EP2303006A2 - Emulsifiable concentrate - Google Patents

Abstract

The present application relates to an emulsifiable concentrate (EC) formulation, comprising: a) a fungicidal triazole or an agriculturally acceptable salt or adduct thereof; b) a solvent system, comprising: b1 ) a substituted phenole; b2) one or more organic solvents; c) one or more emulsifiers; d) optionally, further formulation additives, a process for their preparation and a use for controlling harmful fungi.

Description

Emulsifiable Concentrate

The invention relates to emulsifiable concentrates (ECs) comprising fungicidal tria- zoles, a process for the production thereof, and the use of such ECs for controlling harmful fungi.

EP-A 0357 559 discloses an aqueous formulation of a water insoluble crop protection agent, in particular furathiocarb and a substituted phenol, which inhibits the cristallisa- tion of furathiocarb or stabilizes the emulsion.

EP-A 0505 053 discloses an aqueous formulation, which comprises prochloraz, a non- ionic surfactant and a substituted phenol.

Triazoles such as epoxiconazole have been in particular formulated as suspension concentrates (SC). EP-A 0707 445 discloses an aqueous, multiphase, stable formulation of a crop protection active compound comprising a block polymer, an anionic dis- persant, a wetting agent and a thickener.

These SC formulations are difficult to prepare, e.g. by grinding in order to become a homogeneous distribution of the active ingredient to avoid sedimentation.

The SC formulation needs to be stabilized, in particular in the presence of adjuvants or a continuous phase, because the active ingredient tends to crystallize due to solubility in the continuous phase.

It is, therefore, an object of the present invention to provide a formulation of the above mentioned compounds which is stable in storage and application and which has a high biological activity.

It has now been found that this object can be achieved by using an EC formulation of the present invention.

Accordingly, in one aspect of the invention there is provided an emulsifiable concentrate (EC) formulation, comprising

a) a fungicidal triazole or an agriculturally acceptable salt or adduct thereof,

b) a solvent system, comprising

b1 ) a substituted phenole b2) one or more organic solvents

c) one or more emulsifiers,

d) optionally, further formulation additives.

The EC formulation according to the invention shows excellent storage stability and biological activity.

Suitable fungicidal triazole or agriculturally acceptable salt or adduct thereof are azaconazole, bitertanol, bromuconazole, cyproconazole, cifenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebu- conazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1-(4- chloro-phenyl)-2-([1 ,2,4]triazol-1 -yl)-cycloheptanol.

These triazoles are known and described in www.alanwood.nel/pesticides/inclex_cn _frame.html.

Preferred triazoles are epoxiconazole, fluquinconazole, ipconazole, metconazole, propiconazole, prothioconazole, tebuconazole and triticonazole.

Most preferred is epoxiconazole.

Owing to the basic character of their nitrogen atoms, the compound I is capable of forming salts or adducts with inorganic or organic acids or with metal ions.

Examples of inorganic acids are hydrohalic acids, such as hydrogen fluoride, hydrogen chloride, hydrogen bromide und hydrogen iodide, carbonic acid, sulfuric acid, phospho- ric acid and nitric acid.

Suitable organic acids are, for example, formic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals of 1 to 20 carbon atoms), arylsulfonic acids or aryldisulfonic acids (aromatic radicals, such as phenyl and naphthyl, which carry one or two sulfonic acid groups), alkylphos- phonic acids (phosphonic acids having straight-chain or branched alkyl radicals of 1 to 20 carbon atoms), arylphosphonic acids or aryldiphosphonic acids (aromatic radicals, such as phenyl and naphthyl, which carry one or two phosphoric acid groups), where the alkyl or aryl radicals may carry further substituents, for example p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.

Suitable metal ions are in particular the ions of the elements of the second main group, in particular calcium and magnesium, of the third and fourth main group, in particular aluminum, tin and lead and also of the elements of transition groups one to eight, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc, and others. Particu- lar preference is given to the metal ions of the elements of transition groups of the fourth period. The metals can be present in the various valencies that they can assume.

The EC formulation according to the invention generally comprises 0.1 to 30% by weight, preferably 3 to 20% by weight, in particular 5 to 15% by weight, of the fungicidal triazole of component a).

The EC formulation according to the present invention generally comprises 6 to 97% by weight, preferably 10 to 90% by weight, in particular 15 to 80% by weight, of the sol- vent system (b).

Component b1 ) is a substituted phenol of the formula

R¹— O-X , wherein R¹ is phenyl, substituted by one to three Ci-Ci2-alkyl and X is hydrogen, an alkali metal, an alkaline earth metal or NR3, in which each R is the same or different and is hydrogen or d-Cs-alkyl, optionally substituted by hydroxy.

Ci-Ci2-Alkyl is a linear or branched alkyl group having 1 to 12 carbon atoms. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1 ,1-dimethylpropyl, 1 ,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1 ,1 ,2- trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and positional isomers thereof.

Examples of suitable substituted phenols are 2,3,6-trimethylphenol, p-tert-butylphenol, o-sec-butylphenol, 2-tert-butylphenol, p-tert-amylphenol, heptyl derives (p- heptylphenol), p-tert-octylphenol, p-octylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert- butylphenol, p-(alpha, alpha-dimethylbenzyl)phenol, p-nonylphenol, 2,4-di-tert- pentylphenol, p-dodecylphenol, 4-sec-butyl-2,6-di-tert-butylphenol, 2,4,6-tri-tert- butylphenol and 2,4-bis(alpha, alpha-dimethylbenzyl)phenol.

Preferred substituted phenols are p-tert-butylphenol, o-sec-butylphenol, 2-tert- butylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 4-sec-butyl-2,6-di-tert- butylphenol and 2,4,6-tri-tert-butylphenol.

Most preferred is o-sec-butylphenol.

The solvent system comprises organic solvents as component (b2). Preferably, mixtures of alkylaromatics, in particular alkylbenzenes and alkylnaphthalenes, whose alkyl groups have 1 to 20 carbon atoms, are employed. Such mixtures are commercially available, e.g. as the Solvesso^®, e.g. Solvesso 200 (Exxon Mobil, USA), Aromatic, e.g. Aromatic 200 (Exxon Mobil), or Shellsol^® products (Deutsche Shell Chemie GmbH, Germany). Other suitable organic solvents as component (b2) are paraffins, alcohols, pyrrolidons, acetates, glycols, fatty acids, dimethylamides, fatty acid dimethylamide, fatty acid esters, and mixtures thereof.

Examples of suitable solvents (b2) are: methanol, ethanol, isopropanol, butanol, pen- tanol, 2-ethylhexanol, 1 ,3-dimethyl-2-imidazolinone, 2-methyl-2,4-pentanediol, acetone, acetophenone, propanoic acid, 2-hydroxy-2-ethylhexylester, di-n-octylcarbonate, ben- zylacetate, benzylalcohol, benzylbenzoate, cyclohexane, cyclohexanol, cyclohexanone, butyllactate, 2-ethylhexyllactate, ethyllactate, methyllactate, n-propyllactate, tetrahydro- furfurylalcohol, xylole, diethylenglykole, dimethylformamide, dimethylsulfoxide, dipro- pylenglycole, 5-methyl-3-heptanone, ethylenglycole, γ-butyrolactone, glycerine, hexa- nol, iso-propanol, butylencarbonate, propylencarbonate, methylbenzoate, methyl-ethyl- ketone, methyl-isobutyl-ketone, n-ethyl-2-pyrrolidone, n-methylcaprolactame, n-octyl-2- pyrrolidone, propionic acid, and mixtures thereof.

Particularly preferred as component (b2) are Solvesso 200, Solvesso 200 ND, Solvesso 150 ND, Caromax 28 LN, Aromatic 200 and Hydrosol A 230/270 ND.

The organic solvents component (b2) generally amounts to 1 to 35% by weight, pref- erably 1 to 30% by weight, in particular 5 to 25% by weight of the formulation.

The EC formulation of the present invention also contains at least one emulsifier. The emulsifier serves to reduce surface tension between the continuous and the disperse phase, thereby stabilizing the droplets of the disperse phase. The emulsifier also as- sists in the solubilisation of the triazole. Suitable emulsifiers are well known in the art, e.g. from McCutcheon's Detergents and Emulsifiers, Int. Ed., Ridgewood, New York. Suitable emulsifiers include non-ionic, anionic, cationic and zwitterionic emulsifiers and mixtures thereof. The emulsifiers may be polymeric emulsifiers or non-polymeric emulsifiers. Non-polymeric emulsifiers, in contrast to polymeric emulsifiers, will generally have a molecular weight of below 2000 (number average), in particular from 150 to 2000, preferably from 200 to 1500.

The emulsifiers contained in the EC according to the invention can be nonionic or ionic, or a combination of both. It is preferred to use at least two, preferably three to five emulsifiers, preferably with different HLB values to achieve a good physicochemical behaviour of the EC at different temperatures.

The HLB (Hydrophile-Lipophile-Balance) is an empirical scale defined by W.C. Griffin (J. Soc. Cosmetic Chemists, 1 , 31 1 (1949)) which expresses the amphiphilic nature of emulsifying agents (particularly nonionic emulsifiers). The least hydrophilic emulsifiers are assigned the lowest HLB values.

Suitable nonionic emulsifiers are, for example, alkoxylated fats or oils of animal or vegetable origin such as maize oil ethoxylates, castor oil ethoxylates, tallow fat ethoxy- lates, glycerol esters such as glycerol monostearate, fatty alcohol alkoxylates and oxo- alcohol alkoxylates, fatty acid alkoxylates such as oleic acid ethoxylate, alkylphenyl alkoxylates such as isononyl-, isooctyl-, tributyl- and tristearylphenyl ethoxylates, fatty amine alkoxylates, fatty acid amide alkoxylates, sugar emulsifiers such as sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkylpolyglycosides, N-alkylgluconamides, alkylmethyl sulfoxides, alkyldi- methylphosphine oxides such as tetradecyldimethylphosphine oxide, ethylene ox- ide/propylene oxide copolymers and mixtures of such nonionic emulsifiers.

Non-ionic emulsifiers include in particular polyoxy-C2-C3-alkylene Cs-C22-alkyl ethers, in particular polyethoxylates and poly- ethoxylates-co-propoxylates of linear or branched C8-C22-alkanols, more preferably polyethoxylated fatty alcohols and polyethoxylated oxoalcohols, such as polyethoxy- lated lauryl alcohol, polyethoxylated isotridecanol, polyethoxylated cetyl alcohol, polyethoxylated stearyl alcohol, and esters thereof, such as acetates; polyoxy-C2-C3-alkylene aryl ethers and polyoxy-C2-C3-alkylene Ci-Ci6-alkylaryl ethers, such as polyoxy-C2-C3-alkylene Cs-C22-alkylbenzene ethers, in particular polyethoxylates of Ci-Ci6-alkylphenoles, such as polyethoxylates of nonylphenol, decyl- phenol, isodecylphenol, dodecylphenol or isotridecylphenol, polyoxy-C2-C3-alkylene mono-, di- or tristyryl phenyl ethers, in particular polyethoxylates of mono-, di- und tristyrylphenoles; and the formaldehyde condensates thereof and the esters thereof, e.g. the acetates; C6-C22-alkylglucosides and C6-C22-alkyl polyglucosides; polyethoxylates of C6-C22-alkylglucosides and polyethoxylates of C6-C22-alkyl polyglucosides; polyethoxylates of fatty amines; - polyethoxylates of fatty acids and polyethoxylates of hydroxyl fatty acids; partial esters of polyols with C6-C22-alkanoic acids, in particular mono- and diest- ers of glycerine and mono-, di- and triesters of sorbitan, such as glycerine monostearate, sorbitanmonooleat, sorbitantristearat; polyethoxylates of partial esters of polyols with C6-C22-alkanoic acids, in particular polyethoxylates of mono- and diesters of glycerine and polyethoxylates of mono-, di- and triesters of sorbitan, such as polyethoxylates of glycerine monostearate, polyethoxylates of sorbitanmonooleat, polyethoxylates of sorbitanmonostearat and polyethoxylates of sorbitantristearat; polyethoxylates of vegetable oils or animal fats such as corn oil ethoxylate, castor oil ethoxylate, tallow oil ethoxylate; acetylene glycols such as 2,4,7,9-tetramethyl-4,7-bis(hydroxy)-5-decyne; polyoxyethylene-polyoxypropylene-blockcopolymers; and polyethoxylates of fatty amines, fatty amides or of fatty acid diethanolamides.

The term polyoxy-C2-C3-alkylene ether refers to polyether radicals derived from ethyle- neoxide or propyleneoxide. The term polyethoxylate refers to a polyether radical derived from ethyleneoxide. Likewise, the term polyoxyethylene-co-polyoxypropylene refers to a polyether radical derived from a mixture of ethyleneoxide and propylenoxide. The number of repeating units in the polyether radicals will generally vary from 4 to 100, in particular from 5 to 50.

Preferred nonionic emulsifiers are, for example, sorbitan fatty acid esters, in particular partial esters of sorbitol and its anhydrides, e.g. sorbitan monooleate, polyoxyethylene sorbitan fatty acid esters, such as polyethoxylated (preferably with approximately 20 moles of ethylene oxide) sorbitan monolaurate and sorbitan monooleate, castor oil eth- oxylates, preferably with approximately 40 moles of ethylene oxide), and ethylene ox- ide/propylene oxide copolymers, such as alkyl ethylene oxide/propylene oxide copolymers, preferably with a molecular weight in the range of 2000 to 5000.

Ionic emulsifiers can be anionic emulsifiers or cationic emulsifiers or mixtures of anionic and cationic emulsifiers.

Examples of anionic emulsifiers are phosphate esters and sulfate esters of poly (preferably 2 to 30) ethoxylated (preferably Cβ to C22) fatty alcohols such as ethoxylated (2EO (EO means an ethylene oxyde unit) oleyl alcohol phosphate ester (e.g. Em- piphos^® O3D, Albright & Wilson, UK), ethoxylated oleyl alcohol phosphate esters (e.g. Crodafos^® N serie, Croda Oleochemicals, UK), ethoxylated (2-10 EO) ceto/stearyl alcohol phosphate esters (e.g. Crodafos^® CS serie, Croda Oleochemicals, UK), ethoxylated (4-6 EO) tridecyl alcohol phosphate esters (e.g. Emphos^® PS serie, CK Witco, USA), ethoxylated fatty alcohol phosphate esters (e.g. Crafol^® AP serie, Henkel Iberica, Spain), ethoxylated (3-6 EO) fatty alcohol phosphate esters (e.g. Rhodafac^® serie, Rhodia Chimie, France), free acids of complex organic phosphate esters (e.g. Bey- costat^® serie, Ceca S.A., France), phosphate esters of polyethoxylated (8 to 25 EO) arylphenols (such as polyethoxylated di- and tristyrylphenols) (e.g. Soprophor 3D33, Rhodia Chimie, France), sulfate esters of polyethoxylated arylphenols (such as polyethoxylated di- and tristyrylphenols) (e.g. Soprophor DSS/7, Soprophor 4D384, Rhodia Chimie, France).

Anionic emulsifiers include in particular the sodium, potassium, calcium or ammonium salts of

C6-C22-alkylsulfonat.es such as lauryl sulfonate, isotridecylsulfonate; C6-C22-alkylsulfat.es such as lauryl sulfate, isotridecylsulfate, cetylsulfate and stearylsulfate; aryl- and sulfonates, in particular Ci-Ci6-alkylbenzene sulfonates, such as cumylsulfonate, octylbenzene sulfonate, nonylbenzene sulfonate, and dodecylbenzene sulfonate, naphthylsulfonate, mono- and di-Ci-Ci6-alkylnaphthyl sulfonates such as dibutylnaphtylsulfonate; mono- and di-Ci-Ci6-alkyldiphenylether (di)sulfonates such as dodecyldi- phenylether disulfonate; - sulfates and sulfonates of fatty acids and fatty acid esters; polyoxy-C2-C3-alkylene Cs-C22-alkyl ether sulfates, in particular sulfates of ethoxylated Cs-C22 alkanols such as sulfates of ethoxylated lauryl alcohol; polyoxy-C2-C3-alkylene Ci-Ci6-alkylbenzene ether sulfates, in particular sulfates of ethoxylated Ci-Ci6-alkylphenols; - di C4-C18 alkylesters of sulfosuccinic acid (=C4-Ci8-dialkyl sulfosuccinates) such as dioctylsulfosuccinate; condensates of naphthalinesulfonic acid, Ci-Ci6-alkyl naphthalinesulfonic acid or phenolsulfonic acid with formaldehyde (= (Ci-Ci6-alkyl) naphthalene sulfonate- formaldehyde condensates and phenolsulfonate formaldehyde condensates); - polyoxy-C2-C3-alkylene mono- di- or tristyryl phenyl ether sulfates, in particular polyethoxylates of mono-, di- or tristyrylphenol; mono- and di-C8-C22-alkyl sulfates; polyoxy-C2-C3-alkylene Cs-C22-alkyl ether phosphates; polyoxy-C2-C3-alkylene Ci-Ci6-alkylbenzene ether phosphates; - polyoxy-C2-C3-alkylene mono- di- or tristyryl phenyl etherphosphates; polyoxyethylene polycarboxylates, in particular homo- and copolymers of mono- ethylenically unsaturated mono- or dicarboxylic acids having from 3 to 8 carbon atoms, the copolmyers also having polyethylene oxide side chains; salts of fatty acids such as stearates; and - polyphosphates such as hexametaphosphates and triphosphates (= tripolyphos- phate).

Examples of cationic emulsifiers include alkyltrimethylammonium halides or alkyl- trimethylammonium alkyl sulfates, alkylpyridinium halides or dialkyldimethylammonium halides and dialkyldimethylammonium alkyl sulfates.

Of the ionic emulsifiers anionic emulsifiers are preferred.

In a preferred embodiment of the invention, the emulsifier component comprises at least one emulsifier from the group of the sorbitan fatty monoesters, in particular sorbi- tan monooleate, and one or more, preferably two, emulsifiers from the group of the polyoxyethylene sorbitan fatty esters, in particular sorbitan monooleate and sorbitan monolaurate, each ethoxylated with approximately 20 moles ethylene oxide.

In a particularly preferred embodiment of the invention, the emulsifier component comprises an emulsifier from the group of the sorbitan fatty monoesters, one or more emulsifiers, preferably two, from the group of the polyethoxylated sorbitan fatty esters, and one or more emulsifiers from the group of the castor oil ethoxylates and ethylene ox- ide/propylene oxide copolymers.

The referenced nonionic emulsifiers are all commercially available. For example, sorbitan fatty acids are available as the S-MAZ^® (BASF, Germany) or the Span^® (UNIQEMA, US) series, polyoxyethylene sorbitan fatty esters as the T-MAZ^® (BASF, Germany) or the Tween^® (UNIQEMA, US) series, castor oil ethoxylates as Trylox 5909 (Cognis, Germany), and ethylene oxide/propylene oxide copolymers as the Tergitol series, such as Tergitol^® XD (Dow, USA) or the Surfonic^® LPP series.

The emulsifiers in the EC generally amount to from 2 to 20% by weight, preferably 5 to 15% by weight of the formulation.

In the preferred and particularly preferred embodiments, the sorbitan fatty monoesters generally amount to from 0.1 to 15% by weight, preferably 1 to 5 % by weight of the formulation; the polyethoxylated sorbitan fatty esters generally amount to 1 to 5% by weight, preferably 1 to 5 % by weight of the formulation, the polyethoxylated castor oil generally amounts to 0 to 15% by weight, preferably 0 to 5% by weight of the formula- tion, and the ethylene oxide/propylene oxide copolymer generally amounts to 0 to 15% by weight, preferably 0 to 5% by weight of the formulation.

In another embodiment, the non-ionic and anionic emulsifier are selected from poly- meric emulsifiers. Polymeric emulsifiers comprise statistical (random) polymers and copolymers, block copolymers, graft polymers and copolymers.

The non-ionic block copolymer emulsifier comprise at least one poly(ethylene oxide) moiety PEO and at least one hydrophobic polyether moiety PAO. The PAO moiety usually comprises at least 3, preferably at least 5, in particular 10 to 100 repeating units (number average) which are derived from C3-Cio alkylene oxides, such as propylene oxide, 1 ,2-butylene oxide, cis- or trans-2,3-butylene oxide or isobutylene oxide, 1 ,2- pentene oxide, 1 ,2-hexene oxide, 1 ,2-decene oxide and styrene oxide, among which C3-C4 alkylene oxides are preferred. Preferably, the PAO moieties comprise 10 to 60% by weight of repeating units derived from propylene oxide. The PEO moieties usually comprise 2 to 6, preferably 3 to 5, and more preferably 3 or 4 repeating units derived from ethylene oxide (number average). Those emulsifier c.12 are preferred which have a number average molecular weight MN ranging from more than 600 to 8000 Dalton, preferably from 1000 to 6000 Dalton and in particular from 1500 to 5000 Dalton.

The non-ionic block copolymer emulsifier are commercially available e.g. under the trade names Pluronic®, such as Pluronic® P 65, P84, P 103, P 105, P 123 and PIu- ronic® L 31 , L 43, L 62, L 62 LF, L 64, L 81 , L 92 and L 121 , Pluraflo® such as Plura- flo® L 860, L1030 and L 1060; Tetronic®, such as Tetronic® 704, 709, 1 104, 1304, 702, 1 102, 1302, 701 , 901 , 1 101 , 1301 (BASF Aktiengesellschaft), Agrilan® AEC 167 and Agrilan® AEC 178 (Akcros Chemicals), Antarox® B/848 (Rhodia), Berol® 370 and Berol® 374 (Akzo Nobel Surface Chemistry), Dowfax® 50 C15, 63 N10, 63 N30, 64 N40 and 81 N10 (Dow Europe), Genapol® PF (Clariant), Monolan®, such as Monolan® PB, Monolan® PC, Monolan® PK (Akcros Chemicals), Panox® PE (Pan Asian Chemical Corporation), Symperonic®, such as Symperonic® PE/L, Symperonic® PE/F, Symperonic® PE/P, Symperonic® PE/T (ICI Surfactants), Tergitol® XD, Tergi- tol® XH and Tergitol® XJ (Union Carbide), Triton® CF-32 (Union Carbide), Teric PE Series (Huntsman), Toximul® 8320 (Stepan Co.) and Witconol®, such as Witconol® APEB, Witconol® NS 500 K and the like.

In another embodiment, the non-ionic polymeric emulsifier is an ethylene oxide- propylene oxide block copolymer comprising alkyl or alkyphenol ether bases, such as butyl ether, methyl ether, propyl ether, ethyl ether, or mixtures thereof. As an example of such emulsifier, the commercially available product Toximul® 8320 (Stepan Co.) may be mentioned, i.e. a butyl ether derivative of ethylene oxide-propylene oxide block copolymer. The amount of the aforementioned block copolymer is usually from 2 to 20% by weight, in particular from 5 to 17 % by weight and more preferably from 5 to 12 % by weight, based on the total weight of the formulation.

In another embodiment, the non-ionic polymeric emulsifier is a polyalkylene oxide modified dimethyl polysiloxane, such as the organosilicone emulsifier marketed under the Silwet® trademark, in particular Silwet® L-77 (GE Silicones). These emulsifiers are disclosed in US 2,970,150. The amount of the organosilicone emulsifier is usually from 0 to 6 % by weight, in particular from 0.5 to 5 % by weight and more preferably from 1 to 4 % by weight, based on the total weight of the formulation.

In another embodyment, the non-ionic polymeric emulsifier is a water soluble polymer selected from the polymer class of polyvinylpyrrolidone, vinylpyrrolidone-vinylacetate- copolymers, polyvinylcaprolactame, polyvinylformamide, polyvinylacetamide, polyacry- late, polymethacrylate, polyacrylamide, polyethylenimine, polyvinylamine, hydroxyalkyl- cellulose, alkyl-hydroxyalkylcellulose, carboxyalkylcellulose, alkyl- hydroxyalkylcelluloseacetatsuccinate, alkyl-hydroxyalkylcelluloseacetatephthalate, al- kyl-hydroxyalkylcellulosephthalate, celluloseacetatephthalate, starches, hydroxyalkyl- starches, carboxyalkylstarches, modified starches, octenylsuccinatstarches, dextranes, polyoxyethylene-polyoxypropylene-blockcopolomers, polyethyleneoxides, polypropyle- neoxides, polyaminoacids.

In another embodiment, the anionic polymeric emulsifier is a random radical copolymer comprising, as monomers, at least one olefinically unsaturated sulfonic acid of the for- mula I

in which X is oxygen or NR⁵, R¹ is hydrogen or methyl, n can take a value from 0 to 10, R² and R³ are, independently of one another, d-Cε-alkyl, and R⁵ is hydrogen, alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, aryloxyalkyl, alkoxyaryl, hydroxyalkyl,

(di)alkylaminoalkyl, (di)alkylaminoaryl, (di)arylaminoalkyl, alkylarylaminoalkyl or alky- larylaminoaryl, it being possible for the aryl radicals to be substituted, and where the olefinically unsaturated sulfonic acid can be present in the acid or salt form or as a mix- ture of the acid and salt forms, at least one olefinically unsaturated monomer of the formula Il

R⁶

in which Y is oxygen or NR⁵, R⁴ is hydrogen or methyl, and R⁵ and R⁶ are, independently of one another, hydrogen, alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, aryloxyalkyl, alkoxyaryl, hydroxyalkyl, (di)alkylaminoalkyl, (di)alkylaminoaryl, (di)arylaminoalkyl, alky- larylaminoalkyl or alkylarylaminoaryl and optionally additional monomers.

Salts of the sulfonic acid of the formula I are preferably alkali metal or ammonium salts.

Ci-C2o-alkyl are suitable as alkyl radicals, alone or in the abovementioned combinations. Mention may in particular be made of d-Cε-alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1 ,1-dimethylethyl, pentyl, 1- methylbutyl, 2-methylbutyl, 3-methylbutyl, 1 ,1-dimethylpropyl, 1 ,2-dimethylpropyl, 2,2- dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2- trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl, cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, decyl, isodecyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl or stearyl.

Aryl radicals is to be understood as meaning mono- or polycyclic, if appropriate substituted, aromatic hydrocarbon radicals. Mention may be made, by way of examples, of phenyl, naphthyl or phenyl substituted by halogen, such as fluorine or chlorine.

Alkoxy is an alkyl radical bonded via an oxygen atom (-O-) to the backbone. Aryloxy is an aryl radical bonded via an oxygen atom (-O-) to the backbone.

Additional monomers can comprise, for example, vinylaromatic monomers, such as styrene and styrene derivatives, such as α-methylstyrene, vinyltoluene, ortho-, meta- and para-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylene and the corresponding halogenated vinylaromatic monomers, or vinylaromatic monomers carrying nitro, alkoxy, haloalkyl, alkoxycarbonyl, carboxyl, amino and alkylamino groups, α- olefins, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, isobutene, or α- olefins comprising long-chain (Cio-C2o)alkyls, dienes, such as butadiene and isoprene, vinyl alcohol esters, such as vinyl acetate, vinyl halides, such as vinyl chloride, vinyl bromide or vinyl fluoride, vinylidene chloride, vinylidene fluoride, vinylidene bromide, vinylnitrile, vinyl carboxylates, 1-vinylamides, such as 1-vinylpyrrolidone, 1- vinylpiperidone, 1-vinylcaprolactam, 1-vinylformamide, 1-vinylacetamide or 1-methyl-1- vinylacetamide, N-vinylimidazole, Ci-C24-alkyl esters and mono- and disubstituted and unsubstituted Ci-C24-alkylamides of monoethylenically unsaturated monomers, such as acrylic acid, methacrylic acid, fumaric acid, maleic acid and itaconic acid, vinylsulfonic acid, anhydrides, such as maleic anhydride, unsaturated aldehydes, such as acrolein, or unsaturated ethers, such as 1 ,4-cyclohexanedimethanol divinyl ether, 1 ,4- cyclohexanedimethanol monovinyl ether, butanediol divinyl ether, butanediol monovinyl ether, cyclohexyl vinyl ether, diethylene glycol divinyl ether, ethylene glycol monovinyl ether, ethyl vinyl ether, methyl vinyl ether, n-butyl vinyl ether, octadecyl vinyl ether, tri- ethylene glycol vinyl methyl ether, vinyl isobutyl ether, vinyl (2-ethylhexyl) ether, vinyl propyl ether, vinyl isopropyl ether, vinyl dodecyl ether, vinyl tert-butyl ether, hexanediol divinyl ether, hexanediol monovinyl ether, diethylene glycol monovinyl ether, diethyl- aminoethyl vinyl ether, polytetrahydrofuran-290 divinyl ether, tetraethylene glycol divinyl ether, ethylene glycol butyl vinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether or aminopropyl vinyl ether.

A polymer described with "radical" is to be understood as meaning a polymer prepared by a radical polymerization.

A copolymer described with "random" is to be understood as meaning a copolymer in which the monomer sequence is determined by the copolymerization parameters of the monomers. This is correspondingly valid also for copolymers consisting of more than two types of monomer. Polymers of this type are also described as statistical copolymers.

In an additional preferred embodiment, the random radical copolymer is formed from monomers of the above formula I, in particular 2-acrylamido-2-methyl-1- propanesulfonic acid, and at least one olefinically unsaturated monomer of the formula Il

R⁶

in which Y is oxygen or NR⁵, R⁴ is hydrogen or methyl, and R⁵ and R⁶ are hydrogen, alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, aryloxyalkyl, alkoxyaryl, hydroxyalkyl, (di)alkylaminoalkyl, (di)alkylaminoaryl, (di)arylaminoalkyl, alkylarylaminoalkyl or alky- larylaminoaryl, in which alkyl and aryl have the abovementioned meanings, and optionally additional monomers. In an additional particularly preferred embodiment, the random radical copolymer comprises, as monomers, 2-acrylamido-2-methyl-1-propanesulfonic acid and at least one olefinically unsaturated monomer of the formula II, in which Y is oxygen, R⁴ is hydrogen and R⁶ is hydrogen or alkyl.

Accordingly, the random radical copolymer comprises, in this particularly preferred embodiment, as monomers, 2-acrylamido-2-methyl-1-propanesulfonic acid and at least one ester of acrylic acid.

Such esters of acrylic acid are, for example, methyl acrylate, ethyl acrylate, propyl acry- late, isopropyl acrylate, butyl acrylate, 2-methylpropyl acrylate, tert-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, iso- decyl acrylate, undecyl acrylate, lauryl acrylate, tridecyl acrylate, myristyl acrylate, pen- tadecyl acrylate, cetyl acrylate, heptadecyl acrylate or stearyl acrylate.

These copolymers and processes for their preparation are disclosed in WO 05/046328.

In a preferred embodiment, component c) comprises at least one polymeric emulsifier.

In another preferred embodiment, component c) comprises at least one water soluble polymeric emulsifier.

In another preferred embodiment, component c) comprises at least one anionic polymeric emulsifier.

In another preferred embodiment, component c) comprises at least two emulsifiers, preferably three to five emulsifiers.

In still another preferred embodiment, component c) comprises one polymeric and one non-polymeric emulsifier.

In another preferred embodiment, component c) comprises one water soluble polymeric emulsifier and at least one non-polymeric emulsifier.

In another preferred embodiment, component c) comprises one anionic polymeric emulsifier and at least one non-polymeric emulsifier.

In a further preferred embodiment, component c) comprises one water soluble polymeric emulsifier, one nonionic non-polymeric emulsifier and one anionic non-polymeric emulsifier. In another preferred embodiment, component c) comprises one anionic polymeric emulsifier, one nonionic non-polymeric emulsifier and one anionic non-polymeric emul- sifier.

The combination of several different emulsifiers increases the stability of the EC formulation.

In addition, the EC according to the invention may comprise other conventional formulation additives, such as cosolvents, antifoams, antifreezes, preservatives, colorants, and wetting agents.

Suitable antifoams are, for example, aliphatic or aromatic monoalcohols having 4 to 14, preferably 6 to 10 carbon atoms, such as n-octanol or n-decanol, or silicone emulsifiers. The antifoams generally amount to from 0 to 10% by weight, preferably 0.01 to 1 % by weight, of the formulation.

Typical antifreezes are, for example, ethylenglykol, propylenglykol, and glycerol.

Typical preservatives are, for example, vitamin E acetate, benzoic acid, sorbic acid, formaldehyde and traces of microbicidal compounds. Preservatives generally amount to from 0 to 10% by weight, preferably 0 to 1 % by weight of the formulation.

Typical colorants include oil soluble dyes, such as Vitasyn^® Patentblau (Clariant, Germany).

Typical wetting agents are, for example, polyethoxylated alkyl phenols (containing 1 to 30 moles ethylene oxide), polyethoxylated fatty alcohols (containing 1 to 30 moles ethylene oxide), tridecyl alcohol polyglykol ethers, and alkyl- or alkylphenyl-sulfonates. Wetting agents generally amount to from 0 to 50% by weight, preferably 0 to 10% by weight of the formulation.

The total content of further formulation additives generally amounts to from 0 to 52% by weight, preferably 0 to 30% by weight, more preferred 5 to 25% by weight of the formulation.

The EC formulation according to the invention is prepared in a manner known per se by mixing the components, if appropriate with stirring and/or heating. The products thus obtainable are normally homogeneous emulsion concentrates. Containers which are suitable for the formulations are all containers conventionally used for crop protection products, mainly bottles, canisters, and bags made of chemical-resistant polymers. The use of water-soluble containers, mainly water-soluble film bags, in particular based on polyvinyl alcohol, is advantageous.

For application against fungi the EC formulation is usually diluted with a suitable diluent, generally water, preferably with an at least 10 to 400, preferably 10 to 150 fold excess of diluent.

The spray liquids thus obtained can be used in a conventional manner for controlling fungi on crop plants, their environment, seeds or propagation material, in home and garden applications, vector control and public hygiene.

The formulations according to the invention are suitable as fungicides. They are distin- guished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plas- modiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imper- fecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.

The formulations according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, for example wheat, rye, barley, triticale, oats or rice; beet, for example sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; laura- ceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, for example conifers; and on the plant propagation material, such as seeds, and the crop material of these plants. Preferably, the formulations are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.

The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be mentioned. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.

Preferably, treatment of plant propagation materials with compounds I and composi- tions thereof is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.

The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering. Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.

The term "cultivated plants" is to be understood also including plants that have been rendered tolerant to applications of specific classes of herbicides, such as hydroxy- phenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e. g. US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673,

WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imidazolinones (see e. g. US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate (see e. g. WO 92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e. g. EP-A-0242236, EP-A-242246) or oxynil herbicides (see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), for example Clearfield^® summer rape (Canola) being tolerant to imidazolinones, e. g. imazamox. Genetic engineering methods have been used to render cultivated plants, such as soybean, cotton, corn, beets and rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady^® (glyphosate) and LibertyLink^® (glufosinate).

The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as δ-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bi ) or Cryθc; vegetative insecticidal proteins (VIP), e. g.

VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel block- ers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new com- bination of protein domains, (see, for example WO 02/015701 ). Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, for example, in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 und WO 03/052073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of insects, especially to beetles (Coeloptera), two-winged insects (Diptera), and butterflies (Lepidoptera).

Genetically modified plants capable to synthesize one or more insecticidal proteins are, for example, described in the publications mentioned above, and some of which are commercially available such as YieldGard^® (corn cultivars producing the CryiAb toxin), YieldGard^® Plus (corn cultivars producing CrylAb and Cry3Bb1 toxins), Starlink^® (corn cultivars producing the Cry9c toxin), Herculex^® RW (corn cultivars producing Cry34Ab1 , Cry35Ab1 and the enzyme Phosphinothricin-N-Acetyltransferase [PAT]); NuCOTN^® 33B (cotton cultivars producing the Cry1 Ac toxin), Bollgard^® I (cotton culti- vars producing the CryiAc toxin), Bollgard^® Il (cotton cultivars producing Cry1 Ac and Cry2Ab2 toxins); VIPCOT^® (cotton cultivars producing a VIP-toxin); NewLeaf^® (potato cultivars producing the Cry3A toxin); Bt-Xtra^®, NatureGard^®, KnockOut^®, BiteGard^®, Protecta^®, Bt1 1 (e. g. Agrisure^® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the CryiAb toxin and PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CryiAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).

The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to in- crease the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, for example EP-A 0 392 225), plant disease resistance genes (for example potato cultivars, which express resistance genes acting against Phytophthora in- festans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.

The term "cultivated plants" is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, for ex- ample oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera^® rape).

The term "cultivated plants" is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, for example potatoes that produce increased amounts of amylopectin (e. g. Amflora^® potato).

The formulations are particularly suitable for controlling the following plant diseases:

• Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis),

• Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alter- nata), tomatoes (e. g. A. solani or A. alternata) and wheat,

• Aphanomyces spp. on sugar beets and vegetables,

• Ascochyta species on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. hordei on barley

• Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.) on corn (e. g. D. may- dis), cereals (e. g. B. sorokiniana: spot blotch), rice (e. g. B. oryzae) and turfs,

• Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley),

• Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat,

• Bremia lactucae (downy mildew) on lettuce,

• Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms,

• Cercospora spp. (Cercospora leaf spots) on corn, rice, sugar beets (e. g. C. beti- cola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice,

• Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. her- barum (black ear) on wheat,

• Claviceps purpurea (ergot) on cereals, • Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. mi- yabeanus, anamorph: H. oryzae),

• Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gos- sypii), corn (e. g. C. graminicola), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum),

• Corticium spp., e. g. C. sasakii (sheath blight) on rice,

• Corynespora cassiicola (leaf spots) on soybeans and ornamentals,

• Cycloconium spp., e. g. C. oleaginum on olive trees, • Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nec- tria or Neonectria spp.) on fruit trees, vines (e. g. C. liriodendri, teleomorph: Neonec- tria liriodendri: Black Foot Disease) and ornamentals,

• Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans, • Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans,

• Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf,

• Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamy- dosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa,

• Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. ampelina: anthracnose),

• Entyloma oryzae (leaf smut) on rice, • Epicoccum spp. (black mold) on wheat,

• Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruciferarum),

• Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods, • Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turcicum),

• Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani on soybeans and F. verticil- lioides on corn, • Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and corn,

• Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi: Bakanae disease),

• Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton, • Grainstaining complex on rice,

• Guignardia bidwellii (black rot) on vines,

• Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears,

• Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice,

• Hemileia spp., e. g. Hemileia vastatrix (coffee leaf rust) on coffee,

• lsariopsis clavispora (syn. Cladosporium vitis) on vines,

• Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton, • Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley),

• Microsphaera diffusa (powdery mildew) on soybeans,

• Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants,

• Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas,

• Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica),

• Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans,

• Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot), • Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets,

• Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum),

• Physorma maydis (brown spots) on corn, • Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad-leaved trees (e. g. P. ramorum: sudden oak death)

• Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants, • Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers,

• Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples,

• Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases,

• Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia yallundae) on cereals, e. g. wheat or barley,

• Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop, • Pseudopezicula tracheiphila (red fire disease or .rotbrenner', anamorph: Phialophora) on vines,

• Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. stri- iformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, and asparagus (e. g. P. asparagi), • Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley,

• Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals, • Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum),

• Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets ,

• Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans,

R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley,

• Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes, • Rhynchosporium secalis (scald) on barley, rye and triticale,

• Sarocladium oryzae and S. attenuatum (sheath rot) on rice,

• Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. rolfsii),

• Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals,

• Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines,

• Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf,

• Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane,

• Sphaerotheca fuliginea (powdery mildew) on cucurbits,

• Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases,

• Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat,

• Synchytrium endobioticum on potatoes (potato wart disease),

• Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums,

• Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans),

• Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat, • Typhula incarnata (grey snow mold) on barley or wheat, • Urocystis spp., e. g. U. occulta (stem smut) on rye,

• Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae),

• Ustilago spp. (loose smut) on cereals (e. g. U. nuda und U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane,

• Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears,

• Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.

The formulations are also suitable for controlling harmful fungi in the protection of materials (e. g. wood, paper, paint dispersions, fiber or fabrics) and in the protection of stored products. As to the protection of wood and construction materials, the particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Ser- pula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladospo- rium spp., Penicillium spp., Trichorma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.

The formulations are employed by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.

The formulations and the compositions according to the invention have a strong plant strengthening effect. They are suitable for moilisiing plant defense responses against undesirable microorganisms such s aforementioned harmful fungi, but also viruses and bacteria. The term "plant strengeners (resistance inducing compounds)" is to be understood those compounds in the formulations, which are capable to stimulate the plant defense system in a way that upon a subsequent inoculation with said undesirable microorganisms treated plants develop to a large extent resistance against these microorganisms.

Accordingly, the formulations can be used to protect plants against infestation by unde- sirable microorganisms for a certain period of time after application. The period of time, wherein protection is induced, extends usually from 1 to 28 days, preferably 1 to 14 days after application of the formulations, or in the case of seed treatment, up to 9 months after sowing.

The formulations according to the invention are also suitable to increase the yield of harvest. Furthermore, they are less toxic and show a good plant compatibility.

These formulations can be applied to plant propagation materials, particularly seeds, diluted or undiluted. The formulations in question give, after two-to-tenfold dilution, ac- tive substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before sowing. Methods for applying or treating agrochemical compounds and compositions thereof on to plant propagation material, especially seeds, are known in the art, and include dressing, coating, pelleting and soaking application methods of the propagation material. In a preferred embodiment, the compounds or the compositions thereof are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting and coating.

The active substance concentrations in the ready-to-use products can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1 %.

When employed in plant protection, the amounts applied are, depending on the kind of effect desired, between 0.01 and 2.0 kg of active substance per ha.

In seed treatment, for example by coating or drenching seed, amounts of active substance of from 0.1 g to 10 kg, frequently 1 to 1000 g, preferably from 5 to 100 g, per 100 kilogram of seed are generally required.

When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.

Various types of oils, wetters, adjuvants, herbicides, bactericides, other fungicides and/or pesticides may be added to the formulations, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the formulations according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1. Adjuvants which can be used are in particular organic modified polysiloxanes such as Break Thru S 240^®; alcohol alkoxylates such as Atplus 245^®, Atplus MBA 1303^®, PIu- rafac LF 300^® and Lutensol ON 30^®; EO/PO block polymers, e. g. Pluronic RPE 2035^® and Genapol B^®; alcohol ethoxylates such as Lutensol XP 80^®; and dioctyl sulfosucci- nate sodium such as Leophen RA^®.

The formulations according to the invention can, in the use form as fungicides, also be present together with other active substances, e. g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers, as pre-mix or, if appropriate, not until immeadiately prior to use (tank mix).

Mixing the formulations in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity being obtained or in a prevention of fungicide resistance development. Furthermore, in many cases, synergis- tic effects are obtained.

The following list of fungicides, which could be added to the formulation according to the invention, is intended to illustrate the possible combinations but does not limit them:

A) strobilurins, selected from the group consisting of azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metomi- nostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb, trifloxystrobin, 2- (2-(6-(3-chloro-2-methyl-phenoxy)-5-fluoro-pyrimidin-4-yloxy)-phenyl)-2- methoxyimino-N-methyl-acetamide, 3-methoxy-2-(2-(N-(4-methoxy-phenyl)- cyclopropane-carboximidoylsulfanylmethyl)-phenyl)-acrylic acid methyl ester, methyl (2-chloro-5-[1-(3-methylbenzyloxyimino)ethyl]benzyl)carbamate and 2-(2-(3-

(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-

N-methyl-acetamide;

B) carboxamides, selected from the group consisting of

- carboxanilides: benalaxyl, benalaxyl-M, bixafen, boscalid, carboxin, fenfuram, fen- hexamid, flutolanil, furametpyr, isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl, Metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, penthiopyrad, teclofta- lam, thifluzamide, tiadinil, 2-amino-4-methyl-thiazole-5-carboxylic acid anilide, 2- chloro-N-(1 ,1 ,3-trimethyl-indan-4-yl)-nicotinamide, 3-difluoromethyl-1-methyl-1 H- pyrazole-4-carboxylic acid (2',4'-difluorobiphenyl-2-yl)-amide, 3-difluoromethyl-1- methyl-1 H-pyrazole-4-carboxylic acid (2',4'-dichlorobiphenyl-2-yl)-amide, 3- difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid (2',5'-difluorobiphenyl-2-yl)- amide, 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid (2', 5'- dichlorobiphenyl-2-yl)-amide, 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid (3',5'-difluorobiphenyl-2-yl)-amide, 3-difluoromethyl-1-methyl-1 H-pyrazole-4- carboxylic acid (3',5'-dichlorobiphenyl-2-yl)-amide, 3-difluoromethyl-1 -methyl-1 H- pyrazole-4-carboxylic acid (3'-fluorobiphenyl-2-yl)-amide, 3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxylic acid (3'-chlorobiphenyl-2-yl)-amide, 3-difluoromethyl-1- methyl-1 H-pyrazole-4-carboxylic acid (2'-fluorobiphenyl-2-yl)-amide, 3- difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid (2'-chlorobiphenyl-2-yl)- amide, 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro- biphenyl-2-yl)-amide, 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid (2',4',5'-trifluorobiphenyl-2-yl)-amide, 3-difluoromethyl-1 -methyl-1 H-pyrazole- 4-carboxylic acid [2-(1 ,1 ,2,3,3,3-hexafluoropropoxy)-phenyl]-amide, 3- difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid [2-(1 ,1 ,2,2-tetrafluoro- ethoxy)-phenyl]-amide, 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid (4'- trifluoromethylthiobiphenyl-2-yl)-amide , N-(3',4'-dichloro-5-fluoro-biphenyl-2-yl)-3- difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid amide, N-(2-(1 ,3-dimethyl- butyl)-phenyl)-1 ,3,3-trimethyl-5-fluoro-1 H-pyrazole-4-carboxylic acid amide, N-(4'- chloro-3',5'-difluoro-biphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4- carboxylic acid amide, N-(4'-chloro-3',5'-difluoro-biphenyl-2-yl)-3-trifluoromethyl-1- methyl-1 H-pyrazole-4-carboxylic acid amide, N-(3',4'-dichloro-5'-fluoro-biphenyl-2- yl)-3-trifluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid amide, N-(3',5'-difluoro- 4'-methyl-biphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid amide, N-(3',5'-difluoro-4'-methyl-biphenyl-2-yl)-3-trifluoromethyl-1-methyl- 1 H-pyrazole-4-carboxylic acid amide, N-(2-bicyclopropyl-2-yl-phenyl)-3-difluoro- methyl-1 -methyl-1 H-pyrazole-4-carboxylic acid amide, N-(cis-2-bicyclopropyl-2-yl- phenyl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid amide, N-(trans- 2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid amide;

- carboxylic morpholides: dimethomorph, flumorph;

- benzoic acid amides: flumetover, fluopicolde, fluopyram;

- other carboxamides: carpropamid, dicyclomet, mandiproamid, oxytetracyclin, silthio- farm and N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide;

C) azoles, selected from the group consisting of

- triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, cifenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusi- lazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazol, myclobu- tanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1-(4-chloro-phenyl)-2-([1 ,2,4]triazol-1-yl)-cycloheptanol; imidazoles: cyazofamid, imazalil, pefurazoate, prochloraz, triflumizol; - benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole; - others: ethaboxam, etridiazole and hymexazole;

D) heterocyclic compounds, selected from the group consisting of

- pyridines: fluazinam, pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin- 3-yl]-pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine,

2,3,5,6-tetra-chloro-4-methanesulfonyl-pyridine, 3,4,5-trichloropyridine-2,6-di-carbo- nitrile, N-(1-(5-bromo-3-chloro-pyridin-2-yl)-ethyl)-2,4-dichloronicotinamide, N-[(5-bromo-3-chloro-pyridin-2-yl)-methyl]-2,4-dichloro-nicotinamide; pyrimidines: bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, mepani- pyrim, nitrapyrin, nuarimol, pyrimethanil; piperazines: triforine;

- pyrroles: fenpiclonil, fludioxonil;

- morpholines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tride- morph; - piperidines: fenpropidin;

- dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin;

- non-aromatic 5-membered heterocycles: famoxadone, fenamidone, octhilinone, probenazole, δ-amino^-isopropyl-S-oxo^-ortho-tolyl^^-dihydro-pyrazole-i-carbo- thioic acid S-allyl ester; - others: acibenzolar-S-methyl, amisulbrom, anilazin, blasticidin-S, captafol, captan, chinomethionat, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methyl- sulfate, fenoxanil, Folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quin- oxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo-3-propylchromen-4-one, 5-chloro- 1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, N-(4-(3-methoxy- 1 -(5-methyl-[1 ,2,3]thiadiazol-4-yl)-naphthalen-2-yl)-thiazol-2-yl)-butyramide,

5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo- [1 ,5-a]pyrimidine, 6-(3,4-dichloro-phenyl)-5-methyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine- 7-ylamine, 6-(4-tert-butylphenyl)-5-methyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 5-methyl-6-(3,5,5-trimethyl-hexyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 5-methyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 6-methyl-5-octyl-

[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 6-ethyl-5-octyl-[1 ,2,4]triazolo- [1 ,5-a]pyrimidine-7-ylamine, 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine- 7-ylamine, 5-ethyl-6-(3,5,5-trimethyl-hexyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine- 7-ylamine, 6-octyl-5-propyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 5-methoxy- methyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 6-octyl-5-trifluoromethyl-

[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine and 5-trifluoromethyl-6-(3,5,5-trimethyl- hexyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine;

E) carbamates, selected from the group consisting of - thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasulphocarb, metiram, propineb, thiram, zineb, ziram;

- carbamates: benthiavalicarb, diethofencarb, flubenthiavalicarb, iprovalicarb, propa- mocarb, propamocarb hydrochlorid, valiphenal and N-(1-(1-(4-cyanophenyl)ethane- sulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;

F) other active substances, selected from the group consisting of

- guanidines: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate); - antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, polyo- xine, validamycin A;

- nitrophenyl derivates: binapacryl, Dinobuton, dinocap,, nitrthal-isopropyl, Tecnazen, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fen- tin hydroxide; - sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane;

- organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, iprobenfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl;

- organochlorine compounds: chlorothalonil, dichlofluanid, Dichlorophen, flusul- famide, hexachlorobenzene, pencycuron, pentachlorphenole and its salts, phthalide, quintozene, thiophanate-methyl, tolylfluanid, N-(4-chloro-2-nitro-phenyl)-

N-ethyl-4-methyl-benzenesulfonamide;

- inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;

- others: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamin, metrafenone, mildiomycin, oxin-copper, prohexadione calcium, spiroxamine, tolylfluanid, N-(cyclo- propylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl- N-methyl formamidine, N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl- phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethyl- silanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine and N'-(5-difluoromethyl-

2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine.

The following list of growth regulators, which could be added to the formulation according to the invention, is intended to illustrate the possible combinations but does not limit them:

G) abscisic acid, amidochlor, ancymidol , 6-benzylaminopurine, brassinolide, butra- Nn, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dike- gulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid , trinexapac-ethyl and uniconazole.

The following list of herbicides, which could be added to the formulation according to the invention, is intended to illustrate the possible combinations but does not limit them: H) herbicides such as glyphosate, sulfosate, gluphosinate, tefluthrin, terbufos, chlor- pyrifos, chlorethoxyfos, tebupirimfos, phenoxycarb, diofenolan, pymetrozine, imazethapyr, imazamox, imazapyr, imazapic or dimethenamid-P;

The following list of insecticides, which could be added to the formulation according to the invention, is intended to illustrate the possible combinations but does not limit them: I) insecticides such as fipronil, imidacloprid, acetamiprid, nitenpyram, carbofuran, carbosulfan, benfuracarb, dinotefuran, thiacloprid, thiamethoxam, clothianidin, diflubenzuron, flufenoxuron, teflubenzuron and alpha-cypermethrin.

According to this invention, applying the formulation containing a triazole together with at least one further active substance is to be understood to denote, that at least one triazole and at least one further active substance occur simultaneously at the site of action (i.e. the harmful fungi to be controlled or their habitats such as infected plants, plant propagation materials, particularly seeds, surfaces, materials or the soil as well as plants, plant propagation materials, particularly seeds, soil, surfaces, materials or rooms to be protected from fungal attack) in a fungicidally effective amount. This can be obtained by applying the triazole containing formulation and at least one further ac- tive substance simultaneously, either jointly (e. g. as tank-mix) or sperately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for working of the present invention.

The components can be used individually or already partially or completely mixed with one another to prepare the formulation according to the invention. It is also possible for them to be packaged and used further as combination composition such as a kit of parts.

In one embodiment of the invention, the kits may include one or more, including all, components that may be used to prepare a subject agrochemical composition. For example, kits may include one or more fungicide component(s) and/or an adjuvant component and/or a insecticide component and/or a growth regulator component and/or a herbicide. One or more of the components may already be combined together or pre- formulated. In those embodiments where more than two components are provided in a kit, the components may already be combined together and as such are packaged in a single container such as a vial, bottle, can, pouch, bag or canister. In other embodiments, two or more components of a kit may be packaged separately, i. e. , not pre- formulated. As such, kits may include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical composition. In both forms, a component of the kit may be applied separately from or together with the further components or as a component of a combination composition according to the invention for preparing the formulation ac- cording to the invention.

Preference is also given to formulations comprising a triazole and at least one active substance selected from the strobilurines of group A) and particularly selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picox- ystrobin, pyraclostrobin and trifloxystrobin.

Preference is also given to formulations comprising a triazole and at least one active substance selected from the carboxamides of group B) and particularly selected from fenhexamid, metalaxyl, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolid (pi- cobenzamid), zoxamide, carpropamid and mandipropamid.

Preference is given to formulations comprising a triazole and at least one active substance selected from the azoles of group C) and particularly selected from cyprocona- zole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metcona- zole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadi- menol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamid, benomyl, carbendazim and ethaboxam.

Preference is also given to formulations comprising a triazole and at least one active substance selected from the heterocyclic compounds of group D) and particularly selected from fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforine, fludi- oxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, vinclozolin, fa- moxadone, fenamidone, probenazole, proquinazid, acibenzolar-S-methyl, captafol, folpet, fenoxanil and quinoxyfen.

Preference is also given to formulations comprising a triazole and at least one active substance selected from the carbamates of group E) and particularly selected from mancozeb, metiram, propineb, thiram, iprovalicarb, flubenthiavalicarb and propamo- carb. Preference is also given to formulations comprising a triazole and at least one active substance selected from the fungicides given in group F) and particularly selected from dithianon, fentin salts, such as fentin acetate, fosetyl, fosetyl-aluminium, H3PO3 and salts thereof, chlorthalonil, dichlofluanid, thiophanat-methyl, copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, cymoxanil, metrafenone, spirox- amine and 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]- triazolo[1 ,5-a]pyrimidine.

In such formulations according to the invention comprising one triazole and one further active substance, e. g. one active substance from groups A) to I), the weight ratio of the triazole and the second active substance generally is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 and particularly in the range of from 1 :10 to 10:1.

In such formulations according to the invention comprising one triazole and a first further active substance (component 2) and a second further active substance (component 3), e. g. two active substances from groups A) to I), the weight ratio of the triazole and the second active substance preferably is in the range of from 1 :50 to 50:1 and particularly in the range of from 1 :10 to 10:1 , and the weight ratio of the triazole and the third active substance preferably is in the range of from 1 :50 to 50:1 and particularly in the range of from 1 :10 to 10:1.

The following examples illustrate the invention, but should not be construed to limit it.

1. Preparation Examples

Examples F- 1 to F-3 were prepared by making a mixture of the solvents and adding the technical epoxiconazole with heat and agitation. When the epoxiconazole completely dissolved to form a clear solution, the emulsifiers were added and mixed until a clear EC had been prepared.

F-O is a comparison example of a SC (suspension concentrate) formulation.

Table 1 : Preparation Examples

Use example F-O to F-3: Curative action against Puccinia recondite on wheat (brown rust of wheat)

Leaves of potted wheat seedlings of the cultivar "Kanzler" were dusted with a suspension of spores of brown rust of wheat (Puccinia recondita). The plants were then placed in a chamber with high atmospheric humidity (90 to 95%), at 20-22⁰C, for 24 hours. During this time, the spores germinated and the germinal tubes penetrated into the leaf tissue. The next day, the infected plants were sprayed to runoff point with a formulation having the concentration of active substance stated below. After drying of the sprayed formulation, the test plants were returned into the greenhouse and cultivated at temperatures between 20 and 22°C and at 65 to 70% relative atmospheric humidity for a further 7 days. The extent of the rust development on the leaves was then determined visually.

In this test, the plants which had been treated with the EC formulation showed a much lower infection than the plants which had been treated with the SC formulation or the untreated plants (table 2).

Table 2: Biological examples

Claims

Claims

1. An emulsifiable concentrate (EC) formulation, comprising

a) a fungicidal triazole or an agriculturally acceptable salt or adduct thereof,

b) a solvent system, comprising

b1 ) a substituted phenol b2) one or more organic solvents

c) one or more emulsifiers,

d) optionally further formulation additives.

2. The EC as claimed in claim 1 , where the triazole is selected from the group consisting of azaconazole, bitertanol, bromuconazole, cyproconazole, cifenocona- zole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquincona- zole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metcona- zole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadi- menol, triticonazole, uniconazole, 1-(4-chloro-phenyl)-2-([1 ,2,4]triazol-1-yl)- cycloheptanol.

3. The EC as claimed in claim 2, wherein the triazole is selected from the group consisting of epoxiconazole, fluquinconazole, ipconazole, metconazole, propiconazole, prothioconazole, tebuconazole and triticonazole.

4. The EC as claimed in claim 3, wherein the triazole is epoxiconazole.

5. The EC as claimed in any of the preceding claims, which comprises one or more further crop protection agent.

6. The EC as claimed in claim 5, where the further crop protection agents are se- lected from the group consisting of dimethomorph, fenpropimorph, tridemorph, fenpropidin, prochloraz, kresoxim-methyl, orysastrobin, metconazole, pyraclos- trobin, boscalid and metrafenone.

7. The EC as claimed in any of the preceding claims, consisting essentially of

a) 0.1 to 30% by weight of the triazole, b) 6 to 97% by weight of the solvent system, comprising

b1 ) the substituted phenol, b2) one or more organic solvents;

c) 2 to 20% by weight of one or more emulsifiers, and

d) 0 to 52% of further formulation additives.

8. The EC as claimed in any of the preceding claims, where the solvent system comprises as component (b1 ) a phenol of the formula

R¹— O-X , wherein R¹ is phenyl, substituted by one to three Ci-Ci2-alkyl and X is hydrogen, an alkali metal, an alkaline earth metal or NR3, in which each R is the same or dif- ferent and is hydrogen or d-Cs-alkyl, optionally substituted by hydroxy.

9. The EC as claimed in claim 8, wherein the phenol is selected from the group consisting of 2,3,6-trimethylphenol, p-tert-butylphenol, o-sec-butylphenol, 2-tert- butylphenol, p-tert-amylphenol, heptyl derives (p-heptylphenol), p-tert- octylphenol, p-octylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, p-

(alpha, alpha-dimethylbenzyl)phenol, p-nonylphenol, 2,4-di-tert-pentylphenol, p- dodecylphenol, 4-sec-butyl-2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol and 2,4-bis(alpha, alpha-dimethylbenzyl)phenol.

10. The EC as claimed in claim 9, wherein the phenol is o-sec-butylphenol.

1 1. The EC as claimed in any of the preceding claims, where the solvent system comprises as organic solvent component (b2) an aromatic hydrocarbon.

12. The EC as claimed in any of the preceding claims, where the emulsifier component (c) comprises at least one polymeric emulsifier.

13. The EC as claimed in any of the preceding claims, where the emulsifier component (c) comprises at least one water soluble polymeric emulsifier.

14. The EC as claimed in any of the preceding claims, where the emulsifier component (c) comprises at least one anionic polymeric emulsifier.

15. The EC as claimed in any of the preceding claims, where the emulsifier compo- nent (c) comprises at least two emulsifiers.

16. A process for preparing an EC, comprising the steps of mixing components a, b, c and optionally d according to the definition given in any of the preceding claims if appropriate with stirring and/or heating.

17. The use of an EC according to the definition given in any of claims 1 to 15 for controlling harmful fungi.

18. A method for controlling harmful fungi, comprising the steps of diluting an EC according to the definition given in any of claims 1 to 15 and applying it directly or indirectly to the harmful fungi, their habitat or the plants to be protected against fungicidal attack, the soil or seed.