various crop pIants such as cereals, eg. wheat, rye, barley, oats, rice, rape, sugar beet, corn, soybeans, cof-fee, sugar cane, decorative plants and vegetable plants such as 25 cucumbers, beans and cucurbits. The f~lns;~ q according to the invention are used with particular advantage for fungal control on cereals.
The fungicidal compositions according to the invention are expe-30 diently applied by allowing the fungicidal composition to act inor on the soil on the seed planted in the soil and the plants de-veloping therefrom or on s~ ; nqq . The application of the fungi-cidal composition and the planting of the seed or the planting of the seedlings can take place in separate operations, it being 35 possible for the application of the f1lng;~ l composition to take place before or after the planting of the seed or the plant-ing of the seedlings.
It is particularly advantageous to apply the formulated active 40 ~ , ~lq (a) and (b) together with the seed or the planting of the seedlings.
The following exam~les illustraee the invention.
-0 2179t8t A. Examples of formulations according to the invention c) The active compound ~nY; nnn~ ~nl ~ was processed in the form of a suspension concentrate of the following com-pOSition:
500 g/l of ~pnY; ron:~7n~
30 g/l of 2 block copolymer having a polypropylene oxide core of approximate ~ r weight 3250, to which ethylene oxide up to a molecular weight of approximately 6500 is grafted as a dispersant ( BASF, Germany ), 20 g/l of a sodium salt of a condensation product of phenolsulfonic acid, urea and formaldehyde as a di~persant (BASF, Germany) and the difference to 1 1 of water. The litIuid preparation~ of epoxiconazole used in the following examples were obtained by diluting thi~ suspension concentrate with the appropriate amount o~ water.
2~ ,3) The active compound fenpropimorph was pIo- e3~d as an oil-in-water emul~ion of the following composition:
200 g/l of fenpropimorph, 37 g/l of a p--isononylphenol etherified with 8 ethylene oxide units as an ~mlll~;f;~r (BA3F, Germany), 87.5 g/lof a 1:1 mixture (weight) of 2--ethylh~Y5nn~
acid and a p--isononylphenol eth~r; f; ~d with 7 ethylene oxide units as an emul~ifier (BASF, Germany ) and the difference to 1 1 of water.
40 Example 1 a) Application of ~p~Y; c~n~7nl ~ to NP ~ertilizer A solution of 3.0 g of epoxiconazole, prepared according to (c~), were [ ~ic ] ~prayed onto 4 kg of a nitrogen/pho3phate fertilizer (Nitrophoska~) fertilizer 20-20-0, BASF) with a particle size in the range 2-3 . 5 mm and a bulk weight of 11 ' ' 2 ~ 7~ ~ 8 l 1050 g/l in a fluidized bed coating apparatus (Aeromatic coater MP 1 ), and the fertilizer particles obtained after spraying were then dried. The inlet air temperature to the fluidized bed coating apparatus was 39 C during the spraying process and during the drying.
b) Application of the coating substance The coating substance used was a wax dispersion containing 27% by weight of an ethylene/acrylic acid copolymer compris-ing 20% by weight of acrylic acid and 80& by weight of ethyl-ene, 3 . 68& by weight of ammonia solution ( 25% strength by weight), 0.20% by weight of Na2S2Os and 69.10% by weight of water. A mixture of 740 g of this wax dispersion and 100 ml of water was sprayed in a fluidized bed coating apparatus onto 3 . 8 kg of the fertilizer granules treated with epoxi-conazole as described in section a) above and warmed to 40 C
with ~ ; nn of air at from 39 to 42 C over a period of 70 min. Drying was then carried out at from 39 to 42 C for a further 10 min with further admission of air. The content of the coating layer in the coated fertilizer granules obtained after drying was 5% by weight, based on the coated fertilizer granules .
25 Example 2 The procedure was as described in Example lb), but 4.89 kg of the wax dispersion were sprayed as a coating substance onto 12 kg of the fertilizer granules treated with ~.r~Yi~n~7nle as described 30 in Example la) at an air inlet and air outlet temperature in the range 45-48 C, the total time for the spraying and drying being 175 min. The content of the coating layer, based on the coated fertilizer granules obtained after drying, was 10% by weight.
35 Example 3 The ~L~e~uL~ was as described in Example lb), but three times the amount of the wax dispersion were sprayed on at an air inlet and air outlet temperature of 44-45 C, the total time for the 40 spraying and the subsequent drying being 200 min. The content of the coated layer, based on the coated fertilizer granules ob--tained after drying, was 15% by weight.
-2 1 79 1 8 t 12Example 4 a) Application of fenpropimorph to NP fertilizer 20 g of fenpropimorph ~according to (~), see above) were sprayed in the course of about 11 min at an air inlet temper-ature of 60 C onto 4 kg of a nitrogen~phosphate ~ertilizer (~itrophoska~9 fertilizer 20-20-0 BASF) having a particle size in the range 2-3.5 mm in a fluidized bed coating apparatus (Aeromatic coater MP 1).
b ) Application of the coating substance The coating substance used was a wax dispersion containing 2796 by weight of an ethylene/acrylic acid copolymer compris-ing 209~ by weight of acrylic acid and 80% by weight of ethyl-ene, 3.68% by weight of a_monia solution (25& strength by weight), 0.20~ by weight of Na2520s and 69.1096 by weight of water. A mixture of 713 g of this wax dispersion and 96 ml of water was sprayed in a fl-l;c;;?ed bed coating apparatus onto 3. 8 kg of the fertilizer granules treated with fenpropimorph (according to (,~), see above) as described in section a) above and warmed to 45 C with admission of air at from 40 to 42 C over a period o_ 62 min. Drying was then carried out for a further 5 min with ~urther ~m; r~ n of air at from 40 to 42 C. The content of the coating layer in the coated ferti-lizer granules obtained after drying was about 5~ by weight, based on the coated fertilizer granules.
3 0 Example 5 The ~Lv~eduL-_ was as d~sr~r;h~d in Example 4b), but, as a coating substance, 1.428 kg of the wax dispersion were sprayed onto 3.4 kg of the fertilizer granules treated with fenpropimorph as 35 ~ r; hed in Example 4a) at an air inlet and air outlet temperature in the range 44-45 C, the total time for the spraying and subsequent drying being 125 min. The content of the coating layer, based on the coated fertilizer granules obtained after drying, was about 10~ by weight.
Example 6 The ~Iocadu-~ was as describQd in Example 4b), but 2.142 kg of the wax dispersion were spr~yed onto 3.4 kg of the fertilizer 45 granules treated with fenpropimorph as described in Example 4a) at an air inlet and air outlQt temperature of 44-45 C, the total time for the spraying and the subsequent drying being 190 min.
_ .. .. _ . _ .. . .. . _ . _.. , .. , . , ~, _ _ _ _ __ ___ 13 2179~81 The content of the coating layer, based on the coated fertilizer granules obtained after drying, was 15~ by weight.
Example 7 Corresponding to Examples la) and 4a), two active compound solu-tions were applied by two separate nozzles to 3 . 8 kg of NP
20-20-0 fertilizer granules simultaneously. One solution con-tained 2.5 g of Pr-tY;r~nA7Ol-~ (according to (), see above) and lO the other an oil-in-water emulsion of 15 g of fenpropimorph.
After drying, the granules treated in this way were treated cor-r~pon~;n~ to the spraying ~LvcecluLe lb) or 4b) with 740 g of the wax dispersion described there, the air inlet temperature being 45 C and the total time for the application 62 min.
Example 8 15 g of fenpropimorph were stirred as such into and uniformly dispersed in 740 g of the wax dispersion described in Example 20 lb). Using this preparation, 3.8 kg of NP 20-20-0 fertilizer granules were coated as in Ex. lb) (45 C air inlet ~ ,_L~L~.UL~
52 min application time).
Example 9 The pLvceduLe was as in Example 8, only instead of 15 g of fen-propimorph 2.5 g of eroY;ct~n~7^l0 (according to (c), see above) were stirred in as such.
30 Example 10 The pLV'_edULe was as in Example 8, only in addition to the 15 g of fenpropimorph 2.5 g of ~po~;c~n~7~ (according to (), see above ) werQ also stirred as such into the wax dispersion .
Examples 11 - 16 Examples 11 - 16 were carried out in a similar manner to Examples 1, 2, 4, 5 and 7 in each case using 3.8 kg of NP 20-20-0 ferti-40 lizer granules, but instead of the wax dispersion described aboveusing an aqueous polymer dispersion (of the type Acronal~, BASF) which consisted to 6096 by weight of water and to 40& by weight of a copolymer of methyl methacrylate and n-butyl acrylate ( 1:1 ) as coating substance. The individual application rates and test 45 parameters can be seen from the following table. The inlet air tQmperature in all cases was 40 - 45-C.
.
2 1 79 ~ 8 ~
Ex.No.Fenpropimorph Fr~lr; c~nA701e Acronal TLme for as pure accor~ing to (40% 6trength) spraying substance (a) [g] [g]
511 15 - 500 g 43 min 12 15 - 1000 g 82 min 13 - 2 . 5 500 g 43 min 14 - 2 . 5 1000 g 82 min 1015 15 2.5 500 g 49 min 16 15 2.5 1000 g 87 min The amount of coating in the finished granules was 59~ by weight each in Examples 11, 13 and 15, and 10% by weight each in Exam-15 ples 12, 14 and 16. The product was subsequently also powdered ona disk with 0 . 25% by weight of talc .
Examples 17 - 22 20 Examples 17 -- 22 were carried out in a gimilar manner to Examples 11 - 16, but the active '- were not applied separately but were stirred into the coating dispersion used and then applied together with this. The application rates and the other process parameters remained virtually ~ln-hAn~c~d.
Examples 23 and 24 Examples 23 and 24 were carried out in a similar manner to Exam-ples 11 and 13, but the support material used was 2.0 kg of pum-30 ice split having a particle size of 2 . 0 - 3 . 5 mm and a bulk weight of 460 g/l. On account of the lower density of the pumice split, the co~ting amount in the finished product was in this case 1096 by weight.
3 5 Examples 25 - 3 0 Examples 25 -- 30 ~ULLe~ d in their implementation to the examples described above as follows: Example 25 ouLLe~u,.ds to Example 11, Example 26 ~uLL-~ul~ds to Example 17, Example 27 cor-40 responds to Example 13, Example 28 corresponds to Example 19,Example 29 ~:ULLe~ dS to Example 15 and Example 30 corresponds to Example 21. Instead of the 3 . 8 kg of NP 20-20-0 fertilizer, however, 1.8 kg of corn meal (product of Eurama S.A. (France~ of thQ type Eu-Grit 8/10) having a particle si_e of 2.0 - 3.15 mm 45 and a bulk weight of 450 g/l was used as the carrier material.
The amount of coating substance was also 10% by weight here because of the lower bulk weight. The air inlet temperature was . .. _ _ . .. ... . .. . .
2~7918~
50 C and the time for spraying from 40 to 50 min. The finished granules were also treated with 1% by weight of talc.
Example 3 1 Corresponding to Example 7, solutions of 7 . 5 g of ~enpropimorph (according to (~), see above) and of 1.25 g of epoxiconazole ~according to (a), see above) in 38.75 g of water were first ap-plied to 3. 8 kg of NP 20-20-0 fertilizer and dried. A mixture of 10 500 g of the Acronal dispersion described in Examples 11 - 16, 5 g of fenpropimorph (according to (,~), see above) and 0.83 g of p~Y;c~nA7ole (according to (), see above) was then applied as a coating and dried (time: 45 min, temp.: 45 C inlet air). Finally, 301utions of 2.5 g of fenpropimorph (according to (,~), see above) 15 in 10.8 g of water and 0.42 g of ~pAY;r~rA7A~ (according to (a), see above ) were again applied to the coating on the outside. The finished product contains 59~ by weight of coating material and half of the active ~ are dispersed under the coating, a third in the coating matrix and a sixth on the outside on the 20 coating.
Example 32 This example was carried out in a similar manner to Example 31, 25 but instead of the Acronal dispersion 740 g of the wax dispersion described in Example lb) were used (time: 55 min, temp.: 50 C).
The product contained 59~ by weight of coating material and has the active compound distribution shown in Example 31.
30 Example 33 The example was carried out in a similar manner to Example 31.
E~owever, the individual application rates of the active ~ ~~
were varied such that their distribution in the finished product 35 changed such that one third of the active ~ ~c were applied under the coating and two thirds were embedded in the coating material .
Example 3 4 This example was carried out in a similar manner to Example 33, but 740 g of the wax dispersion as ~3~s~r; h~ in Example lb were used as coating material.
.
-Example 35 This example was carried out in a similar manner to Examples 31 and 33, but instead of the fertilizer 1.8 kg of corn meal as de-5 scribed in Examples 25 - 30 were used as carrier granules. Be-cause of the lower bulk weight, in this case a coating amount of 10% by weight again resulted in the finished product. Active com-pound dispersion was carried out by applying two thirds under the coating layer and '-; n~ one third in the coating layer.
B. Use examples Testing of the fungicide granules having delayed release of ac-tive compound for the control of seed- and airborne harmful fungi 15 on cereals Fungicide granules having delayed release of active compound were mixed with winter wheat seed of the variQty Rektor such that dur-ing simultaneous sowing of 200 kg~ha of loose smut- and covered 20 smut-infected wheat and [sic] 100 kg/ha of th~ fungicide granules according to the invention were applied to the same drill row using a drilling machi~e. The amounts of active compound were, per ha, 300 g of fenpropimorph or 50 g of epoxiconazole or, on combination of both active c ~c, 125 g of fenpropimorph and 25 25 g of epoxiconazole ~Use Example 1 ) . On complete ripening of the wheat (development stage 89), the cobs attacked by loose smut ~Ustilago tritici) and covered smut (Tilletia caries) were counted and the effectiveness of the fungicide granules was con-verted to efficiencies according to Abbott (0 = without effect, 30 100 = harmful fungus completely controlled). The results are shown in Use Example 1.
The application of seed and granules was also carried out with barley seed of the variety Beate and the fungicide granules hav-35 ing delayed release of active compound in the same manner as withthe wheat seed. 200 kg/ha of barley and 200 kg/ha of the fungi-cide granules according to the invention were sown simul-taneously. The amount of active compound per ha was 750 g of fen-propimorph or 125 g of ~rnY; ~ n~7~ or, in combination, 375 g of 40 fenpropimorph and 125 g of ~r~Yirr~n~7ole (Use Example 2). At the end o~ the barley blooming period (development stage 69), attack by mildew (Erysiphe graminis ) and net blotch (Pyrenophora teres ) was determined as total plant attack and the effect of the fungi-cide granules was converted into C~ft~ nri~s according to 45 Abbott. USQ Example 2 shows the results of this test.
0050/44517 17 2 ~ 7 9 ~ ~ ~
rD
~ - ' I~ Ll .,.1, I 0 0 O . ~ ~ J
3 ~ o; a O O O ~D o o ~
S ;~ ' ~D O O
m 0 ~ ~ a~
_ E ~ a 3 '' Ll ; 0 ,, ' r ,~ ~ L V J_) .1 ,~, ~ ,~ ~ o ' , a , ~,, , O O O ", O O q~ 0 --2; , ~ '' a~
a s m o a 0 ~ rD , O
C ~ 0 0, ~, - O
~; , ' 0 1 1 1 0 ~~ ~ r,~l ., ~
- 0 ' : n 0 a _ 8 ~.
J ~ rri ~ r 53 '~ I '~
~ 0 ' O .~ .~
rD . ~ ~ ~ m r ~ o ~ -; ' '.~ ~ ' ' x x ~ x x ' 3 3 3 3 + 0 0 .
.
O rD
_, g , a L~ a L~ S .C
q.l ~ ~ N~ L R
O C, .~ .~ .r~ .~ .rl r ~ rD . a a L~ La rD
r_ ~ q- ~ ~ 4-D ~ , z z z z Z ~ ~
, ~ _ 0050t44517 18 2179~81 rl rD m o L
~, rd r1 C~
O ~ i ~ rr rD r O
S
Cl ~ Q r r U~
>- ~ V O
r~ D rD S ~
n ~ ~ 3 ~5 S rd r ^ ^ O ( ~D rl ~ . O ~
D r ~ ~ O O o D ~
~ I C r ri rl .
Z Cl~ .
L rd ., c S ~ . r .
r~ rl 0 D d I I I
D - ~ . ~ q~ U
r ~ ~ O rr~
, r~
~ ,. ,, ~ + +
~ ~1 1 ~ _ r~
O
D ~ ~ ~ ' + +
~ .
r~ ~ D D D D D
' r~
D D r D D
_~ ~ J ' ~ 1 Z Z ~ Z Z
, _ , .. .. . -- ~ -- -- --0050/4g517 r O ~, t ~ ' ~ ~ ~o O h ~J
~ ~ 8 q~ .,, CJ .
., a r ~ C~
,~ ~
~c ~ o ru r" c " a a~
o o ,~ . r' ~ - ~
a1 ~ a r ~' ~ . .
~hese fllnr~ compositions arQ preferably formulated in the form of granules or pellets having delayed release of active com-pound. The control of fungi using the f~lnr; r~ ~Al composition3 in 15 a formulation having delayed release of active compound is expe-diently carried out by allowing a fllnriri~7l ly active amount of the ~llnriri~l composition to act in or on the soil on the seed planted in the soil or on the plants developing therefrom or on seedlings .
Owing to the delayed release of the active ~ ~, the release rates of the active _ in the soil can be controlled such that an effective protection frora fungal diseases can be main-tained over the whole vegetation period. Absorption of the active 25 compound takes place continuously via the roots to the extent of the controlled release of the active ~ '- from the active compounds formulated according to the invention, and the active compounds are then distributed in the plants systemically via the roots .
::ompared with the spray application of the active ~ (a) and (b) customary hitherto for fungal control, the process ac-cording to the invention for fungal control offers the following advantages:
- Effective protection of the plants against fungal diseases can be achieved over the whole vegetation period by a single application of the active ~Q formulated according to the invention to soil, which advantageously is carried out together with the seed or with the planting of g~e~ll in~8.
- ~he hitherto customary use of several spray applications to the growing crop hereby becomes llnn~r~Qs~ry~ whereby a sig-nif Lcant expenditure of labor can be saved.
. 3 2179181 - The contact of a part of the active _ ' with the sur-rounding air taking place during foliar application according to the prior processes and the loss of active compound associated therewith and a pollution of the environment which may be associated therewith do not apply.
- The process according to the invention makes possible a more specific application of active compound to a smaller area.
10 - ~ower amounts of the active _ .1~ to be applied thereby result .
-- When using the process according to the invention, the seed dressing necessary according to the conventional process does not apply.
Tridemorph is 2, 6-dimethyl-4-tridecylmorpholine .
Fenpropidine is N- [ 3- ( 4-tert-butylphenyl ) -2-methylpropyl-20 piperidine [sic].
The component fenpropimorph can be present in two stereoisomericforms (morpholine ring), the cis isomer being preferred. The in-vention includes mixtures which contain the pure isomers of the 25 compound fenpropimorph, in particular the Ci8 isomer, and mix-tures which contain mixtures of the isomers.
The following is [sic] suitable, for example, as further fungi-cidal crop protection active compound ( b ):
( + ) -cis--1- ( 4-chlorophenyl ) -2- ( lH-1, 2, 4--triazol--1--yl ) cyclohepta-nol, metsulfovax, cyprodinil, methyl (E)-2--{2--[6--(2--cyano-phenoxy ) pyrimidin- 4--yloxy ] phenyl } - 3--methoxyacryl ate and, i n particular, the azole active _ N-propyl-N- [ 2, 4, 6-tri-35 chlorophenoxy)ethyl]imida2ole-l- ~-~rh~Y~rn;de (prochloraz), (Z)-2-(1,2,4-triazol-1-ylmethyl)-2-(4-fluorophenyl)-3-(2-chloro-phenyl)oxirane (~rnY;~ n~7ol~) of the formula N
! ~ ~J
- 4 2~79l8i 1-butyl-1-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)ethanol (h~Y:Ir~nA7nl,0), 1-[(2-chlorophenyl)methyl]-1-(1,1-dimethyl)-2-(1,2,4-triazol-1-ylethanol [sic], 1-(4-fluorophenyl)-1-(2-fluorophenyl)-2-(1,2,4-triazol-l-yl)ethanol (flutriafol), 5 (RS)-4-(4-chlorophenyl)-2-phenyl-2-(lH-1,2,4-triazol-l-yl-methyl)butyronitrile, 1-[(2 RS, 4 RS; 2 RS, 4 SR)-4-bromo-2-(2,4-dichlorophenyl)tetrahy.lLuruL~uLyl]-lH-1,2,4-triazole, 3-(2,4-dichlorophenyl)-2-(lH-1,2,4-triazol-l-yl)q~l;n~7nl;n_ 4- ( 3H ) -one, ( RS ) -2, 2-dimethyl-3- ( 2-chlorobenzyl ) -4- ( lH-1, 2, 4-tri-10 azol-1-yl)-butan-3-ol, bitertanol, triadimefon, tr; ;-.1; nnl ~
I~L- ~7nl~ cyproconazole, dichlobutrazole, difl~nn~nnA7c~l e, ~l;n;rnns~7nl~ et~rnn~701P, fluqll;nr~ 7nl-~, ;m;hc~nrnn~7n~
prnp; c~nn~7nl ~ flllQ; 1 :l7nl F~, tl~hurnnsl7c~ imazalil, p~.nrnn;l7nl F., tetraconazole, triflumizole, metconazole, fluqll;nrnnsl7nl~ [8ic]~
15 fc~nhllrnn~7ol~-~ triticonazole.
The following are preferred as azole active compound (b): pro-chloraz, ~pnY;cnn~7n1~, h~yArnn~7r~le~ cyprornn~7nlF~ difenocona--zole, pro~;cnn:~7nl~ fl~lQ;l5l7ol~ ;n;rnn:~7ole~ triticonazole and 20 teb~rnn~7nl-~, epoxiconazole being used with particular advantage.
The active ~ (a) and (b) can also be present in the form of their salt3 or metal complexes. These mixtures are also in-cluded by the invention.
The salts are prepared by reaction with acids, eg. hydrohalic acids such as hydrofluoric acid, hydrochloric acid, ~ydLublu.,ic acid or hydriodic acid, or sulfuric acid, phosphoric acid, nitric acid or organic acids such as acetic acid, trifluoroacetic acid, 30 tri--chloroacetic acid, propionic acid, glycolic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, bc~n7~npslll fonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p_~m; nns~l; rylic acid or 1,2-naphth~ n~-l;Qulfonic acid.
By choice, metal 1~Y-~Q can contain only one component (a) or one component (b) or alternatively several components (a) or (b).
Metal complexes can also be prepared which contain both compo-nents ( a ) and ( b ) together in a mixed complex .
Metal ~ yl~q are prepared from the organic molecule on which they are based and an inorganic or organic metal salt, for exam-ple the halides, nitrates, sulfates, phosphates, acetates, tri-fluoroacetates, trichloroacetates, propionates, tartrates, sulfo-45 nates, salicylates or benzoates of the metals of the second maingroup, such as calcium and r-~n~; , and of the third and fourth main group, such as aluminum, tin or lead, and of the first to 5 2179l81 eighth subgroup, such as chromium, manganese, iron, cobalt, nick-el, copper or zinc. The subgroup elements of the 4th period and in particular copper are preferred. The metals can in this case be present in the various valencies befitting them. The metal 5 complexes can contain one or more organic molecule components as ligands .
It is an essential feature of the present invention that the com-ponents (a) and the components (b) are present in a formulation 10 having delayed release of active compound. By means of such a controlled release of active compound, it is possible to maintain an effective protection of the crop plants against fungal attack over the entire vegetation period using one application of the ~llnqi ~ composition8 according to the invention to the soil.
Preferably, the fungicides according to the invention are formu-lated as granules or pellets having delayed release of active compound .
20 Suitable granules are prepared, for eYample, as coated granules by first applying the active . to solid granule-shaped carriers. The active substance-containing granules obtained are then coated with suitable coating substances which cause a delayed, controlled release of active compound.
Suitable solid carriers for the coated granules are, for example, mineral earths such as silica gel, silicic acids, silica gels [sic], silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diat~ earth, calcium sulfate and 30 magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammo--nium nitrate and ureas, eg. crotonylidenediurea or isobutylidene-diurea, and vegetable products such as grain flour, corn flour, tree bark, wood and nutshell meal, corn meal and cellulose 35 powder. Fertilizers are advantageously used as carriers. Ferti-lizer granules or pellets are preferred as carriers, in particu-lar those containing phosphate.
The granules in general have a grain size range of from 0.1 to 40 10 mm, preferably from 0.5 to 8 mm, in particular from 1 to 6 mm.
The active ~1~ are as a rule applied to the carriers by spraying them on in the form of oil--in-water emulsions, emulsion concentrates, ~uaL - 1 ~ions, suspension concentrates or in or-45 ganic solvents, or preferably dissolved in water.
- ` ~ 6 217918~
In the case of the active ~ ( a ), the use of oil-in-water 1 q;onc~ emulsion concentrates or the solutions mentioned is pref erred .
5 The spraying--on i8 carried out eg. in fluidized bed apparatuses or in drums or rotary disks in which the carrier granules are rolled, in perforated vessels with controlled conduct of the dry-ing medium, expediently air, or in air suspension processes. In general, temperatures of from 10 C to 110 C are used for the 10 spraying-on and the drying.
~he carrier containing the applied active compound is then coated with suitable coating substances. Suitable coating substances for the controlled release of active compound from the coated gran-15 ules are eg. polymers and copolymers of acrylic acid and/ormethacrylic acid and/or their esters, preferably copolymers based on Cl-C6-alkyl acrylates and Cl-C6-alkyl methacrylates, for exam-ple based on butyl acrylate and methyl methacrylate; copolymers of acrylic and methacrylic acid esters with a low content of 20 ammonium groups (eg. Eudragit~9 RS), copolymers of acrylic and methacrylic acid esters and trimethylammonium methacrylate; poly-vinyl acetate; hydroxypropylmethylcellulose phthalate or acetate succinate; cellulose acetate phthalate, starch acetate phthalate and polyvinyl acetate phthalate; carboxymethylcellulose; methyl-25 cellulose phthalate, succinate, phthalate succinate and hemi-phthalate, ethyl~ se and ethylcellulose succinate; shellac;
ethylcarboxyethylcellulose; methacrylate/maleic anhydride copoly-mer; maleic anhydride/vinyl methyl ether copolymer; styrene/
maleic acid copolymer3; 2-ethylhexyl acrylate/maleic anhydride, 30 crotonic acidtvinyl acetate copolymer; carboxymethylethylcellu-lose glycerol monooctanoate; r~ 11 ose acetate succinate; poly-ethylene, polypropylene and copolymers of ethylene or propylene with acrylates and methacrylates and also acrylic acid and meth-acrylic acid.
Aqueous wax dispersions are advantageously employed as coating ~ubstances, containing, based on the aqueous wax dispersion, from 5 to 40& by weight of an ethylene copolymer wax, consisting of from 10 to 25% by weight of an -olefinically unsaturated mono-40 or dicarboxylic acid having 3 to 8 C atoms and from 90 to 75t byweight of ethylene having an MFI value, measured at 190 C and~a loading of 2.16 kp, of from 1 to 600, preferably from 5 to 500, in particular from 15 to 300, or an MFI value, measured at 160 C
and 325 p, of from 1 to 600, from 0.1 to 5& by weight of alkali 45 metal hydroxide, ammonia, an ~lkAnolAmino or a ~l;AlkAnolAm;n~ and their mixtures and, as the .. -; nr3rr~ water to 100% .
___ _ __ _ 7 2~7918 The copolymers of ethylene to be used for the wax dispersions contain from 10 to 25, preferably from 15 to 24, ~ by weight of C-ol~f;n;cAl1y unsaturated mono-- or dicarboxylic acids having 3 to 8 C atoms, of which, for example, acrylic acid, methacrylic 5 acid, crotonic acid, maleic acid, fumaric acid and itaconic acid may be mentioned. Of these, methacrylic acid and, in particular, acrylic acid and their mixtures are preferred.
The ethylene copolymer waxes are characterized according to the 10 invention by a specific MFI (melt flow index) or melt index. The MFI indicates the amount of the polymer melt in grams which can be forced at a specific t- .ILuLe through a nozzle of specific dimensions with a specific expenditure of force (loading~. The determination of the melt indices (MFI units) is carried out 15 according to the following standard ~Lu~:dur~s, ASTM D 1238-65 T, ISo R 1133-1696 (E) or DIN 53 735 (1970), which are identical with one another.
The wax dispersions furthermore contain mostly bases, namely, as 20 a rule, from 0.1 to 5, preferably from 1 to 3, ~ by weight of alkali metal hydroxide, preferably potassium hydroxide or sodium hydroxide, ammonia, a mono-, di- or tr;AlkAnr~1Am;n~ in each case having from 2 to 18 C atoms in the hydroxyalkyl radical, prefer-ably from 2 to 6 C atoms, or mixtures of the AlkAn~-lAm;n~Q men-25 tioned or a dialky1n~n~A1kAnolamine in each case having from 2 to8 C atoms in the alkyl or hydroxyalkyl radical, or their mix-tures. Amines which may be mentioned are, for example, diethanol-amine, triethAn~l ;n~ 2-amino--2-methylpropanol or dimethyl-ethanolamine. Ammonia is preferably used.
t~wing to the base content in the wax dispersions, the carboxylic acid groups in the copolymer waxes are at least partly present in the salt form. Preferably, these groups are neutralized to 50 to 90 and, especially, to 60 to 859~.
One or more of the coating substances mentioned can be used for the coating layer. The coating layer can additionally contain substances for controlling the release of the active ~Q.
These are eg. water-soluble substances such as polyethylene gly-40 cols, polyvinylpyrrolidone, or copolymers of polyvinylpyrrolidoneand polyvinyl acetate. The amount thereof iB, for example, from 0.1 to 5% by weight, preferably from 0.1 to 396 by weight, based on the coating 3ubstance.
45 The application of the coating layer is expediently carried out by spraying on solutions, dispersions or dispersion [sic] of the coating substances mentioned in organic solvents or ~ater. An 2 ~ 79 1 8 t a~ueous suspension or an emulsion of the coating substance is preferably used which ha~, in particular, a content of polymer substance of from 0.1 to 50 and especially of from 1 to 35~ by weight. Further auxiliaries can be added in this case to optimize 5 the processability, eg. surface-active substances and solids such as talc and/or magnesium stearate.
A wax dispersion is particularly preferred which contains from 5 to 40~ by weight of an ethylene copolymer wax, from 0.1 to 596 by 10 weight of ammonia and from 55 to 94.9% by weight of water or con-sists of the8e components, thQ ethylene copolymer wax being com-posed of from 75 to 90~ by weight of ethylene units and of from 10 to 251; by weight of units of an ~ f~n;c~lly unsaturated mono-- or dicarboxylic acid having 3 to 8 carbon atoms.
Spraying-on is carried out, for example, in fluidized bed appara-tuses or in drums or rotating disks in which the carrier granules are rolled, in perforated vessels with controlled conduct of the drying medium or in air suspension processes. In general, the 20 process is carried out at from 10 C to 110 C.
The fungicidal compositions thus obtained and provided with the coating layer can be used as such for the control of fungi according to the invention with controlled release of active 25 compound.
However, it can also be advantageous additionally to apply active compound from outside to these compositions. The flln~ Al com-positions thus obtained enable a further graduation of the con-30 trolled release of active compound, the active _ ` appliedto the coating layer on the outside being important for a more specific initial action. It may :~A~l;t;~ lly be advantageous also to use a second coating layer, by means of which a further possi-bility of control for the delayed release of the active 35 results.
In addition to th~ coating technique described above, there is a further advantageous technique for the production of the fungi-cidal compositions according to the invention in a formulation 40 having delayed release of active compound in which the active c _ .iq are incorporated into suitable matrix substances from which the active ~ _ ~- are relQased in a delayed and con-' trolled manner. The matrix used in this case can be, for example, the material employed for the coating. Preparation is expediently 45 carried out here by dissolving or dispersing the active ~
in the solution or dispersion of the coating material and then applying this preparation, as described above for the coating _ _ _ _ _ _ .
g substances, to the carrier material. It is ensured by this means that the active flC are dispersed uniformly in the coating layer. As a rule, release from these formulations i8 diffusion-controlled .
The fungicidal compositions in general contain from 0.01 to gS, preferably from 0.05 to 90, 96 by weight of active compound (a) and (b).
10 D~rF~n~;n~ on the effect desired, the application rates are from 0.02 to 5 kg, preferably from 0.05 to 3 kg, of active ~ '-( a ) and ( b ) per ha . The ratio of active compound ( a ) to active compound (b) in the flln~ l mixture in this case is in general from 50:1 to 1:10, preferably from 20:1 to 1:5, in particular 15 from 10:1 to 1:2.
The mixtures are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the Ascomycetes and R~q; ~ es classes .
They are of particular importance for the control of a multiplic-ity of fungi on various crop pIants such as cereals, eg. wheat, rye, barley, oats, rice, rape, sugar beet, corn, soybeans, cof-fee, sugar cane, decorative plants and vegetable plants such as 25 cucumbers, beans and cucurbits. The f~lns;~ q according to the invention are used with particular advantage for fungal control on cereals.
The fungicidal compositions according to the invention are expe-30 diently applied by allowing the fungicidal composition to act inor on the soil on the seed planted in the soil and the plants de-veloping therefrom or on s~ ; nqq . The application of the fungi-cidal composition and the planting of the seed or the planting of the seedlings can take place in separate operations, it being 35 possible for the application of the f1lng;~ l composition to take place before or after the planting of the seed or the plant-ing of the seedlings.
It is particularly advantageous to apply the formulated active 40 ~ , ~lq (a) and (b) together with the seed or the planting of the seedlings.
The following exam~les illustraee the invention.
-0 2179t8t A. Examples of formulations according to the invention c) The active compound ~nY; nnn~ ~nl ~ was processed in the form of a suspension concentrate of the following com-pOSition:
500 g/l of ~pnY; ron:~7n~
30 g/l of 2 block copolymer having a polypropylene oxide core of approximate ~ r weight 3250, to which ethylene oxide up to a molecular weight of approximately 6500 is grafted as a dispersant ( BASF, Germany ), 20 g/l of a sodium salt of a condensation product of phenolsulfonic acid, urea and formaldehyde as a di~persant (BASF, Germany) and the difference to 1 1 of water. The litIuid preparation~ of epoxiconazole used in the following examples were obtained by diluting thi~ suspension concentrate with the appropriate amount o~ water.
2~ ,3) The active compound fenpropimorph was pIo- e3~d as an oil-in-water emul~ion of the following composition:
200 g/l of fenpropimorph, 37 g/l of a p--isononylphenol etherified with 8 ethylene oxide units as an ~mlll~;f;~r (BA3F, Germany), 87.5 g/lof a 1:1 mixture (weight) of 2--ethylh~Y5nn~
acid and a p--isononylphenol eth~r; f; ~d with 7 ethylene oxide units as an emul~ifier (BASF, Germany ) and the difference to 1 1 of water.
40 Example 1 a) Application of ~p~Y; c~n~7nl ~ to NP ~ertilizer A solution of 3.0 g of epoxiconazole, prepared according to (c~), were [ ~ic ] ~prayed onto 4 kg of a nitrogen/pho3phate fertilizer (Nitrophoska~) fertilizer 20-20-0, BASF) with a particle size in the range 2-3 . 5 mm and a bulk weight of 11 ' ' 2 ~ 7~ ~ 8 l 1050 g/l in a fluidized bed coating apparatus (Aeromatic coater MP 1 ), and the fertilizer particles obtained after spraying were then dried. The inlet air temperature to the fluidized bed coating apparatus was 39 C during the spraying process and during the drying.
b) Application of the coating substance The coating substance used was a wax dispersion containing 27% by weight of an ethylene/acrylic acid copolymer compris-ing 20% by weight of acrylic acid and 80& by weight of ethyl-ene, 3 . 68& by weight of ammonia solution ( 25% strength by weight), 0.20% by weight of Na2S2Os and 69.10% by weight of water. A mixture of 740 g of this wax dispersion and 100 ml of water was sprayed in a fluidized bed coating apparatus onto 3 . 8 kg of the fertilizer granules treated with epoxi-conazole as described in section a) above and warmed to 40 C
with ~ ; nn of air at from 39 to 42 C over a period of 70 min. Drying was then carried out at from 39 to 42 C for a further 10 min with further admission of air. The content of the coating layer in the coated fertilizer granules obtained after drying was 5% by weight, based on the coated fertilizer granules .
25 Example 2 The procedure was as described in Example lb), but 4.89 kg of the wax dispersion were sprayed as a coating substance onto 12 kg of the fertilizer granules treated with ~.r~Yi~n~7nle as described 30 in Example la) at an air inlet and air outlet temperature in the range 45-48 C, the total time for the spraying and drying being 175 min. The content of the coating layer, based on the coated fertilizer granules obtained after drying, was 10% by weight.
35 Example 3 The ~L~e~uL~ was as described in Example lb), but three times the amount of the wax dispersion were sprayed on at an air inlet and air outlet temperature of 44-45 C, the total time for the 40 spraying and the subsequent drying being 200 min. The content of the coated layer, based on the coated fertilizer granules ob--tained after drying, was 15% by weight.
-2 1 79 1 8 t 12Example 4 a) Application of fenpropimorph to NP fertilizer 20 g of fenpropimorph ~according to (~), see above) were sprayed in the course of about 11 min at an air inlet temper-ature of 60 C onto 4 kg of a nitrogen~phosphate ~ertilizer (~itrophoska~9 fertilizer 20-20-0 BASF) having a particle size in the range 2-3.5 mm in a fluidized bed coating apparatus (Aeromatic coater MP 1).
b ) Application of the coating substance The coating substance used was a wax dispersion containing 2796 by weight of an ethylene/acrylic acid copolymer compris-ing 209~ by weight of acrylic acid and 80% by weight of ethyl-ene, 3.68% by weight of a_monia solution (25& strength by weight), 0.20~ by weight of Na2520s and 69.1096 by weight of water. A mixture of 713 g of this wax dispersion and 96 ml of water was sprayed in a fl-l;c;;?ed bed coating apparatus onto 3. 8 kg of the fertilizer granules treated with fenpropimorph (according to (,~), see above) as described in section a) above and warmed to 45 C with admission of air at from 40 to 42 C over a period o_ 62 min. Drying was then carried out for a further 5 min with ~urther ~m; r~ n of air at from 40 to 42 C. The content of the coating layer in the coated ferti-lizer granules obtained after drying was about 5~ by weight, based on the coated fertilizer granules.
3 0 Example 5 The ~Lv~eduL-_ was as d~sr~r;h~d in Example 4b), but, as a coating substance, 1.428 kg of the wax dispersion were sprayed onto 3.4 kg of the fertilizer granules treated with fenpropimorph as 35 ~ r; hed in Example 4a) at an air inlet and air outlet temperature in the range 44-45 C, the total time for the spraying and subsequent drying being 125 min. The content of the coating layer, based on the coated fertilizer granules obtained after drying, was about 10~ by weight.
Example 6 The ~Iocadu-~ was as describQd in Example 4b), but 2.142 kg of the wax dispersion were spr~yed onto 3.4 kg of the fertilizer 45 granules treated with fenpropimorph as described in Example 4a) at an air inlet and air outlQt temperature of 44-45 C, the total time for the spraying and the subsequent drying being 190 min.
_ .. .. _ . _ .. . .. . _ . _.. , .. , . , ~, _ _ _ _ __ ___ 13 2179~81 The content of the coating layer, based on the coated fertilizer granules obtained after drying, was 15~ by weight.
Example 7 Corresponding to Examples la) and 4a), two active compound solu-tions were applied by two separate nozzles to 3 . 8 kg of NP
20-20-0 fertilizer granules simultaneously. One solution con-tained 2.5 g of Pr-tY;r~nA7Ol-~ (according to (), see above) and lO the other an oil-in-water emulsion of 15 g of fenpropimorph.
After drying, the granules treated in this way were treated cor-r~pon~;n~ to the spraying ~LvcecluLe lb) or 4b) with 740 g of the wax dispersion described there, the air inlet temperature being 45 C and the total time for the application 62 min.
Example 8 15 g of fenpropimorph were stirred as such into and uniformly dispersed in 740 g of the wax dispersion described in Example 20 lb). Using this preparation, 3.8 kg of NP 20-20-0 fertilizer granules were coated as in Ex. lb) (45 C air inlet ~ ,_L~L~.UL~
52 min application time).
Example 9 The pLvceduLe was as in Example 8, only instead of 15 g of fen-propimorph 2.5 g of eroY;ct~n~7^l0 (according to (c), see above) were stirred in as such.
30 Example 10 The pLV'_edULe was as in Example 8, only in addition to the 15 g of fenpropimorph 2.5 g of ~po~;c~n~7~ (according to (), see above ) werQ also stirred as such into the wax dispersion .
Examples 11 - 16 Examples 11 - 16 were carried out in a similar manner to Examples 1, 2, 4, 5 and 7 in each case using 3.8 kg of NP 20-20-0 ferti-40 lizer granules, but instead of the wax dispersion described aboveusing an aqueous polymer dispersion (of the type Acronal~, BASF) which consisted to 6096 by weight of water and to 40& by weight of a copolymer of methyl methacrylate and n-butyl acrylate ( 1:1 ) as coating substance. The individual application rates and test 45 parameters can be seen from the following table. The inlet air tQmperature in all cases was 40 - 45-C.
.
2 1 79 ~ 8 ~
Ex.No.Fenpropimorph Fr~lr; c~nA701e Acronal TLme for as pure accor~ing to (40% 6trength) spraying substance (a) [g] [g]
511 15 - 500 g 43 min 12 15 - 1000 g 82 min 13 - 2 . 5 500 g 43 min 14 - 2 . 5 1000 g 82 min 1015 15 2.5 500 g 49 min 16 15 2.5 1000 g 87 min The amount of coating in the finished granules was 59~ by weight each in Examples 11, 13 and 15, and 10% by weight each in Exam-15 ples 12, 14 and 16. The product was subsequently also powdered ona disk with 0 . 25% by weight of talc .
Examples 17 - 22 20 Examples 17 -- 22 were carried out in a gimilar manner to Examples 11 - 16, but the active '- were not applied separately but were stirred into the coating dispersion used and then applied together with this. The application rates and the other process parameters remained virtually ~ln-hAn~c~d.
Examples 23 and 24 Examples 23 and 24 were carried out in a similar manner to Exam-ples 11 and 13, but the support material used was 2.0 kg of pum-30 ice split having a particle size of 2 . 0 - 3 . 5 mm and a bulk weight of 460 g/l. On account of the lower density of the pumice split, the co~ting amount in the finished product was in this case 1096 by weight.
3 5 Examples 25 - 3 0 Examples 25 -- 30 ~ULLe~ d in their implementation to the examples described above as follows: Example 25 ouLLe~u,.ds to Example 11, Example 26 ~uLL-~ul~ds to Example 17, Example 27 cor-40 responds to Example 13, Example 28 corresponds to Example 19,Example 29 ~:ULLe~ dS to Example 15 and Example 30 corresponds to Example 21. Instead of the 3 . 8 kg of NP 20-20-0 fertilizer, however, 1.8 kg of corn meal (product of Eurama S.A. (France~ of thQ type Eu-Grit 8/10) having a particle si_e of 2.0 - 3.15 mm 45 and a bulk weight of 450 g/l was used as the carrier material.
The amount of coating substance was also 10% by weight here because of the lower bulk weight. The air inlet temperature was . .. _ _ . .. ... . .. . .
2~7918~
50 C and the time for spraying from 40 to 50 min. The finished granules were also treated with 1% by weight of talc.
Example 3 1 Corresponding to Example 7, solutions of 7 . 5 g of ~enpropimorph (according to (~), see above) and of 1.25 g of epoxiconazole ~according to (a), see above) in 38.75 g of water were first ap-plied to 3. 8 kg of NP 20-20-0 fertilizer and dried. A mixture of 10 500 g of the Acronal dispersion described in Examples 11 - 16, 5 g of fenpropimorph (according to (,~), see above) and 0.83 g of p~Y;c~nA7ole (according to (), see above) was then applied as a coating and dried (time: 45 min, temp.: 45 C inlet air). Finally, 301utions of 2.5 g of fenpropimorph (according to (,~), see above) 15 in 10.8 g of water and 0.42 g of ~pAY;r~rA7A~ (according to (a), see above ) were again applied to the coating on the outside. The finished product contains 59~ by weight of coating material and half of the active ~ are dispersed under the coating, a third in the coating matrix and a sixth on the outside on the 20 coating.
Example 32 This example was carried out in a similar manner to Example 31, 25 but instead of the Acronal dispersion 740 g of the wax dispersion described in Example lb) were used (time: 55 min, temp.: 50 C).
The product contained 59~ by weight of coating material and has the active compound distribution shown in Example 31.
30 Example 33 The example was carried out in a similar manner to Example 31.
E~owever, the individual application rates of the active ~ ~~
were varied such that their distribution in the finished product 35 changed such that one third of the active ~ ~c were applied under the coating and two thirds were embedded in the coating material .
Example 3 4 This example was carried out in a similar manner to Example 33, but 740 g of the wax dispersion as ~3~s~r; h~ in Example lb were used as coating material.
.
-Example 35 This example was carried out in a similar manner to Examples 31 and 33, but instead of the fertilizer 1.8 kg of corn meal as de-5 scribed in Examples 25 - 30 were used as carrier granules. Be-cause of the lower bulk weight, in this case a coating amount of 10% by weight again resulted in the finished product. Active com-pound dispersion was carried out by applying two thirds under the coating layer and '-; n~ one third in the coating layer.
B. Use examples Testing of the fungicide granules having delayed release of ac-tive compound for the control of seed- and airborne harmful fungi 15 on cereals Fungicide granules having delayed release of active compound were mixed with winter wheat seed of the variQty Rektor such that dur-ing simultaneous sowing of 200 kg~ha of loose smut- and covered 20 smut-infected wheat and [sic] 100 kg/ha of th~ fungicide granules according to the invention were applied to the same drill row using a drilling machi~e. The amounts of active compound were, per ha, 300 g of fenpropimorph or 50 g of epoxiconazole or, on combination of both active c ~c, 125 g of fenpropimorph and 25 25 g of epoxiconazole ~Use Example 1 ) . On complete ripening of the wheat (development stage 89), the cobs attacked by loose smut ~Ustilago tritici) and covered smut (Tilletia caries) were counted and the effectiveness of the fungicide granules was con-verted to efficiencies according to Abbott (0 = without effect, 30 100 = harmful fungus completely controlled). The results are shown in Use Example 1.
The application of seed and granules was also carried out with barley seed of the variety Beate and the fungicide granules hav-35 ing delayed release of active compound in the same manner as withthe wheat seed. 200 kg/ha of barley and 200 kg/ha of the fungi-cide granules according to the invention were sown simul-taneously. The amount of active compound per ha was 750 g of fen-propimorph or 125 g of ~rnY; ~ n~7~ or, in combination, 375 g of 40 fenpropimorph and 125 g of ~r~Yirr~n~7ole (Use Example 2). At the end o~ the barley blooming period (development stage 69), attack by mildew (Erysiphe graminis ) and net blotch (Pyrenophora teres ) was determined as total plant attack and the effect of the fungi-cide granules was converted into C~ft~ nri~s according to 45 Abbott. USQ Example 2 shows the results of this test.
0050/44517 17 2 ~ 7 9 ~ ~ ~
rD
~ - ' I~ Ll .,.1, I 0 0 O . ~ ~ J
3 ~ o; a O O O ~D o o ~
S ;~ ' ~D O O
m 0 ~ ~ a~
_ E ~ a 3 '' Ll ; 0 ,, ' r ,~ ~ L V J_) .1 ,~, ~ ,~ ~ o ' , a , ~,, , O O O ", O O q~ 0 --2; , ~ '' a~
a s m o a 0 ~ rD , O
C ~ 0 0, ~, - O
~; , ' 0 1 1 1 0 ~~ ~ r,~l ., ~
- 0 ' : n 0 a _ 8 ~.
J ~ rri ~ r 53 '~ I '~
~ 0 ' O .~ .~
rD . ~ ~ ~ m r ~ o ~ -; ' '.~ ~ ' ' x x ~ x x ' 3 3 3 3 + 0 0 .
.
O rD
_, g , a L~ a L~ S .C
q.l ~ ~ N~ L R
O C, .~ .~ .r~ .~ .rl r ~ rD . a a L~ La rD
r_ ~ q- ~ ~ 4-D ~ , z z z z Z ~ ~
, ~ _ 0050t44517 18 2179~81 rl rD m o L
~, rd r1 C~
O ~ i ~ rr rD r O
S
Cl ~ Q r r U~
>- ~ V O
r~ D rD S ~
n ~ ~ 3 ~5 S rd r ^ ^ O ( ~D rl ~ . O ~
D r ~ ~ O O o D ~
~ I C r ri rl .
Z Cl~ .
L rd ., c S ~ . r .
r~ rl 0 D d I I I
D - ~ . ~ q~ U
r ~ ~ O rr~
, r~
~ ,. ,, ~ + +
~ ~1 1 ~ _ r~
O
D ~ ~ ~ ' + +
~ .
r~ ~ D D D D D
' r~
D D r D D
_~ ~ J ' ~ 1 Z Z ~ Z Z
, _ , .. .. . -- ~ -- -- --0050/4g517 r O ~, t ~ ' ~ ~ ~o O h ~J
~ ~ 8 q~ .,, CJ .
., a r ~ C~
,~ ~
~c ~ o ru r" c " a a~
o o ,~ . r' ~ - ~
a1 ~ a r ~' ~ . .
Claims (5)
1. A composition suitable as a fungicide, composed essentially of a) a granule-or pellet-shaped carrier, which is treated with a fungicidally active amount of 4-(2-methyl-3-[4-tert-butylphenyl]propyl)-2,6-dimethylmorpholine(fenpropi-morph) and/or tridemorph and/or fenpropidine and a fur ther fungicidal crop protection active compound, and b) a coating consisting essentially of a copolymer wax which is composed of from 75 to 90% by weight of ethylene and from 10 to 25% by weight of an -olefinically unsaturated mono- or dicarboxylic acid having 3 to 8 carbon atoms, where the copolymer wax has an MFI value of from 1 to 600, measured at 160°C and 325 p [sic], and the mono- or dicarboxylic acid can be present completely or partially in the form of salts with alkali metal ions, ammonium ions or identical or different alkanolammonium ions as cations .
2. A composition as claimed in claim 1, which comprises using, as a further fungicidal crop protection active compound, an azole active compound.
3. A composition as claimed in claim 2, wherein the azole active compound is selected from the following group: prochloraz, epoxiconazole, hexaconazole, cyproconazole, difenoconazole, propiconazole, flusilazole, tebuconazole, diniconazole, tri-ticonazole.
4. A composition as claimed in any of claims 1 to 3, wherein the granule- or pellet-shaped carrier is a phosphate-containing fertilizer .
5. A method of controlling fungi, which comprises allowing a fungicidally active amount of a composition as claimed in any of claims 1 to 4 to act in or on the soil on the seed planted in the soil or on the plants developing therefrom or on seed-lings .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4343176A DE4343176A1 (en) | 1993-12-17 | 1993-12-17 | Fungicidal mixture |
| DEP4343176.3 | 1993-12-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2179181A1 true CA2179181A1 (en) | 1995-06-22 |
Family
ID=6505336
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002178655A Expired - Fee Related CA2178655C (en) | 1993-12-17 | 1994-12-07 | Coated solid crop protection composition formulation |
| CA002179181A Abandoned CA2179181A1 (en) | 1993-12-17 | 1994-12-07 | Fungicide |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002178655A Expired - Fee Related CA2178655C (en) | 1993-12-17 | 1994-12-07 | Coated solid crop protection composition formulation |
Country Status (22)
| Country | Link |
|---|---|
| EP (2) | EP0734204B1 (en) |
| JP (1) | JPH09506598A (en) |
| KR (1) | KR960706290A (en) |
| CN (2) | CN1141578A (en) |
| AT (1) | ATE172356T1 (en) |
| AU (2) | AU691856B2 (en) |
| BR (2) | BR9408347A (en) |
| CA (2) | CA2178655C (en) |
| CZ (2) | CZ291989B6 (en) |
| DE (2) | DE4343176A1 (en) |
| DK (1) | DK0734204T3 (en) |
| ES (1) | ES2123229T3 (en) |
| GE (1) | GEP20002203B (en) |
| HU (1) | HU214219B (en) |
| MD (1) | MD1605G2 (en) |
| PL (1) | PL180822B1 (en) |
| RO (1) | RO116939B1 (en) |
| RU (1) | RU2145478C1 (en) |
| SK (1) | SK281727B6 (en) |
| UA (1) | UA44723C2 (en) |
| WO (2) | WO1995016350A1 (en) |
| ZA (1) | ZA9410001B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU760827B2 (en) * | 1998-08-05 | 2003-05-22 | Basf Aktiengesellschaft | Soil granulates with controlled active ingredient release (CR soil granulates) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19521502A1 (en) | 1995-06-13 | 1996-12-19 | Basf Ag | Enveloped fertilizer granules |
| EA001085B1 (en) * | 1995-08-18 | 2000-10-30 | Новартис Аг | Microbicidal compositions |
| AU2387297A (en) * | 1996-04-19 | 1997-11-12 | Dr. Wolman Gmbh | Process for treating wood against infection by moulds harmful to wood |
| AU739591B2 (en) * | 1996-08-09 | 2001-10-18 | Buckman Laboratories International, Inc. | Treatment of fungal infections using a combination of an anti-fungal compound and an N-alkyl heterocyclic compound |
| DE59804901D1 (en) * | 1997-06-04 | 2002-08-29 | Basf Ag | FUNGICIDAL MIXTURE |
| EP0953282A1 (en) * | 1998-03-02 | 1999-11-03 | Novartis AG | Pesticidal compositions |
| DE19834028A1 (en) | 1998-07-28 | 2000-02-03 | Wolman Gmbh Dr | Process for treating wood against infestation by wood-damaging fungi |
| US20060150489A1 (en) * | 1999-08-26 | 2006-07-13 | Legro Robert J | Protection of germinating seed and pills containing pesticides |
| NL1012918C2 (en) * | 1999-08-26 | 2001-02-27 | Incotec Internat B V | Method for protecting seed to be germinated and pesticide-containing pill. |
| EP1758456B1 (en) * | 2004-06-17 | 2008-03-05 | Basf Se | Use of (e)-5-(4-chlorbenzyliden)-2,2-dimethyl-1-(1h-1,2,4-triazol-1-ylmethyl)cyclopentanol for combating rust attacks on soya plants |
| GB0706665D0 (en) * | 2007-04-04 | 2007-05-16 | Syngenta Participations Ag | Method of pest and fungal control |
| GB0818906D0 (en) | 2008-10-15 | 2008-11-19 | Syngenta Participations Ag | Fungicidal mixtures |
| CN104488888A (en) * | 2014-12-03 | 2015-04-08 | 广东中迅农科股份有限公司 | Bactericidal composition containing famoxadone and fenpropidin |
| CN111763128A (en) * | 2020-07-17 | 2020-10-13 | 山东农业大学 | Special resin-coated controlled-release pesticide fertilizer for wheat |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2708977A1 (en) * | 1977-03-02 | 1978-09-07 | Basf Ag | FUNGICIDE |
| US4343790A (en) * | 1979-02-06 | 1982-08-10 | American Cyanamid Company | Controlled release acrylic polymer coated granular pesticidal compositions with attendant reduced dermal toxicity |
| DE3333411A1 (en) * | 1983-09-16 | 1985-04-04 | Bayer Ag, 5090 Leverkusen | FUNGICIDAL AGENT |
| EP0201702A3 (en) * | 1985-04-06 | 1989-09-20 | BASF Aktiengesellschaft | Aquous wax dispersions as preservatives for metal and painted surfaces, their use and process to preserve metal and painted surfaces |
| PH24256A (en) * | 1985-12-20 | 1990-05-04 | Rhone Poulenc Agrochimie | Fungicide with triazole and oligoether group and association |
| US4753954A (en) * | 1986-02-14 | 1988-06-28 | Ciba-Geigy Corporation | Fungicidal compositions and methods of combatting fungi employing a synergistic combination of propiconazol and fenpropidin |
| GB8622900D0 (en) * | 1986-09-23 | 1986-10-29 | Shell Int Research | Fungicidal compositions |
| US4801498A (en) * | 1986-10-27 | 1989-01-31 | Exxon Research And Engineering Company | Substrates coated with neutralized carboxylated polymers |
| US4970117A (en) * | 1986-10-27 | 1990-11-13 | Exxon Research And Engineering Company | Coatings with neutralized carboxylated polymers |
| US4756844A (en) * | 1986-12-29 | 1988-07-12 | The Dow Chemical Company | Controlled-release composition having a membrane comprising submicron particles |
| DE3736651C2 (en) * | 1987-10-29 | 1995-11-23 | Bayer Ag | Fungicidal active ingredient combinations |
| US5206279A (en) * | 1991-01-25 | 1993-04-27 | The Dow Chemical Company | Method of preparing aqueous dispersions of ethylene/α,β-unsaturated carboxylic acid interpolymers |
| US5188654A (en) * | 1991-03-28 | 1993-02-23 | Exxon Research And Engineering Company | Coatings with ionically and covalently crosslinked neutralized carboxylated polymers |
-
1993
- 1993-12-17 DE DE4343176A patent/DE4343176A1/en not_active Withdrawn
-
1994
- 1994-12-07 RU RU96115119A patent/RU2145478C1/en not_active IP Right Cessation
- 1994-12-07 PL PL94314978A patent/PL180822B1/en not_active IP Right Cessation
- 1994-12-07 AU AU12426/95A patent/AU691856B2/en not_active Ceased
- 1994-12-07 ES ES95903325T patent/ES2123229T3/en not_active Expired - Lifetime
- 1994-12-07 AT AT95903325T patent/ATE172356T1/en not_active IP Right Cessation
- 1994-12-07 CZ CZ19961774A patent/CZ291989B6/en not_active IP Right Cessation
- 1994-12-07 DK DK95903325T patent/DK0734204T3/en active
- 1994-12-07 GE GEAP19943287A patent/GEP20002203B/en unknown
- 1994-12-07 CZ CZ961773A patent/CZ177396A3/en unknown
- 1994-12-07 CA CA002178655A patent/CA2178655C/en not_active Expired - Fee Related
- 1994-12-07 BR BR9408347A patent/BR9408347A/en not_active IP Right Cessation
- 1994-12-07 EP EP95903325A patent/EP0734204B1/en not_active Expired - Lifetime
- 1994-12-07 HU HU9601655A patent/HU214219B/en not_active IP Right Cessation
- 1994-12-07 CA CA002179181A patent/CA2179181A1/en not_active Abandoned
- 1994-12-07 EP EP95903796A patent/EP0734205A1/en not_active Withdrawn
- 1994-12-07 KR KR1019960703183A patent/KR960706290A/en not_active Application Discontinuation
- 1994-12-07 WO PCT/EP1994/004069 patent/WO1995016350A1/en active IP Right Grant
- 1994-12-07 MD MD96-0237A patent/MD1605G2/en not_active IP Right Cessation
- 1994-12-07 RO RO96-01168A patent/RO116939B1/en unknown
- 1994-12-07 CN CN94194830A patent/CN1141578A/en active Pending
- 1994-12-07 WO PCT/EP1994/004068 patent/WO1995016349A1/en not_active Application Discontinuation
- 1994-12-07 UA UA96072818A patent/UA44723C2/en unknown
- 1994-12-07 DE DE59407155T patent/DE59407155D1/en not_active Expired - Lifetime
- 1994-12-07 BR BR9408345A patent/BR9408345A/en unknown
- 1994-12-07 SK SK746-96A patent/SK281727B6/en not_active IP Right Cessation
- 1994-12-07 CN CN94194829A patent/CN1108750C/en not_active Expired - Fee Related
- 1994-12-07 AU AU12735/95A patent/AU1273595A/en not_active Abandoned
- 1994-12-07 JP JP7516505A patent/JPH09506598A/en active Pending
- 1994-12-15 ZA ZA9410001A patent/ZA9410001B/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU760827B2 (en) * | 1998-08-05 | 2003-05-22 | Basf Aktiengesellschaft | Soil granulates with controlled active ingredient release (CR soil granulates) |
Also Published As
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2179181A1 (en) | Fungicide | |
| AU2002255560B2 (en) | Treated plant seeds with controlled release of active agents | |
| EP0994650B1 (en) | Microparticles containing agricultural active ingredients | |
| CN1111475A (en) | Fungicidal mixtures | |
| AU2002255560A1 (en) | Treated plant seeds with controlled release of active agents | |
| JP2009526772A (en) | A method for controlling harmful fungi using micronutrients as a safener for triazoles | |
| CN102204546A (en) | Bactericidal composition containing thifluzamide and triazole compounds | |
| WO2007065843A2 (en) | Use of gibberellin as safener for azoles for prevention of fungal pests | |
| WO2006102657A2 (en) | Method of protecting a soybean plant with flutriafol | |
| CN102217604A (en) | Bacteriocidal composition containing boscalid and triazole compounds | |
| JPS58162509A (en) | Bactericide | |
| CN113423262B (en) | Flowable concentrate composition for agricultural seeds | |
| CN101731230A (en) | Famoxadone-containing sterilizing composition | |
| EP2334184B1 (en) | Fungicidal mixture, containing fenpropidin and penconazole | |
| CN111758734A (en) | Pesticide composition and application thereof | |
| CN102210310A (en) | Sterilizing composite containing famoxadone and triazole compound | |
| AU2021106121A4 (en) | Plant growth regulator formulation comprising uniconazole-p | |
| CN102047904B (en) | Bactericidal composition containing biphenyl triadimenol and triazole type compound | |
| JP7231816B2 (en) | fungicide formulation | |
| JP3741457B2 (en) | Herbicide composition for paddy field | |
| CN103858893A (en) | Famoxadone and triazole bactericide-containing composition and application | |
| CN102258034A (en) | Germicide composition containing prothioconazole and triazole | |
| CN102057944A (en) | Bactericide composition containing triticonazole and triazole compound | |
| UA79403C2 (en) | Fungicide mixture and agent, control method, inoculum and use of compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |