Fungicidal Mixtures

(19) TZZ¥¥Z___T

(11) EP 3 530 118 A1

(12) EUROPEAN PATENT APPLICATION

(43) Date of publication: (51) Int Cl.: 28.08.2019 Bulletin 2019/35 A01P 3/00 (2006.01) A01N 43/40 (2006.01) A01N 43/56 (2006.01) (21) Application number: 18158566.2

(22) Date of filing: 26.02.2018

(84) Designated Contracting States: (72) Inventors: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB • SANTOS, Paulo Sergio Jose Dos GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO 67117 Limburgerhof (DE) PL PT RO RS SE SI SK SM TR • GEWEHR, Markus Designated Extension States: 67117 Limburgerhof (DE) BA ME • VONEND, Michael Designated Validation States: 67056 Ludwigshafen (DE) MA MD TN (74) Representative: BASF IP Association (71) Applicant: BASF SE BASF SE 67056 Ludwigshafen am Rhein (DE) G-FLP-C006 67056 Ludwigshafen (DE)

(54) FUNGICIDAL MIXTURES

(57) The present invention relates to fungicidal mixtures comprising, as active components, Fluxapy-roxad (I) and Florylpicoxamid (II), and optionally a third fungicidal compound III, wherein compound III is selected from groups (A) to (E), as well as methods to combat phytopathogenic fungi based on such mixtures. EP 3 530 118 A1

Printed by Jouve, 75001 PARIS (FR) 1 EP 3 530 118 A1 2

Description tetralin-1-yl-pyridine-2-carboxamide, 4-[1-[2-[3-(difluoromethyl)-5-(trifluorome- [0001] The present invention relates to fungicidal mix- thyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin- tures comprising, as active components, Fluxapyroxad 1-yl-pyridine-2-carboxamide, 4-[1-[2-[5-cyclo- (I) and Florylpicoxamid (II), and optionally a third fungi- 5 propyl-3-(difluoromethyl)pyrazol-1-yl]acetyl]-4- cidal compound III, wherein compound III is selected from piperidyl]-N-tetralin-1-yl-pyridine-2-carboxam- groups (A) to (E) consisting of: ide, 4-[1-[2-[5-methyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyri- A) Respiration inhibitors dine-2-carboxamide, 4-[1-[2-[5-(difluorome- 10 thyl)-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-

- Inhibitors of complex III at Q o site: azoxystrobin, piperidyl]-N-tetralin-1-yl-pyridine-2-carboxam- dimoxystrobin, kresoxim-methyl, picoxystrobin, ide, 4-[1-[2-[3,5-bis(trifluoromethyl)pyrazol-1- pyraclostrobin, trifloxystrobin, famoxadone; yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2- carboxamide, (4-[1-[2-[5-cyclopropyl-3-(trifluor- 15 - inhibitors of complex III at Qi site: cyazofamid; omethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide; - inhibitors of complex II: bixafen, boscalid, fluopyram, penthiopyrad, pydiflumetofen, inpyr- D) Inhibitors with Multi Site Action: mancozeb, me- fluxam isoflucypram, 2-(difluorome-tiram, zineb, chlorothalonil, folpet, dithianon; thyl)-N-(1,1,3-trimethyl-indan-4-yl)pyridine-3- 20 carboxamide, 2-(difluoromethyl)-N-[(3R)-1,1,3- E) Other fungicides: fosetyl, fosetyl-aluminum; met- trimethylindan-4-yl]pyridine-3-carboxamide, alaxyl, metalaxyl-M, carbendazim, thiophanate-me- 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-in- thyl, fluopicolide, metrafenone, pyrimethanil; fludiox- dan-4-yl)pyridine-3-carboxamide, 2-(difluor- onil; quinoxyfen; cymoxanil, proquinazid,N’-(4-(4- omethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4- 25 chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl- yl]pyridine-3-carboxamide,2-(difluorome- phenyl)-N-ethyl-N-methyl formamidine, N’-(4-(4- thyl)-N-(1,1-dimethyl-3-propyl-indan-4-yl)pyrid- fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethylphe- ine-3-carboxamide, 2-(difluoromethyl)-N-[(3R)- nyl)-N-ethyl-N-methyl formamidine, picarbutrazox, 1,1-dimethyl-3-propyl-indan-4-yl]pyridine-3- pentyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl- carboxamide, 2-(difluoromethyl)-N-(3-isobutyl- 30 methylene]amino]oxymethyl]-2-pyridyl]carbamate, 1,1-dimethyl-indan-4-yl)pyridine-3-carboxam- but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl- ide, 2-(difluoromethyl)-N-[(3R)-3-isobutyl-1,1- methylene]amino]oxymethyl]-2-pyridyl]carbamate. dimethyl-indan-4-yl]pyridine-3-carboxamide; [0002] Moreover, the invention relates to a method for - other respiration inhibitors: fluazinam, meptyldi- 35 controlling phytopathogenic fungi, using the inventive nocap, ametoctradin; mixtures of compounds I, II and optionally III, and to the use of compounds I, II and optionally a compound III as B) Sterol biosynthesis inhibitors (SBI fungicides): defined abovefor preparing such mixtures, and also com- difenoconazole, epoxiconazole, fluquinconazole, positions comprising such mixtures. metconazole, myclobutanil, penconazole, propico- 40 [0003] Additionally, the present invention also com- nazole, prothioconazole, mefentrifluconazole, dode- prises a method for protection of plant propagation ma- morph, fenpropimorph, tridemorph; terial (preferably seed) from phytopathogenic fungi or comprising contacting the plant propagation materials C) Lipid and membrane synthesis inhibitors (preferably seeds) with an inventive mixture in fungicid- 45 ally effective amounts. - Phospholipid biosynthesis inhibitors: dimetho- [0004] The term "plant propagation material" is to be morph, mandipropamid, valifenalate, propamo- understood to denote all the generative parts of the plant carb, oxathiapiprolin, 2-{3-[2-(1-{[3,5-bis(dif- such as seeds and vegetative plant material such as cut- luoromethyl-1H-pyrazol-1-yl]acetyl}piperidin-4- tings and tubers (e. g. potatoes), which can be used for yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5- 50 the multiplication of the plant. This includes seeds, roots, yl}phenyl methanesulfonate 2-{3-[2-(1-{[3,5- fruits, tubers, bulbs, rhizomes, shoots, sprouts and other bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}pip- parts of plants, including seedlings and young plants, eridin-4-yl) 1,3-thiazol-4-yl]-4,5-dihydro-1,2-ox- which are to be transplanted after germination or after azol-5-yl}-3-chlorophenyl methanesul-emergence from soil. These young plants may also be fonate,4-[1-[2-[3-(difluoromethyl)-5-methyl- 55 protected before transplantation by a total or partial treat- pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl- ment by immersion or pouring. In a particularly preferred pyridine-2-carboxamide, 4-[1-[2-[3,5-bis(dif- embodiment, the term propagation material denotes luoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N- seeds.

2 3 EP 3 530 118 A1 4

[0005] Additionally, the present invention also com- [0011] Another problem encountered concerns the prises a method for protection of plant propagation ma- need to have available control agents which are effective terial (preferably seed) from phytopathogenic fungi com- against a broad spectrum of harmful fungi. prising contacting the plant propagation materials (pref- [0012] There also exists the need for control agents erably seeds) with the inventive mixture in fungicidally 5 that combine fast action with long lasting action. effective amounts. [0013] Another difficulty in relation to the use of fungi- [0006] Moreover, the invention relates to a method for cides is that the repeated and exclusive application of an controlling phytopathogenic fungi using the inventive individual compound leads in many cases to a rapid se- mixtures and to the use of the compounds present in the lection of harmful fungi, which have developed natural or inventive mixtures for preparing such mixtures, and also 10 adapted resistance against the active compound in ques- to compositions comprising such mixtures. tion. Therefore, there is a need for control agents that [0007] The present invention further relates to plant- help prevent or overcome resistance. protecting active ingredient mixtures having synergisti- [0014] Another problem underlying the present inven- cally enhanced action of improving the health of plants tion is the desire for compositions that improve plants, a and to a method of applying such inventive mixtures to 15 process which is commonly and hereinafter referred to the plants. as "plant health". [0008] Compound I , its preparation as well as its fun- [0015] The term plant health comprises various sorts giicidal is known from WO 2006/087343. Compound II, of improvements of plants that are not connected to the its preparation as well as its fungicidal activity is known control of fungi. For example, advantageous properties from WO 2016/122802. 20 that may be mentioned are improved crop characteristics [0009] Compounds III as well as their fungicidal activity including: emergence, crop yields, protein content, oil and methods for producing them are generally known content, starch content, more developed root system (im- (cf.: http://www.alanwood.net/pesticides/); these sub- proved root growth), improved stress tolerance (e.g. stances are commercially available. The compounds de- against drought, heat, salt, UV, water, cold), reduced eth- scribed by IUPAC nomenclature, their preparation and 25 ylene (reduced production and/or inhibition of reception), their pesticidal activity are also known (cf. Can. J. Plant tillering increase, increase in plant height, bigger leaf Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031; blade, less dead basal leaves, stronger tillers, greener EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 leaf color, pigment content, photosynthetic activity, less 941; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; input needed (such as fertilizers or water), less seeds EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE 30 needed, more productive tillers, earlier flowering, early 19650197; DE 10021412; DE 102005009458; US grain maturity, less plant verse (lodging), increased shoot 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; growth, enhanced plant vigor, increased plant stand and WO 99/24413; WO 99/27783; WO 00/29404; WO early and better germination; or any other advantages 00/46148; WO 00/65913; WO 01/54501; WO 01/56358; familiar to a person skilled in the art. WO 02/22583; WO 02/40431; WO 03/10149; WO35 [0016] It was therefore an object of the present inven- 03/11853; WO 03/14103; WO 03/16286; WO 03/53145; tion to provide fungicidal mixtures which solve the prob- WO 03/61388; WO 03/66609; WO 03/74491; WO lems of reducing the dosage rate and / or enhancing the 04/49804; WO 04/83193; WO 05/120234; WOspectrum of activity and / or combining fast activity with 05/123689; WO 05/123690; WO 05/63721; WOprolonged control and / or to resistance management 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; 40 and/or promoting the health of plants. WO 06/87343; WO 07/82098; WO 07/90624, WO [0017] We have found that this object is in part or in 10/139271, WO 11/028657, WO 12/168188, WO whole achieved by the fungicidal mixtures comprising, 07/006670, WO 11/77514; WO 13/047749, WOas active components, Fluxapyroxad (I) and Florylpicox- 10/069882, WO 13/047441, WO 03/16303, WOamid (II), and optionally a third fungicidal compound III 09/90181, WO 13/007767, WO 13/010862, 45 WOas defined earlier. 13/127704, WO 13/024009, WO 13/24010, WO[0018] Especially, it has been found that the mixtures 13/047441, WO 13/162072, WO 13/092224, WO as defined in the outset show markedly enhanced action 11/135833, CN 1907024, CN 1456054, CN 103387541, against phytopathogenic fungi compared to the control CN 1309897, WO 12/84812, CN 1907024, WOrates that are possible with the individual compounds 09094442, WO 14/60177, WO 13/116251, 50 WOand/or is suitable for improving the health of plants when 08/013622, WO 15/65922, WO 94/01546, EP 2865265, applied to plants, parts of plants, seeds, or at their locus WO 07/129454, WO 12/165511, WO 11/081174, WO of growth. 13/47441). [0019] It has been found that the action of the inventive [0010] One typical problem arising in the field of fungi mixtures comprising compounds I, II and optionally a control lies in the need to reduce the dosage rates of the 55 compound III goes far beyond the fungicidal and/or plant active ingredients in order to reduce or avoid unfavorable health improving action of the active compounds present environmental or toxicological effects whilst still allowing in the mixture alone (synergistic action). effective fungal control. [0020] Moreover, we have found that simultaneous,

3 5 EP 3 530 118 A1 6 that is joint or separate, application of the compounds I, glycols; DMSO; ketones, e.g. cyclohexanone; esters, II and optionally III, or successive application of com- e.g. lactates, carbonates, fatty acid esters, gamma-bu- pounds I, II and optionally III, allows enhanced control of tyrolactone; fatty acids; phosphonates; amines; amides, harmful fungi, compared to the control rates that are pos- e.g. N-methylpyrrolidone, fatty acid dimethylamides; and sible with the individual compounds (synergistic mix- 5 mixtures thereof. tures). [0029] Suitable solid carriers or fillers are mineral [0021] Moreover, we have found that simultaneous, earths, e.g. silicates, silica gels, talc, kaolins, limestone, that is joint or separate, application of compounds I, II lime, chalk, clays, dolomite, diatomaceous earth, ben- and optionally III, or successive application of com- tonite, calcium sulfate, magnesium sulfate, magnesium pounds I, II and optionally III, provides enhanced plant 10 oxide; polysaccharides, e.g. cellulose, starch; fertilizers, health effects compared to the plant health effects that e.g. ammonium sulfate, ammonium phosphate, ammo- are possible with the individual compounds. nium nitrate, ureas; products ofvegetable origin, e.g. ce- [0022] The ratio by weight of compound I and com- real meal, tree bark meal, wood meal, nutshell meal, and pound II in binary mixtures is from 10000:1 to 1:10000, mixtures thereof. from 500:1 to 1:500, preferably from 100:1 to 1:100 more 15 [0030] Suitable surfactants are surface-active com- preferably from 50:1 to 1:50, most preferably from 20:1 pounds, such as anionic, cationic, nonionic and ampho- to 1:20, including also ratios from 10:1 to 1:10, 1:5 to 5:1, teric surfactants, block polymers, polyelectrolytes, and or 1:1. mixtures thereof. Such surfactants can be used as emul- [0023] All above-referred mixtures are herein below re- sifier, dispersant, solubilizer, wetter, penetration enhanc- ferred to as "inventive mixtures". 20 er, protective colloid, or adjuvant. Examples of sur- [0024] The inventive mixtures can further contain one factants are listed in McCutcheon’s, Vol.1: Emulsifiers & or more insecticides, fungicides, herbicides. Detergents, McCutcheon’s Directories, Glen Rock, USA, [0025] The inventive mixtures can be converted into 2008 (International Ed. or North American Ed.). customary types of agrochemical compositions, e. g. so- [0031] Suitable anionic surfactants are alkali, alkaline lutions,emulsions, suspensions, dusts, powders, pastes, 25 earth or ammonium salts of sulfonates, sulfates, phos- granules, pressings, capsules, and mixtures thereof. Ex- phates, carboxylates, and mixtures thereof. Examples of amples for composition types are suspensions (e.g. SC, sulfonates are alkylarylsulfonates, diphenylsulfonates, OD, FS), emulsifiable concentrates (e.g. EC), emulsions alpha-olefin sulfonates, lignine sulfonates, sulfonates of (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, fatty acids and oils, sulfonates of ethoxylated alkylphe- pastilles, wetable powders or dusts (e.g. WP, SP, WS, 30 nols, sulfonates of alkoxylated arylphenols, sulfonates of DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, condensed naphthalenes, sulfonates of dodecyl- and tri- SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as decylbenzenes, sulfonates of naphthalenes and alkyl- well as gel formulations for the treatment of plant prop- naphthalenes, sulfosuccinates or sulfosuccinamates. agation materials such as seeds (e.g. GF). These and Examples of sulfates are sulfates of fatty acids and oils, further compositions types are defined in the "Catalogue 35 of ethoxylated alkylphenols, of alcohols, of ethoxylated of pesticide formulation types and international coding alcohols, or of fatty acid esters. Examples of phosphates system", Technical Monograph No. 2, 6th Ed. May 2008, are phosphate esters. Examples of carboxylates are alkyl CropLife International. carboxylates, and carboxylated alcohol or alkylphenol [0026] The compositions are prepared in a known ethoxylates. manner, such as described by Mollet and Grubemann, 40 [0032] Suitable nonionic surfactants are alkoxylates, Formulation technology, Wiley VCH, Weinheim, 2001; or N-subsituted fatty acid amides, amine oxides, esters, Knowles, New developments in crop protection product sugar-basedsurfactants, polymeric surfactants, and mix- formulation, Agrow Reports DS243, T&F Informa, Lon- tures thereof. Examples of alkoxylates are compounds don, 2005. such as alcohols, alkylphenols, amines, amides, arylphe- [0027] Suitable auxiliaries are solvents, liquid carriers, 45 nols, fatty acids or fatty acid esters which have been solid carriers or fillers, surfactants, dispersants, emulsi- alkoxylated with 1 to 50 equivalents. Ethylene oxide fiers, wetters, adjuvants, solubilizers, penetration en- and/or propylene oxide may be employed for the alkox- hancers, protective colloids, adhesion agents, thicken- ylation, preferably ethylene oxide. Examples of N-subsi- ers, humectants, repellents, attractants, feeding stimu- titued fatty acid amides are fatty acid glucamides or fatty lants, compatibilizers, bactericides, anti-freezing agents, 50 acid alkanolamides. Examples of esters are fatty acid anti-foaming agents, colorants, tackifiers and binders. esters, glycerol esters or monoglycerides. Examples of [0028] Suitable solvents and liquid carriers are water sugar-based surfactants are sorbitans, ethoxylated sorb- and organic solvents, such as mineral oil fractions of me- itans, sucrose and glucose esters or alkylpolyglucosides. dium to high boiling point, e.g. kerosene, diesel oil; oils Examples of polymeric surfactants are home- or copol- of vegetable or animal origin; aliphatic, cyclic and aro- 55 ymers of vinylpyrrolidone, vinylalcohols, or vinylacetate. matic hydrocarbons, e. g. toluene, paraffin, tetrahydro- [0033] Suitable cationic surfactants are quaternary naphthalene, alkylated naphthalenes; alcohols, e.g. eth- surfactants, for example quaternary ammonium com- anol, propanol, butanol, benzylalcohol, cyclohexanol; pounds with one or two hydrophobic groups, or salts of

4 7 EP 3 530 118 A1 8 long-chain primary amines. Suitable amphoteric sur- 5-40 wt% of an inventive mixture and 1-10 wt% emul- factants arealkylbetains and imidazolines. Suitable block sifiers (e.g. calcium dodecylbenzenesulfonate and polymers are block polymers of the A-B or A-B-A type castor oil ethoxylate) are dissolved in 20-40 wt% wa- comprising blocks of polyethylene oxide and polypropyl- ter-insoluble organic solvent (e.g. aromatic hydro- ene oxide, or of the A-B-C type comprising alkanol, pol- 5 carbon). This mixture is introduced into water ad 100 yethylene oxide and polypropylene oxide. Suitable poly- wt% by means of an emulsifying machine and made electrolytes are polyacids or polybases. Examples of into a homogeneous emulsion. Dilution with water polyacids are alkali salts of polyacrylic acid or polyacid gives an emulsion. comb polymers. Examples of polybases are polyvi- v) Suspensions (SC, OD, FS) nylamines or polyethyleneamines. 10 In an agitated ball mill, 20-60 wt% of an inventive [0034] Suitable adjuvants are compounds, which have mixture are comminuted with addition of 2-10 wt% a neglectable or even no pesticidal activity themselves, dispersants and wetting agents (e.g. sodium ligno- and which improve the biological performance of the in- sulfonate and alcohol ethoxylate), 0.1-2 wt% thick- ventive mixtures on the target. Examples are surfactants, ener (e.g. xanthan gum) and water ad 100 wt% to mineral or vegetable oils, and other auxilaries. Further 15 give a fine active substance suspension. Dilution examples are listed by Knowles, Adjuvants and additives, with water gives a stable suspension of the active Agrow Reports DS256, T&F Informa UK, 2006, chapter 5. substance. For FS type composition up to 40 wt% [0035] Suitable thickeners are polysaccharides (e.g. binder (e.g. polyvinylalcohol) is added. xanthan gum, carboxymethylcellulose), inorganic clays vi) Water-dispersible granules and water-soluble (organically modified or unmodified), polycarboxylates, 20 granules (WG, SG) and silicates. 50-80 wt% of an inventive mixture are ground finely [0036] Suitable bactericides are bronopol and isothia- with addition of dispersants and wetting agents (e.g. zolinone derivatives such as alkylisothiazolinones and sodium lignosulfonate and alcohol ethoxylate) ad benzisothiazolinones. 100 wt% and prepared as water-dispersible or water- [0037] Suitable anti-freezing agents are ethylene gly- 25 soluble granules by means of technical appliances col, propylene glycol, urea and glycerin. (e. g. extrusion, spray tower, fluidized bed). Dilution [0038] Suitable anti-foaming agents are silicones, long with water gives a stable dispersion or solution of chain alcohols, and salts of fatty acids. the active substance. [0039] Suitable colorants (e.g. in red, blue, or green) vii) Water-dispersible powders and water-soluble are pigments of low water solubility and water-soluble 30 powders (WP, SP, WS) dyes. Examples are inorganic colorants (e.g. iron oxide, 50-80 wt% of an inventive mixture are ground in a titan oxide, iron hexacyanoferrate) and organic colorants rotor-stator mill with addition of 1-5 wt% dispersants (e.g. alizarin-, azo- and phthalocyanine colorants). (e.g. sodium lignosulfonate), 1-3 wt% wetting agents [0040] Suitable tackifiers or binders are polyvinylpyr- (e.g. alcohol ethoxylate) and solid carrier (e.g. silica rolidons, polyvinylacetates, polyvinyl alcohols, polyacr- 35 gel) ad 100 wt%. Dilution with water gives a stable ylates, biological or synthetic waxes, and cellulose dispersion or solution of the active substance. ethers. viii) Gel (GW, GF) [0041] Examples for composition types and their prep- In an agitated ball mill, 5-25 wt% of an inventive mix- aration are: ture are comminuted with addition of 3-10 wt% dis- 40 persants (e.g. sodium lignosulfonate), 1-5 wt% thick- i) Water-soluble concentrates (SL, LS) ener (e.g. carboxymethylcellulose) and water ad 100 10-60 wt% of an inventive mixture and 5-15 wt% wet- wt% to give a fine suspension of the active sub- ting agent (e.g. alcohol alkoxylates) are dissolved in stance. Dilution with water gives a stable suspension water and/or in a water-soluble solvent (e.g. alco- of the active substance. hols) ad 100 wt%. The active substance dissolves 45 ix) Microemulsion (ME) upon dilution with water. 5-20 wt% of an inventive mixture are added to 5-30 ii) Dispersible concentrates (DC) wt% organic solvent blend (e.g. fatty acid dimethyl- 5-25 wt% of an inventive mixture and 1-10 wt% dis- amide and cyclohexanone), 10-25 wt% surfactant persant (e. g. polyvinylpyrrolidone) are dissolved in blend (e.g. alcohol ethoxylate and arylphenol ethox- organic solvent (e.g. cyclohexanone) ad 100 wt%. 50 ylate), and water ad 100 %. This mixture is stirred Dilution with water gives a dispersion. for 1 h to produce spontaneously a thermodynami- iii) Emulsifiable concentrates (EC) callystable microemulsion. 15-70 wt% of an inventive mixture and 5-10 wt% x) Microcapsules (CS) emulsifiers (e.g. calcium dodecylbenzenesulfonate An oil phase comprising 5-50 wt% of an inventive and castor oil ethoxylate) are dissolved in water-in- 55 mixture, 0-40 wt% water insoluble organic solvent soluble organic solvent (e.g. aromatic hydrocarbon) (e.g. aromatic hydrocarbon), 2-15 wt% acrylic mon- ad 100 wt%. Dilution with water gives an emulsion. omers (e.g. methylmethacrylate, methacrylic acid iv) Emulsions (EW, EO, ES) anda di- or triacrylate) aredispersed into an aqueous

5 9 EP 3 530 118 A1 10

solution of a protective colloid (e.g. polyvinyl alco- seed dressing, pelleting, coating and dusting. hol). Radical polymerization initiated by a radical in- [0045] When employed in plant protection, the itiator results in the formation of poly(meth)acrylate amounts of active substances applied are, depending on microcapsules. Alternatively, an oil phase compris- the kind of effect desired, from 0.001 to 2 kg per ha, pref- ing 5-50 wt% of an inventive mixture according to 5 erably from 0.005 to 2 kg per ha, more preferably from the invention, 0-40 wt% water insoluble organic sol- 0.01 to 1.0 kg per ha, and in particular from 0.05 to 0.75 vent (e.g. aromatic hydrocarbon), and an isocyanate kg per ha. monomer (e.g. diphenylmethene-4,4’-diisocyana- [0046] In treatment of plant propagation materials such tae) are dispersed into an aqueous solution of a pro- as seeds, e. g. by dusting, coating or drenching seed, tective colloid (e.g. polyvinyl alcohol). The addition 10 amounts of active substance of from 0.01-10kg, prefer- of a polyamine (e.g. hexamethylenediamine) results ably from 0.1-1000 g, more preferably from 1-100 g per in the formation of polyurea microcapsules. The 100 kilogram of plant propagation material (preferably monomers amount to 1-10 wt%. The wt% relate to seeds) are generally required. the total CS composition. [0047] When used in the protection of materials or xi) Dustable powders (DP, DS) 15 stored products, the amount of active substance applied 1-10 wt% of an inventive mixture are ground finely depends on the kind of application area and on the de- and mixed intimately with solid carrier (e.g. finely di- sired effect. Amounts customarily applied in the protec- vided kaolin) ad 100 wt%. tion of materials are 0.001 g to 2 kg, preferably 0.005 g xii) Granules (GR, FG) to 1 kg, of active substance per cubic meter of treated 0.5-30 wt% of an inventive mixture is ground finely 20 material. and associated with solid carrier (e.g. silicate) ad 100 [0048] Various types of oils, wetters, adjuvants, ferti- wt%. Granulation is achieved by extrusion, spray- lizer, or micronutrients, and further pesticides (e.g. her- drying or fluidized bed. bicides, insecticides, fungicides, growth regulators, xiii) Ultra-low volume liquids (UL) safeners) may be added to the active substances or the 1-50 wt% of an inventive mixture are dissolved in 25 compositions comprising them as premix or, if appropri- organic solvent (e.g. aromatic hydrocarbon) ad 100 ate not until immediately prior to use (tank mix). These wt%. agents can be admixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, pref- [0042] The compositions types i) to xiii) may optionally erably 1:10 to 10:1. comprise further auxiliaries, such as 0.1-1 wt% bacteri- 30 [0049] The user applies the composition according to cides, 5-15 wt% anti-freezing agents, 0.1-1 wt% anti- the invention usually from a predosage device, a knap- foaming agents, and 0.1-1 wt% colorants. sack sprayer, a spray tank, a spray plane, or an irrigation [0043] The resulting agrochemical compositions gen- system. Usually, the agrochemical composition is made erally comprise between 0.01 and 95%, preferably be- up with water, buffer, and/or further auxiliaries to the de- tween 0.1 and 90%, and in particular between 0.5 and 35 sired application concentration and the ready-to-use 75%, by weight of active substances. The active sub- spray liquor or the agrochemical composition according stances are employed in a purity of from 90% to 100%, to the invention is thus obtained. Usually, 20 to 2000 lit- preferably from 95% to 100% (according to NMR spec- ers, preferably 50 to 400 liters, of the ready-to-use spray trum). liquor are applied per hectare of agricultural useful area. [0044] Solutions for seed treatment (LS), Suspoemul- 40 [0050] According to one embodiment, individual com- sions (SE), flowable concentrates (FS), powders for dry ponents of the composition according to the invention treatment (DS), water-dispersible powders for slurry such as parts of a kit or parts of a binary mixture may be treatment (WS), water-soluble powders (SS), emulsions mixed by the user himself in a spray tank or any other (ES), emulsifiable concentrates (EC) and gels (GF) are kind of vessel used for applications (e. g. seed treater usually employed for the purposes of treatment of plant 45 drums, seed pelleting machinery, knapsack sprayer) and propagation materials, particularly seeds. The composi- further auxiliaries may be added, if appropriate. tions in question give, after two-to-tenfold dilution, active [0051] Consequently, one embodiment of the inven- substance concentrations of from 0.01 to 60% by weight, tion is a kit for preparing a usable pesticidal composition, preferably from 0.1 to 40%, in the ready-to-use prepara- the kit comprising a) a composition comprising compo- tions. Application can be carried out before or during sow- 50 nent 1) as defined herein and at least one auxiliary; and ing. Methods for applying the inventive mixtures and b) a composition comprising component 2) as defined compositions thereof, respectively, on to plant propaga- herein and at least one auxiliary; and optionally c) a com- tion material, especially seeds include dressing, coating, position comprising at least one auxiliary and optionally pelleting, dusting, soaking and in-furrow application a further active component 3) as defined herein. methods of the propagation material. Preferably, the in- 55 [0052] As said above, the present invention comprises ventive mixtures or the compositions thereof, respective- a method for controlling harmful fungi, wherein the fungi, ly, are applied on to the plant propagation material by a their habitat, their locus or the plants to be protected method such that germination is not induced, e. g. by against fungal attack, the soil or plant propagation ma-

6 11 EP 3 530 118 A1 12 terial (preferably seed) are treated with a fungicidally ef- on corn, cereals, such as barley (e. g. D. teres, net fective amount of an inventive mixture. blotch) and wheat (e. g. D. tritici-repentis: tan spot), [0053] Advantageously, the inventive mixtures are rice and turf; Esca (dieback, apoplexy) on vines, suitable for controlling the following fungal plant diseas- caused by Formitiporia (syn. Phellinus) punctata, F. es: 5 mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoa- Albugo spp. (white rust) on ornamentals, vegetables cremonium aleophilum and/or Botryosphaeria obtu- (e. g. A. candida) and sunflowers (e. g. A. tragopo- sa; Elsinoe spp. on pome fruits (E. pyri), soft fruits gonis); Alternaria spp. (Alternaria leaf spot) on veg- (E. veneta: anthracnose) and vines ( E. ampelina: an- etables, rape A. ( brassicola or brassicae), sugar 10 thracnose); Entyloma oryzae (leaf smut) on rice; Ep- beets (A. tenuis), fruits, rice, soybeans, potatoes (e. icoccum spp. (black mold) on wheat; Erysiphe spp. g. A. solani or A. alternata), tomatoes (e. g. A. solani (powdery mildew) on sugar beets (E. betae), vege- or A. alternata) and wheat; Aphanomyces spp. on tables (e. g. E. pisi), such as cucurbits (e. g. E. ci- sugar beets and vegetables; Ascochyta spp. on ce- choracearum), cabbages, rape (e. g. E. cruciferar- reals and vegetables, e. g. A. tritici (anthracnose) on 15 um); Eutypa lata (Eutypa canker or dieback, an- wheat and A. hordei on barley;Bipolaris and amorph: Cytosporina lata, syn. Libertella blepharis) Drechslera spp. (teleomorph: Cochliobolus spp.), e. on fruit trees, vines and ornamental woods; Exsero- g. Southern leaf blight (D. maydis) or Northern leaf hilum (syn. Helminthosporium) spp. on corn (e. g. E. blight (B. zeicola) on corn, e. g. spot blotch (B. so- turcicum); Fusarium (teleomorph: Gibberella) spp. rokiniana) on cereals and e. g. B. oryzae on rice and 20 (wilt, root or stem rot) on various plants, such as F. turfs; Blumeria (formerly Erysiphe) graminis (pow- graminearum or F. culmorum (root rot, scab or head dery mildew) on cereals (e. g. on wheat or barley); blight) on cereals (e. g. wheat or barley), F. oxyspo- Botrytis cinerea (teleomorph: Botryotinia fuckeliana: rum on tomatoes, F. solani (f. sp. glycines now syn. grey mold) on fruits and berries (e. g. strawberries), F. virguliforme)and F. tucumaniaeand F. brasiliense vegetables (e. g. lettuce, carrots, celery and cabbag- 25 each causing sudden death syndrome on soybeans, es), rape, flowers, vines, forestry plants and wheat; and F. verticillioides on corn; Gaeumannomyces Bremia lactucae (downy mildew) on lettuce; Cerato- graminis (take-all) on cereals (e. g. wheat or barley) cystis (syn. Ophiostoma) spp. (rot or wilt) on broad- and corn; Gibberella spp. on cereals (e. g. G. zeae) leaved trees and evergreens, e. g.C. ulmi (Dutch and rice (e. g. G. fujikuroi: Bakanae disease); Glom- elm disease) on elms; Cercospora spp. (Cercospora 30 erella cingulata on vines, pome fruits and other leaf spots) on corn (e. g. Gray leaf spot:C. zeae- plants and G. gossypii on cotton; Grainstaining com- maydis), rice, sugar beets (e. g. C. beticola), sugar plex on rice; Guignardia bidwellii (black rot) on vines; cane, vegetables, coffee, soybeans (e. g. C. sojina Gymnosporangium spp. on rosaceous plants and ju- or C. kikuchii) and rice; Cladosporium spp. on toma- nipers, e. g. G. sabinae (rust) on pears; Helminthos- toes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. 35 porium spp. (syn. Drechslera, teleomorph: Coch- herbarum (black ear) on wheat; Claviceps purpurea liobolus) on corn, cereals and rice; Hemileia spp., e. (ergot) on cereals;Cochliobolus (anamorph: g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis Helminthosporium of Bipolaris) spp. (leaf spots) on clavispora (syn. Cladosporium vitis) on vines; Mac- corn (C. carbonum), cereals (e. g. C. sativus, an- rophomina phaseolina(syn. phaseoli) (root and stem amorph: B. sorokiniana) and rice (e. g. C. miyabea- 40 rot) on soybeans and cotton;Microdochium (syn. nus, anamorph: H. oryzae); Colletotrichum (teleo- Fusarium) nivale (pink snow mold) on cereals (e. g. morph: Glomerella) spp. (anthracnose) on cotton (e. wheat or barley); Microsphaera diffusa (powdery mil- g. C. gossypii), corn (e. g. C. graminicola: Anthrac- dew) on soybeans; Monilinia spp., e. g. M. laxa, M. nose stalk rot), soft fruits, potatoes (e. g.C. coc- fructicola and M. fructigena (bloom and twig blight, codes: black dot), beans (e. g. C. lindemuthianum) 45 brown rot) on stone fruits and other rosaceous and soybeans (e. g. C. truncatum or C. gloeospori- plants; Mycosphaerella spp. on cereals, bananas, oides); Corticium spp., e. g. C. sasakii (sheath blight) soft fruits and ground nuts, such as e. g. M. gramin- on rice; Corynespora cassiicola (leaf spots) on soy- icola (anamorph: Septoria tritici, Septoria blotch) on beans and ornamentals; Cycloconium spp., e. g. C. wheat or M. fijiensis (black Sigatoka disease) on ba- oleaginum on olive trees; Cylindrocarpon spp. (e. g. 50 nanas; Peronospora spp. (downy mildew) on cab- fruit tree canker or young vine decline, teleomorph: bage (e. g. P. brassicae), rape (e. g. P. parasitica), Nectria or Neonectria spp.) on fruit trees, vines (e. onions (e. g. P. destructor), tobacco (P. tabacina) g. C. liriodendri, teleomorph: Neonectria liriodendri: and soybeans (e. g. P. manshurica); Phakopsora Black Foot Disease) and ornamentals; Dematopho- pachyrhizi and P. meibomiae (soybean rust) on soy- ra (teleomorph: Rosellinia) necatrix(root and stem 55 beans; Phialophora spp. e. g. on vines (e. g. P. tra- rot) on soybeans; Diaporthe spp., e. g. D. phaseolo- cheiphila and P. tetraspora) and soybeans (e. g. P. rum (damping off) on soybeans;Drechslera (syn. gregata: stem rot); Phoma lingam (root and stem rot) Helminthosporium, teleomorph: Pyrenophora) spp. on rape and cabbage and P. betae (root rot, leaf spot

7 13 EP 3 530 118 A1 14 and damping-off) on sugar beets; Phomopsis spp. (syn. Erysiphe) necator(powdery mildew, an- on sunflowers, vines (e. g. P. viticola: can and leaf amorph: Oidium tuckeri) on vines; Setospaeria spp. spot) and soybeans (e. g. stem rot: P. phaseoli, tel- (leaf blight) on corn (e. S. g. turcicum, syn. eomorph: Diaporthe phaseolorum); Physoderma Helminthosporium turcicum) and turf; Sphacelothe- maydis (brown spots) on corn;Phytophthora spp. 5 ca spp. (smut) on corn, (e. g. S. reiliana: head smut), (wilt, root, leaf, fruit and stem root) on various plants, sorghum und sugar cane; Sphaerotheca fuliginea such as paprika and cucurbits (e. g. P. capsici), soy- (powdery mildew) on cucurbits; Spongospora sub- beans(e. g. P. megasperma,syn. P.sojae ), potatoes terranea (powdery scab) on potatoes and thereby and tomatoes (e. g.P. infestans: late blight) and transmittedviral diseases; Stagonospora spp. on ce- broad-leaved trees (e. g. P. ramorum: sudden oak 10 reals, e. g. S. nodorum (Stagonospora blotch, tele- death); Plasmodiophora brassicae (club root) on omorph: Leptosphaeria [syn. Phaeosphaeria] nodo- cabbage, rape, radish and other plants; Plasmopara rum) on wheat; Synchytrium endobioticum on pota- spp., e. g. P. viticola (grapevine downy mildew) on toes (potato wart disease); Taphrina spp., e.g. T. de- vines and P. halstedii on sunflowers; Podosphaera formans (leaf curl disease) on peaches and T. pruni spp. (powdery mildew) on rosaceous plants, hop, 15 (plum pocket) on plums; Thielaviopsis spp. (black pome and soft fruits, e. g. P. leucotricha on apples; root rot) on tobacco, pome fruits, vegetables, soy- Polymyxa spp., e. g. on cereals, such as barley and beans and cotton, e. g.T. basicola (syn. Chalara wheat (P. graminis) and sugar beets (P. betae) and elegans); Tilletia spp. (common bunt or stinking thereby transmitted viral diseases;Pseudocer- smut) on cereals, such as e. g. T.tritici (syn. T. caries, cosporella herpotrichoides (eyespot, teleomorph: 20 wheat bunt) and T. controversa (dwarf bunt) on Tapesia yallundae) on cereals, e. g. wheat or barley; wheat; Typhula incarnata(grey snow mold) on barley Pseudoperonospora (downy mildew) on various or wheat; Urocystis spp., e. g. U. occulta (stem smut) plants, e. g. P. cubensis on cucurbits or P. humili on on rye; Uromyces spp. (rust) on vegetables, such as hop; Pseudopezicula tracheiphila (red fire disease beans (e. g. U.appendiculatus, syn. U. phaseoli)and or ,rotbrenner’, anamorph: Phialophora) on vines; 25 sugar beets (e. g. U. betae); Ustilago spp. (loose Puccinia spp. (rusts) on various plants, e. g. P. trit- smut) on cereals (e. g. U. nuda and U. avaenae), icina (brown or leaf rust), P. striiformis (stripe or yel- corn (e. g. U. maydis: corn smut) and sugar cane; low rust), P. hordei (dwarf rust), P. graminis (stem Venturia spp. (scab) on apples (e. g. V. inaequalis) or black rust) or P. recondita (brown or leaf rust) on and pears; and Verticillium spp. (wilt) on various cereals, such as e. g. wheat, barley or rye, P. kueh- 30 plants, such as fruits and ornamentals, vines, soft nii(orange rust) on sugar cane and P. asparagi on fruits, vegetables and field crops, e. g. V. dahliae on asparagus; Pyrenophora (anamorph: Drechslera) strawberries, rape, potatoes and tomatoes. tritici-repentis (tan spot) on wheat orP. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae [0054] The inventive mixtures are particularly suitable (teleomorph: Magnaporthe grisea, rice blast) on rice 35 for controlling wheat diseases caused by Alternaria spp. and P. grisea on turf and cereals;Pythium spp. (Alternaria leaf spot), Ascochyta tritici (anthracnose), (damping-off) on turf, rice, corn, wheat, cotton, rape, Blumeria (formerly Erysiphe) graminis(powdery mildew), sunflowers, soybeans, sugar beets, vegetables and Botrytis cinerea (teleomorph: Botryotiniafuckeliana : grey various other plants (e. g. P. ultimum or P. aphani- mold), Cladosporium herbarum (black ear), Drechslera dermatum); Ramularia spp., e. g. R. collo-cygni (Ra- 40 (syn. Helminthosporium, teleomorph: Pyrenophora) trit- mularialeaf spots,Physiological leafspots) onbarley ici-repentis (tan spot), Epicoccum spp. (black mold), and R. beticola on sugar beets; Rhizoctonia spp. on Fusarium (teleomorph: Gibberella)graminearum or cotton, rice, potatoes, turf, corn, rape, potatoes, sug- Fusarium culmorum (root rot, scab or head blight), Gae- ar beets, vegetables and various other plants, e. g. umannomyces graminis (take-all), Microdochium (syn. R. solani (root and stem rot) on soybeans, R. solani 45 Fusarium) nivale (pink snow mold),Mycosphaerella (sheath blight) on rice orR. cerealis (Rhizoctonia graminicola (anamorph: Septoria tritici, Septoria blotch), spring blight) on wheat or barley; Rhizopus stolonifer Polymyxa graminis, Pseudocercosporella herpotri- (black mold, soft rot) on strawberries, carrots, cab- choides (eyespot, teleomorph: Tapesia yallundae), Puc- bage, vines and tomatoes; Rhynchosporium secalis cinia graminis (stem or black rust), Puccinia recondita (scald) on barley, rye and triticale;Sarocladium 50 (brown or leaf rust),Pyrenophora (anamorph: oryzae and S. attenuatum (sheath rot) on rice; Scle- Drechslera) tritici-repentis (tan spot),Pythium spp. rotinia spp. (stem rot or white mold) on vegetables (damping-off), Rhizoctonia cerealis (Rhizoctonia spring and field crops, such as rape, sunflowers (e. g. S. blight), Septoria tritici (Septoria blotch), Stagonospora sclerotiorum) and soybeans (e. g . S. rolfsii or S. scle- nodorum (Stagonospora blotch, teleomorph: Lept- rotiorum); Septoria spp. on various plants, e. g.S. 55 osphaeria [syn. Phaeosphaeria] nodorum), Tilletia. tritici glycines (brown spot) on soybeans, S. tritici (Septo- (syn. Tilletia caries, wheat bunt), T. controversa (dwarf ria blotch) on wheat and S. (syn. Stagonospora) no- bunt) or Typhula incarnata (grey snow mold). dorum (Stagonospora blotch) on cereals; Uncinula [0055] The mixtures according to the present inven-

8 15 EP 3 530 118 A1 16 tion, respectively, are also suitable for controlling harmful [0061] The inventive mixtures are employed by treat- fungi in the protection of stored products or harvest and ing the fungi or the plants, plant propagation materials in the protection of materials. (preferably seeds), materials or soil to be protected from [0056] The term "protection of materials" is to be un- fungal attack with a fungicidally effective amount of the derstood to denote the protection of technical and non- 5 active compounds. The application can be carried out living materials, such as adhesives, glues, wood, paper both before and after the infection of the materials, plants and paperboard, textiles, leather, paint dispersions, plas- or plant propagation materials (preferably seeds) by the tics, cooling lubricants, fiber or fabrics, against the infes- pests. tation and destruction by harmful microorganisms, such [0062] In the context of the present invention, the term as fungi and bacteria. As to the protection of wood and 10 plant refers to an entire plant, a part of the plant or the other materials, the particular attention is paid to the fol- propagation material of the plant. lowing harmful fungi: Ascomycetes such as Ophiostoma [0063] The inventive mixtures and compositions there- spp., Ceratocystis spp., Aureobasidium pullulans, Scle- of are particularly important in the control of a multitude rophoma spp., Chaetomium spp., Humicola spp., Petri- of phytopathogenic fungi on various cultivated plants, ella spp., Trichurus spp.; Basidiomycetes such as Coni- 15 such as cereals, e. g. wheat, rye, barley, triticale, oats or ophora spp., Coriolus spp., Gloeophyllum spp., Lentinus rice; beet, e. g. sugar beet or fodder beet; fruits, such as spp., Pleurotus spp., Poria spp., Serpula spp. and Tyro- pomes, stone fruits or soft fruits, e. g. apples, pears, myces spp., Deuteromycetes such as Aspergillus spp., plums, peaches, almonds, cherries, strawberries, rasp- Cladosporium spp., Penicillium spp., Trichoderma spp., berries, blackberries or gooseberries; leguminous plants, Alternaria spp., Paecilomyces spp. and Zygomycetes 20 such as lentils, peas, alfalfa or soybeans; oil plants, such such as Mucor spp., and in addition in the protection of as rape, mustard, olives, sunflowers, coconut, cocoa stored products and harvest the following yeast fungi are beans, castor oil plants, oil palms, ground nuts or soy- worthy of note: Candida spp. and Saccharomyces cere- beans; cucurbits, such as squashes, cucumber or mel- visae. ons; fiber plants, such as cotton, flax, hemp or jute; citrus [0057] In general, "fungicidally effective amount"25 fruit, such as oranges, lemons, grape-fruits or mandarins; means the amount of the inventive mixtures or of com- vegetables, such as spinach, lettuce, asparagus, cab- positions comprising the mixtures needed to achieve an bages, carrots, onions, tomatoes, potatoes, cucurbits or observable effect on growth, including the effects of paprika; lauraceous plants, such as avocados, cinnamon necrosis, death, retardation, prevention, and removal, or camphor; energy and raw material plants, such as destruction, or otherwise diminishing the occurrence and 30 corn, soybean, rape, sugar cane or oil palm; corn; tobac- activity of the target organism. The fungicidally effective co; nuts; coffee; tea; bananas; vines (table grapes, grape amount can vary for the various mixtures / compositions juice, grape vines); hop; turf; sweet leaf (also called Ste- used in the invention. A fungicidally effective amount of via); natural rubber plants or ornamental and forestry the mixtures / compositions will also vary according to plants, such as flowers, shrubs, broad-leaved trees or the prevailing conditions such as desired pesticidal effect 35 evergreens, e. g. conifers; and on the plant propagation and duration, weather, target species, locus, mode of material, such as seeds, and the crop material of these application, and the like. plants. [0058] As said above, the present invention comprises [0064] Preferably, the inventive mixtures and compo- a method for improving the health of plants, wherein the sitions thereof, respectively are used for controlling a plant, the locus where the plant is growing or is expected 40 multitude of fungi on field crops, such as potatoes, sugar to grow or plant propagation material, from which the beets, tobacco, wheat, rye, barley, oats, rice, corn, cot- plant grows, is treated with a plant health effective ton, soybeans, rape, legumes, sunflowers, coffee or sug- amount of an inventive mixture. ar cane; fruits; vines; ornamentals; or vegetables, such [0059] The term "plant effective amount" denotes an as cucumbers, tomatoes, beans or squashes. amount of the inventive mixtures, which is sufficient for 45 [0065] Preferably, treatment of plant propagation ma- achieving plant health effects as defined herein below. terials with the inventive mixtures and compositions More exemplary information about amounts, ways of ap- thereof, respectively, is used for controlling a multitude plication and suitable ratios to be used is given below. of fungi on cereals, such as wheat, rye, barley and oats; Anyway, the skilled artisan is well aware of the fact that potatoes, tomatoes, vines, rice, corn, cotton and soy- such an amount can vary in a broad range and is de- 50 beans. pendent on various factors, e.g. the treated cultivated [0066] Very preferred are the inventive mixtures for use plant or material and the climatic conditions. in small grain cereals (e.g. wheat, rye, barley, triticale, [0060] When preparing the mixtures, it is preferred to especially wheat. employ the pure active compounds, to which further ac- [0067] The term "cultivated plants" is to be understood tive compounds against pests, such as insecticides, her- 55 as including plants which have been modified by breed- bicides, fungicides or else herbicidal or growth-regulating ing, mutagenesis or genetic engineering including but active compounds or fertilizers can be added as further not limiting to agricultural biotech products on the market active components according to need. or in development (cf. http://cera-gmc.org/, see GM crop

9 17 EP 3 530 118 A1 18 database therein).Genetically modified plants areplants, e. g. CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), Cry- which genetic material has been so modified by the use IIIA, CryIIIB(b1) or Cry9c; vegetative insecticidal proteins of recombinant DNA techniques that under natural cir- (VIP), e. g. VIP1, VIP2, VIP3 or VIP3A; insecticidal pro- cumstances cannot readily be obtained by cross breed- teins of bacteria colonizing nematodes, e. g. Photorhab- ing, mutations or natural recombination. Typically, one 5 dus spp. or Xenorhabdus spp.; toxins produced by ani- or more genes have been integrated into the genetic ma- mals, such as scorpion toxins, arachnid toxins, wasp tox- terial of a genetically modified plant in order to improve ins, or other insect-specific neurotoxins; toxins produced certain propertiesof the plant. Such genetic modifications by fungi, such Streptomycetes toxins, plant lectins, such also include but are not limited to targeted post-transla- aspea or barleylectins; agglutinins; proteinase inhibitors, tional modification of protein(s), oligo- or polypeptides e. 10 such as trypsin inhibitors, serine protease inhibitors, g. by glycosylation or polymer additions such as prenylat- patatin, cystatin or papain inhibitors; ribosome-inactivat- ed, acetylated or farnesylated moieties or PEG moieties. ing proteins (RIP), such as ricin, maize-RIP, abrin, luffin, [0068] Plants that have been modified by breeding, saporin or bryodin; steroid metabolism enzymes, such mutagenesis or genetic engineering, e. g. have been ren- as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl- dered tolerant to applications of specific classes of her- 15 transferase, cholesterol oxidases, ecdysone inhibitors or bicides, such as auxin herbicides such as dicamba or HMG-CoA-reductase; ion channel blockers, such as 2,4-D; bleacher herbicides such as hydroxylphenylpyru- blockers of sodium or calcium channels; juvenile hor- vate dioxygenase (HPPD) inhibitors or phytoene desat- mone esterase; diuretic hormone receptors (helicokinin urase (PDS) inhibittors; acetolactate synthase (ALS) in- receptors); stilben synthase, bibenzyl synthase, chitinas- hibitors such as sulfonyl ureas or imidazolinones;20 es or glucanases. In the context of the present invention enolpyruvylshikimate-3-phosphate synthase (EPSPS) these insecticidal proteins or toxins are to be understood inhibitors, such as glyphosate; glutamine synthetase expressly also as pre-toxins, hybrid proteins, truncated (GS) inhibitors such as glufosinate; protoporphyrinogen- or otherwise modified proteins. Hybrid proteins are char- IX oxidase inhibitors; lipid biosynthesis inhibitors such as acterized by a new combination of protein domains, (see, acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. 25 e. g. WO 02/015701). Further examples of such toxins e. bromoxynil or ioxynil) herbicides as a result of conven- or genetically modified plants capable of synthesizing tional methods of breeding or genetic engineering. Fur- such toxins are disclosed, e. g., in EP-A 374 753, WO thermore, plants have been made resistant to multiple 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, classes of herbicides through multiple genetic modifica- WO 03/18810 und WO 03/52073. The methods for pro- tions, such as resistance to both glyphosate and glufosi- 30 ducing such genetically modified plants are generally nate or to both glyphosate and a herbicide from another known to the person skilled in the art and are described, class such as ALS inhibitors, HPPD inhibitors, auxin her- e. g. in the publications mentioned above. These insec- bicides, or ACCase inhibitors. These herbicide resist- ticidal proteins contained in the genetically modified ance technologies are e. g. described in Pest Manag. plants impart to the plants producing these proteins tol- Sci. 61, 2005, 246; 61, 2005, 258; 61, 2005, 277; 61,35 erance to harmful pests from all taxonomic groups of ath- 2005, 269; 61, 2005, 286; 64, 2008, 326; 64, 2008, 332; ropods, especially to beetles (Coeloptera), two-winged Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, insects (Diptera), and moths (Lepidoptera) and to nem- 2007, 708; Science 316, 2007, 1185; and references atodes (Nematoda). Genetically modified plants capable quoted therein. Several cultivated plants have been ren- to synthesize one or more insecticidal proteins are, e. g., dered tolerant to herbicides by conventional methods of 40 described in the publications mentioned above, and breeding (mutagenesis), e. g. Clearfield® summer rape some of which are commercially available such as (Canola, BASF SE, Germany) being tolerant to imida- YieldGard® (corn cultivars producing the Cry1Ab toxin), zolinones, e. g. imazamox, or ExpressSun® sunflowers YieldGard® Plus (corn cultivars producing Cry1Ab and (DuPont, USA) being tolerant to sulfonyl ureas, e. g. Cry3Bb1 toxins), Starlink® (corn cultivars producing the tribenuron. Genetic engineering methods have been45 Cry9c toxin), Herculex® RW (corn cultivars producing used to render cultivated plants such as soybean, cotton, Cry34Ab1, Cry35Ab1 and the enzyme Phosphinothricin- corn, beets and rape, tolerant to herbicides such as N-Acetyltransferase [PAT]); NuCOTN® 33B (cotton cul- glyphosate and glufosinate, some of which are commer- tivars producing the Cry1Ac toxin), Bollgard® I (cotton cially available under the trade names RoundupReady® cultivarsproducing the Cry1Ac toxin), Bollgard® II (cotton (glyphosate-tolerant, Monsanto, U.S.A.), Cultivance® 50 cultivars producing Cry1Ac and Cry2Ab2 toxins); VIP- (imidazolinone tolerant, BASF SE, Germany) and Liber- COT® (cotton cultivars producing a VIP-toxin); tyLink® (glufosinate-tolerant, Bayer CropScience, Ger- NewLeaf® (potato cultivars producing the Cry3A toxin); many). Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Pro- [0069] Furthermore, plants are also covered that are tecta®, Bt11 (e. g. Agrisure® CB) and Bt176 from Syn- by the use of recombinant DNA techniques capable to 55 genta Seeds SAS, France, (corn cultivars producing the synthesize one or more insecticidal proteins, especially Cry1Ab toxin and PAT enzyme), MIR604 from Syngenta those known from the bacterial genus Bacillus, particu- Seeds SAS, France (corn cultivars producing a modified larly from Bacillus thuringiensis, such as δ-endotoxins, version of the Cry3A toxin, c.f. WO 03/018810), MON

10 19 EP 3 530 118 A1 20

863 from Monsanto Europe S.A., Belgium (corn cultivars vade into houses and public facilities). producing the Cry3Bb1 toxin), IPC 531 from Monsanto [0076] Customary application rates in the protection of Europe S.A., Belgium (cotton cultivars producing a mod- materials are, for example, from 0.01 g to 1000 g of active ified version of the Cry1Ac toxin) and 1507 from Pioneer compounds per m2 treated material, desirably from 0.1 Overseas Corporation,Belgium (corncultivars producing 5 g to 50 g per m2. the Cry1 F toxin and PAT enzyme). [0077] For use in spray compositions, the content of [0070] Furthermore, plants are also covered that are the mixture of the active ingredients is from 0.001 to 80 by the use of recombinant DNA techniques capable to weight %, preferably from 0.01 to 50 weight % and most synthesize one or more proteins to increase the resist- preferably from 0.01 to 15 weight %. ance or tolerance of those plants to bacterial, viral or10 [0078] The invention shall be illustrated, but not limited fungal pathogens. Examples of such proteins are the so- by the following examples: called "pathogenesis-related proteins" (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. The fungicidal action of the mixtures according to g. potato cultivars, which express resistance genes act- the invention can be shown by the tests described ing against Phytophthorainfestans derived from the mex- 15 below. ican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these pro- [0079] The visually determined percentages of infect- teins with increased resistance against bacteria such as ed leaf areas are converted into efficacies in % of the Erwinia amylvora). The methods for producing such ge- untreated control. netically modified plants are generally known to the per- 20 [0080] The efficacy (E) is calculated as follows using son skilled in the art and are described, e. g. in the pub- Abbot’s formula: lications mentioned above. [0071] Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the produc- 25 tivity (e. g. bio mass production, grain yield, starch con- α corresponds to the fungicidal infection of the treated tent, oil content or protein content), tolerance to drought, plants in % and salinity or other growth-limiting environmental factors or β corresponds to the fungicidal infection of the un- tolerance to pests and fungal, bacterial or viral pathogens treated (control) plants in % of those plants. 30 [0072] Furthermore, plants are also covered that con- [0081] An efficacy of 0 means that the infection level tain by the use of recombinant DNA techniques a modi- of the treated plants corresponds to that of the untreated fied amount of substances of content or new substances control plants; an efficacy of 100 means that the treated of content, specifically to improve human or animal nu- plants were not infected. The expected efficacies of ac- trition, e. g. oil crops that produce health-promoting long- 35 tive compound combinations may be determined using chain omega-3 fatty acids or unsaturated omega-9 fatty Colby’s formula (Colby, S.R. "Calculating synergistic and acids (e. g. Nexera® rape, DOW Agro Sciences, Cana- antagonistic responses of herbicide combinations", da). Weeds, 15, pp. 20-22, 1967) and compared with the ob- [0073] Furthermore, plants are also covered that con- served efficacies. tain by the use of recombinant DNA techniques a modi- 40 fied amount of substances of content or new substances Colby’s formula: of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of [0082] amylopectin (e. g. Amflora® potato, BASF SE, Germa- ny). 45 [0074] The separate or joint application of the compounds of the inventive mixtures is carried out by spray- ing or dusting the seeds, the seedlings, the plants or the E expected efficacy, expressed in % of the untreated soils before or after sowing of the plants or before or after control, when using the mixture of the active com- emergence of the plants. 50 pounds A and B at the concentrations a and b [0075] The inventive mixtures and the compositions x efficacy, expressed in % of the untreated control, comprising them can be used for protecting wooden ma- when using the active compound A at the concen- terials such as trees, board fences, sleepers, etc. and tration a buildings such as houses, outhouses, factories, but also y efficacy, expressed in % of the untreated control, construction materials, furniture, leathers, fibers, vinyl ar- 55 when using the active compound B at the concen- ticles, electric wires and cables etc. from ants and/or ter- tration b. mites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests in-

11 21 EP 3 530 118 A1 22

Microtest: morph; C) Lipid and membrane synthesis inhibitors [0083] The active compounds, separately or jointly, are prepared as a stock solution comprising 25 mg of active - Phospholipid biosynthesis inhibitors: compound(s), which is made up to 10 ml using a mixture 5 dimethomorph, mandipropamid, valife- of acetone and/or DMSO and the emulsifier Uniperol® nalate, propamocarb, oxathiapiprolin, EL (wetting agent having an emulsifying and dispersing 2-{3-[2-(1-{[3,5-bis(difluoromethyl-1H- action based on ethoxylated alkylphenols) in a ratio by pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thia- volume of solvent/emulsifier of 99:1. The mixture is then zol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phe- made up to 100 ml with water. This stock solution is di- 10 nyl methanesulfonate 2-{3-[2-(1-{[3,5- luted with the solvent/emulsifier/water mixture described bis(difluoromethyl)-1H-pyrazol-1- to give the concentration of active compound stated be- yl]acetyl}piperidin-4-yl) 1,3-thiazol-4-yl]- low. 4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate,4-[1-[2-[3-(difluor- 15 omethyl)-5-methyl-pyrazol-1-yl]acetyl]-4- Claims piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide, 4-[1-[2-[3,5-bis(difluorome- 1. Fungicidal mixtures comprising, as active compo- thyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-te- nents, Fluxapyroxad (I) and Florylpicoxamid (II), and tralin-1-yl-pyridine-2-carboxamide, optionally a third fungicidal compound III, wherein 20 4-[1-[2-[3-(difluoromethyl)-5-(trifluorome- compound III is selected from groups (A) to (E) con- thyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-te- sisting of: tralin-1-yl-pyridine-2-carboxamide, 4-[1-[2-[5-cyclopropyl-3-(difluorome- A) Respiration inhibitors thyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-te- 25 tralin-1-yl-pyridine-2-carboxamide, - Inhibitors of complex III at Q o site: azoxys- 4-[1-[2-[5-methyl-3-(trifluoromethyl)pyra- trobin, dimoxystrobin, kresoxim-methyl, pi- zol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl- coxystrobin, pyraclostrobin, trifloxystrobin, pyridine-2-carboxamide, 4-[1-[2-[5-(difluor- famoxadone; omethyl)-3-(trifluoromethyl)pyrazol-1- 30 - inhibitors of complex III at Qi site: cyazof- yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyrid- amid; ine-2-carboxamide, 4-[1-[2-[3,5-bis(trifluor- - inhibitors of complex II: bixafen, boscalid, omethyl)pyrazol-1-yl]acetyl]-4-piperi- fluopyram, penthiopyrad, pydiflumetofen, dyl]-N-tetralin-1-yl-pyridine-2-carboxam- inpyrfluxam isoflucypram, 2-(difluorome- ide, (4-[1-[2-[5-cyclopropyl-3-(trifluoromethyl)-N-(1,1,3-trimethyl-indan-4-yl)pyrid- 35 thyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-te- ine-3-carboxamide, 2-(difluorome- tralin-1-yl-pyridine-2-carboxamide; thyl)-N-[(3R)-1,1,3-trimethylindan-4-yl]pyridine-3-carboxamide, 2-(difluorome- D) Inhibitors with Multi Site Action: mancozeb, thyl)-N-(3-ethyl-1,1-dimethyl-indan-4- metiram, zineb, chlorothalonil, folpet, dithianon; yl)pyridine-3-carboxamide, 2-(difluorome- 40 E) other fungicides: fosetyl, fosetyl-aluminum; thyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4- metalaxyl, metalaxyl-M, carbendazim, thi- yl]pyridine-3-carboxamide,2-(difluorome- ophanate-methyl, fluopicolide, metrafenone, thyl)-N-(1,1-dimethyl-3-propyl-indan-4- pyrimethanil;fludioxonil; quinoxyfen; cymoxanil, yl)pyridine-3-carboxamide, 2-(difluorome- proquinazid,N’-(4-(4-chloro-3-trifluoromethyl- thyl)-N-[(3R)-1,1-dimethyl-3-propyl-indan- 45 phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-me- 4-yl]pyridine-3-carboxamide, 2-(difluor- thyl formamidine, N’-(4-(4-fluoro-3-trifluorome- omethyl)-N-(3-isobutyl-1,1-dimethyl-indan- thyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N- 4-yl)pyridine-3-carboxamide, 2-(difluor- methyl formamidine, picarbutrazox, pentyl omethyl)-N-[(3R)-3-isobutyl-1,1-dimethyl- N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-meth- indan-4-yl]pyridine-3-carboxamide; 50 ylene]amino]oxymethyl]-2-pyridyl]carbamate, - other respiration inhibitors: fluazinam, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5- meptyldinocap, ametoctradin; yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate. B) Sterol biosynthesis inhibitors (SBI fungicides): difenoconazole, epoxiconazole, fluquin- 55 2. A fungicidal mixture as claimed in claim 1, wherein conazole,metconazole, myclobutanil, pencona- ratio by weight of compound I and compound II is zole, propiconazole, prothioconazole, mefentri- from 100:1 to 1:100. fluconazole, dodemorph, fenpropimorph, tride-

12 23 EP 3 530 118 A1 24

3. A fungicidal composition, comprising a liquid or solid rum), Tilletia. tritici (syn. Tilletia caries, wheat bunt), carrier and a mixture as defined in claim 1 or 2. T. controversa (dwarf bunt) orTyphula incarnata (grey snow mold). 4. A method for controlling phytopathogenic fungi, wherein the fungi, their habitat, their locus or the 5 11. Plant propagation material, comprising the mixture plants to be protected against fungal attack, the soil as defined in claim 1 or 2 in an amount of from 0.01 or plant propagation material are treated with an ef- g to 10 kg per 100 kg of plant propagation material. fective amount of a mixture as defined in claim 1 or 2. 12. Plant propagation material as claimed in claim 10, 5. A method for improving the health of plants, wherein 10 wherein the plant propagation material is seed. the plant, the locus where the plant is growing or is expected to grow or plant propagation material from which the plant grows are treated with an effective amount of a mixture as defined in claims 1 or 2. 15 6. A method for protection of plant propagation material from phytopathogenic fungi comprising contacting the plant propagation materials with a mixture as defined in claim 1 or 2 in fungicidally effective amounts. 20 7. A method as claimed in claim 6, wherein the mixture as defined in claim 1 or 2 is applied in an amount of from 0.01 g to 10 kg per 100 kg of plant propagation material. 25 8. A method as claimed in claims 4 to 7, wherein the mixture as defined in claim 1 or 2 is applied simulta- neously, that is jointly or separately, or in succession.

9. A method as claimed in claims 4 to 8, wherein the 30 plantsor the plant propagation material iswheat, barley, rye, or triticale.

10. A method as claimed in claims 4 to 9, wherein a mixture as defined in claim 1 or 2, or a composition 35 as defined in claim 3, is applied to control wheat diseases caused by Alternaria spp. (Alternaria leaf spot), Ascochyta tritici (anthracnose), Blumeria (formerly Erysiphe) graminis (powdery mildew), Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey 40 mold), Cladosporium herbarum (black ear), Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) tritici-repentis (tan spot), Epicoccum spp. (black mold), Fusarium (teleomorph: Gibberel- la) graminearum or Fusarium culmorum (root rot, 45 scab or head blight), Gaeumannomyces graminis (take-all), Microdochium (syn. Fusarium) nivale(pink snow mold), Mycosphaerella graminicola (anamorph: Septoria tritici, Septoria blotch), Polymyxa graminis, Pseudocercosporella herpotrichoides 50 (eyespot, teleomorph: Tapesia yallundae), Puccinia graminis (stem or black rust),Puccinia recondita (brown or leaf rust),Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot), Pythium spp. (damping-off), Rhizoctonia cerealis (Rhizoctonia 55 spring blight), Septoria tritici (Septoria blotch), Stagonospora nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodo-

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REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

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Non-patent literature cited in the description

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