The invention essentially relates to anhydrous liquid formulations with active ingredients from the class of the dithiocarbamates, in particular metiram. xe2x80x9cEssentially anhydrousxe2x80x9d means for the purposes of the present invention that the water content is 0 to 5% by weight, in particular 0.1 to 2.5% by weight, and advantageously 0.1 to 1% by weight (in each case based on the total weight of the liquid formulation).
Thiocarbamates, dithiocarbamates, and EBTCs (ethylenebisthiocarbamates) and EBDCs (ethylenebisdithiocarbamates) are generally known as fungicidal active ingredients, in particular as contact fungicides or biocides. Specifically, they are active ingredients such as, for example, metiram, mancozeb, maneb, nabam or else the N,N-dimethylthiocarbamates thiram or ziram.
However, a particular problem of these active ingredients is their relatively high instability. This is caused by the low stability of the C-S and S-S bonds and of the thiocarbamate function, in particular at low pH values and to nucleophilic agents.
A possibility for stable formulations for crop protection is to process the materials as solid formulations. Solid powder formulations which are known are, for example, Manzate 200 75 WG (product of DuPont), Polyram DF (product of BASF AG) and Vondozeb 75 WG (product of Elf Atochem).
DE-A 33 38 979 discloses the stabilization of polyethylenethiuram disulfides by means of formaldehyde or paraformaldehyde. Moreover, DE-A 34 26 078 describes the stabilization of, for example, Zineb by means of calcium oxide. Also, EP-A 0 568 378 discloses the use of EBDC formulations in the form of aqueous granules with improved flowability.
In such formulations, the undesired degradation product by-product ethylene thiourea (ETU) needs careful consideration, owing to its high toxicity. It is important to lower the ETU content under defined threshold values by stabilization measures, for example using hydroxymethane sulfinate (HMS) or a salt thereof, see EP-A-460 612.
In many cases, liquid products are preferred nowadays to the abovementioned solid. formulations. The liquid products have the advantage that they show good miscibility with oily tankmix additives, such as, for example, the so-called Spraytex oil, a paraffin derivative (product of Exxon) for a water/oil or pure oil application, even under ULV (ultra-low volume) conditions; see EP-A-435 760 and EP-A 697 171.
Such ULV conditions, or ULV oil/water mixtures, are particularly important for aerial application. Using aircraft, it is possible to apply relatively low application rates per hectare, approximately 10 to 30 l of the fungicidal active ingredient or of the corresponding formulation, in such a fashion that the effect is reliable and drift is low. Target crops which are typically suitable for such an aerial application of EBDCs are, in particular, bananas and coffee. Aerial application, or ULV application, is done for virtually all banana plantations.
In such an application, it is in particular the so-called oil SC variants (SC=suspension concentrate) of the formulations which are advantageous since they are generally distinguished in the tankmix by good miscibility with spray oils. The oil component improves the rainfastness upon use of the formulations during the tropical rainy season. Oil SC formulations which have proved themselves in this context are, for example, those with the active ingredient mancozeb. Commercially available oil SC formulations with the active ingredient mancozeb are, for example, Dithane 35 SC, Ridodur 35 SC (product of Laquinsa), Vondozeb 35 SC (product of Elf Atochem). Formulations of this type frequently comprise, as dispersant, an oil-soluble polymer, see U.S. Pat. Nos. 3,131,119, 3,773,976 and EP-A 875 142. EP-A 245 970 discloses the use of water-soluble, nonionic polymers to improve the rainfastness of the formulations.
However, storage stability is still unsatisfactory, even with these formulations. This applies in particular if the less stable active ingredient metiram, which comprises Zn as metal ion, is to be employed in place of the active ingredients mancozeb or Maneb, which are relatively stable. This is why liquid formulations with this active ingredient have not been disclosed as yet. However, metiram/oil SC formulations would be advantageous over mancozeb, owing to the higher zinc content of metiram, since it is known that even simple zinc salts already have a fungicidal, or biocidal, action.
On the other hand, the known liquid EBTC/oil SC formulations have even more disadvantages. Firstly, their active ingredient component is lower compared with the solid products. This is because, in oil SC formulations, sufficiently low viscosities are generally achieved when the solid component amounts to less than 40%. If not, there is a danger of the products no longer being sufficiently flowable because of unduly high viscosity.
A further disadvantage of the existing oil SC formulations, in particular oil SC formulations with active ingredients from the class of the EBTCs, is that such formulations frequently only have unsatisfactory rheological properties after storage. Thus, storage at elevated temperatures frequently leads to agglomeration effects, lump formation or pronounced settling of the solid phase. In some cases, the effects are even irreversible, i.e. even renewed shearing, for example by stirring, cannot rehomogenize the formulations.
It is an object of the present invention to provide essentially anhydrous liquid formulations with an active ingredient from the class of the dithiocarbamates, in particular metiram-comprising liquid formulations, which exhibit a high active ingredient content per liter, a low viscosity and high storage stability. It is also an object of the present invention to provide a process for the preparation of such essentially anhydrous liquid formulations.
We have found that this object is achieved in a first aspect of the invention by an essentially anhydrous liquid formulation comprising:
a) 10 to 70% by weight, preferably 30 to 60% by weight, of at least one active ingredient from the class of the dithiocarbamates,
b) 10 to 89% by weight, preferably 20 to 60% by weight, of the abovementioned essentially anhydrous oil phase,
c) 1 to 40% by weight, preferably 5 to 20% by weight, of a product selected from polyhydroxystearic acid, a derivative thereof, an alkyl or alkenyl polyether alkoxylate or a mixture thereof,
d) 0 to 40% by weight, preferably 0 to 10% by weight of at lest one anionic surfactant,
(in each case based on the total weight of the formulation).
A second aspect of the invention provides an essentially anhydrous liquid formulation comprising:
a) 10 to 70% by weight, preferably 30 to 60% by weight, of at least one active ingredient of the formula I hereinbelow 
xe2x80x83in which Me=Zn, 1xe2x89xa6xc3x97xe2x89xa65,
b) 10 to 85% by weight, preferably 20 to 60% by weight, of an essentially anhydrous oil phase,
c) 5 to 40% by weight, preferably 7.5 to 25% by weight, of at least one anionic surfactant,
(in each case based on the total weight of the formulation).
In the abovementioned liquid formulation, the value for x is, in particular, in a range of 3 to 4.
Liquid formulation of the first aspect of the invention:
The dithiocarbamate active ingredients thus include the thiuram sulfides. Preferred active ingredients are ziram (zinc dimethyldithiocarbamate), thiram (tetramethylthiuram disulfide) and metham (sodium methyldithiocarbamate). Other preferred compounds are those of the formula (II), 
in which:
Me is a mono- or divalent agriculturally utilizable metal ion, in particular selected from amongst Zn, Mn, Na, Mg, Ca and/or K, preferably Zn and/or Mn, and 1xe2x89xa6xc3x97xe2x89xa64, preferably 3xe2x89xa6xc3x97xe2x89xa64, and y is 1 or 2, depending on the valence of Me.
These active ingredients are, in particular, maneb (manganese ethylenebisdithiocarbamate), mancozeb (the coordination product of maneb with zinc ions), nabam (sodium ethylenebisdithiocarbamate), zineb (zinc ethylenebisdithiocarbamate) and, preferably, metiram (compound of the formula I where x=3). Component b) is preferably an aprotic solvent, in particular at least one of the following components:
ba) a C8- to C30-hydrocarbon of the n- or iso-alkane series or a mixture thereof. Examples of such hydrocarbons are n- and iso-octane, -decane, -hexadecane, -octadecane, -eicosane, and preferably hydrocarbon mixtures such as liquid paraffin (which, in technical-grade quality can contain up to approximately 5% of aromatics), and a C18-C24-mixture which is commercially available from Exxon under the name Spraytex oil.
bb) aromatic or cycloaliphatic C7- to C18-hydrocarbon compounds, or a mixture thereof. These include, in particular, aromatic or cycloaliphatic solvents from the series of the alkyl-aromatics; the compounds can be unhydrogenated, partially hydrogenated or fully hydrogenated. Such solvents of component bb) include, in particular, mono-, di- or trialkylbenzenes, mono-, di-, trialkyl-substituted tetralins and/or mono-, di-, tri- or tetraalkyl-substituted naphthalenes (alkyl preferably represents C1-C6-alkyl). Examples of such solvents are toluene, o-, m-, p-xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene and mixtures such as the Exxon products sold under the names Shellsol and Solvesso, for example Solvesso 100, 150 and 200.
bc) an aliphatic ester which is selected in particular from the group consisting of aliphatic esters, araliphatic esters and natural fats and oils and derivatives and mixtures thereof. Suitable substances are esters of aliphatic, saturated or unsaturated C1-C20-mono- and C2-C20-dicarboxylic acids with C1-C20-alkanols and phenyl-C1-C20-alkanols, the total of the carbon atoms being at least 8. Also suitable are esters of aromatic mono- or dicarboxylic acids, such as benzoic acid and phthalic acid, with C1-C20-alkanols and phenyl-C1-C20-alkanols. Preferred are methyl oleate, di-n-octyl and isooctyl adipate, octyl laurate, 2-ethylhexyl 2-ethylhexanoate, methyl oleate, n-butyl stearate, di-n-butyl adipate, di-n-nonyl and isononyl adipate, rapeseed oil methyl and ethyl esters, n-butyl benzoate, benzyl benzoate and the like.
The abovementioned fats or oils or derivatives which are of natural origin or have been left in their natural state (modified natural fats or oils) include, for example, substances such as soya oil, sunflower oil, rapeseed oil, corn oil and their raffination products.
The preferred component c) is polyhydroxystearic acid, particularly preferably polyhydroxystearic acid with 2 to 10, especially preferably 3 to 6, monomer units. An example is Solsperse 3000, which is commercially available (ICI).
Preferred polyhydroxystearic acid derivatives are reaction products of amines. Such amines include primary and/or secondary, linear C1- to C20 alkylamines and/or branched C3- to C20-alkylamines, or else they may be mono- or dialkylaminoalkylenedioligo- or -polyamines, it being possible for the alkylene group to have 2 to 4 carbon atoms and for the alkyl group to have 1 to 4 carbon atoms.
Examples are ethylenediamine, N,N-diethylenetriamine, triethylenetetramine, N,N-dimethylaminoethylamine, N,N-dimethylaminodiethylenetriamine, N,N-dimethylaminopropylamine, N,N-dimethylaminodipropylenetriamine and polyethyleneimines with a molecular weight of over 500, which may exhibit a low or high degree of branching.
The molar ratio of free acid function of the polyhydroxystearic acid to amine is especially preferably 1:5 to 10:1, in particular 1:1 to 5:1.
The reaction products of the polyhydroxystearic acid can also have cationic character, owing to quaternary nitrogen atoms. Substances which are suitable for quaternizing the nitrogen atoms are, for example, alkyl halides or alkyl sulfates, such as dimethyl sulfate.
Especially preferred are the reaction products of polyhydroxystearic acid with dimethylaminopropylamine, dimethylaminoethylamine and/or polyethyleneimine and the quaternization products thereof, for example the products quaternized with dimethyl sulfate. Examples are the commercially available Solsperse brands (ICI), in particular Solsperse 9.000, 13.000 and 17.000.
The alkyl or alkenyl radical in the alkyl- or alkenyl polyol ether alkoxylates can be straight-chain or branched and generally have 6 to 30 carbon atoms. The alkenyl radical can have one or more double bonds.
The preferred alkyl or alkenyl polyol ether alkoxylates can be obtained by reacting an alcohol with a chain length of 6 to 30, in particular 8 to 22, carbon atoms, which can be straight-chain or branched and can exist with or without double bonds, with epichlorohydrin and subsequently with a polyhydric alcohol such as, preferably neopentyl glycol or glycerin, and then alkoxylating the product with 1 to 20 mol of ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO) or pentylene oxide.
When preparing the alkyl or alkenyl polyol ether alkoxylates, the components can be employed in any desired ratio. Preferred are alkyl glycidol ethers with chain lengths of C12-C18, reacted with polyhydric alcohols such as glycerin or neopentyl glycol in a ratio of 2:1 to 1:3, either unethoxylated or ethoxylated with 1 to 20 mol EO. very especially preferred are reaction products of alkyl glycidol ethers with chain lengths of C16-C18 which are reacted with glycerin and/or neopentyl glycol in a ratio of 1:1 to 1:2 and, if desired, subsequently ethoxylated with 0 to 5 EO units.
A typical representative of the class of the fatty alkyl glycerin ether ethoxylates is Cremophor WO CE 5115 (CAS-No.: 104376-61-6); a product of BASF AG).
If present, the surfactants d) amount to 0.1 to 40% by weight, in particular 5 to 10% by weight.
Useful anionic surfactants d) are soaps (alkali metal/alkaline earth metal/ammonium salts of the fatty acids), for example potassium stearate, alkyl sulfates and their mixtures, alkyl ether sulfates, alkylsulfonates, alkali metal, alkaline earth metal and ammonium salts of arylsulfonic acids and of alkyl-substituted arylsulfonic acids, alkylbenzenesulfonic acids such as, for example, lignin-, phenolsulfonic acid, naphthalene- and dibutylnaphthalenesulfonic acid, or dodecylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl methyl ester sulfonates, acyl glutamates, mono- or dialkylsuccinic ester sulfonates, for example sodium di-isooctylsuccinic ester sulfonate, alkyl mono/diphosphates, sarcosinates, for example sodium lauroylsarcosinate, taurinates.
The anionic surfactants furthermore include condensates of sulfonated naphthalene and derivatives thereof with formaldehyde, condensates of naphthalenesulfonic acids, phenol and/or phenolsulfonic acids with formaldehyde or with formaldehyde and urea.
The sulfate and sulfonate surfactants are preferred. Component d) is especially preferably selected from:
da) alkyl sulfates, alkylsulfonates, alkylbenzene sulfates, alkylarylsulfonates, alkylpolyethoxysulfates, alkylphenol polyethoxysulfates and xcex1-olefinsulfonates. The alkyl or xcex1-olefin radical has, in particular, 6 to 30, preferably 8 to 22, carbon atoms. The number of ethoxy units is generally in the range of 1 to 50, preferably 1 to 25. The aryl radical is phenyl or a naphthyl radical which is substituted by one, two or three straight-chain or, in particular, branched C1-C12-alkyl radicals. The associated cation is an agriculturally utilizable mono- or divalent cation which is preferably selected from Na, Ca, K, Mg and NH4. Examples of the surfactants da) are sodium lauryl sulfate, sodium lauryl ether sulfate, nonylphenol polyethoxysulfate, sodium diisobutylnaphthylsulfonate, and the like;
db) compounds from the group of the mono- and/or di-C6-C30-alkyl ester sulfosuccinates, where the cation is an agriculturally utilizable mono- or divalent cation, preferably selected from Na, Ca, K, Mg, Mn, Zn and NH4. Sodium dioctylsulfosuccinate is preferred; and/or
dc) the anionic polymers of the subsequent formula (III) 
xe2x80x83in which M is an agriculturally utilizable mono- or divalent cation, preferably Na, Ca, K, Mg or NH4, m is 0 or 1, n is an integer in the range 0xe2x89xa6nxe2x89xa64, m is an integer in the range 102xe2x89xa6mxe2x89xa6105, R1 is a C1- to C8-alkyl radical or hydroxyl radical and A a group selected from amongst methylene, 1,1-ethylene, 
Products of the formulae III and IV are commercially available from BASF AG under the name Wettol or Tamol.
Liquid formulation of the second aspect of the invention:
The composition of the essentially anhydrous oil phase corresponds to that of the first aspect of the invention [component b)].
The surfactants c) correspond to those of the first aspect of the invention (component d)).
Auxiliaries contained in the formulations:
The formulations of both the first aspect of the invention and the second aspect of the invention may comprise auxiliaries. If present, then they are present in concentrations of 0.1 to 25% by weight, preferably 0.5 to 15% by weight, based on the total weight of the formulation. The auxiliaries may be further anionic components and/or cationic, zwitterionic or nonionic surfactants, or anionic, cationic or nonionic polymers.
Examples of anionic components are protein hydrolysates and, in particular, lignin-sulfite waste liquors and methylcellulose (dispersants).
The cationic surfactants which may be used include alkyltrimethylammonium halides, alkylpyridinium halides, and dialkyldimethylammonium halides.
The nonionic surfactants include
fatty alcohol polyoxyethylene esters, for example lauryl alcohol polyoxyethylene ether acetate,
or alkenyl
alkoxylated animal and/or vegetable fats and/or oils, for example corn oil ethoxylates, castor oil ethoxylates, tallow fat ethoxylates,
glycerin esters, such as, for example, glycerin monostearate,
fatty alcohol alkoxylates and oxoalcohol alkoxylates of the type RO-(R1O)x(R2O)yR3 in which R1 and R2 independently of one another=C2H4, C3H6, C4H8 and R3=H, or C1-C12-alkyl, R=C3-C30-alkyl or C6-C30-alkenyl, x and y independently of one another are 0 to 50, it not being possible for both to be 0, such as iso-tridecyl alcohol and oleyl alcohol polyoxyethylene ether,
fatty acid alkoxylates such as, for example, oleic acid ethoxylates,
alkylphenol alkoxylates such as, for example, ethoxylated iso-octyl-, octyl- or nonylphenol, tributylphenol polyoxyethylene ether,
fatty amine alkoxylates, fatty acid amide alkoxylates and fatty acid diethanolamide alkoxylates, in particular their ethoxylates,
sugar surfactants, sorbitol esters such as, for example, sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkyl polyglycosides, N-alkylgluconamides,
alkylmethyl sulfoxides,
alkyldimethylphosphine oxides such as, for example, tetradecyldimethylphosphine oxide.
The zwitterionic surfactants include sulfobetaines, carboxybetaines, alkyldimethylamine oxides such as, for example, tetradecyldimethylamine oxide.
Polymer surfactants which can be employed as auxiliaries to be used are, for example, di-, tri- and multi-block copolymers of the type (AB)x-, ABA, BAB, such as, for example, polyethylene oxide block polypropylene oxide block polyethylene oxide, polystyrene block polyethylene oxide, AB-comb polymers such as, for example, poly(meth)acrylate comb polyethylene oxide.
Other surfactants which can be employed, for example, are perfluoro surfactants, silicone surfactants, phospholipids such as, for example, lecithin or chemically modified lecithins, aminoacid surfactants such as, for example, N-lauroylglutamate.
Moreover, surface-active homo- and copolymers may also be employed in the liquid formulations according to the invention as auxiliaries: these include, for example, polyvinylpyrrolidone, polyacrylic acid, polyvinyl alcohol, polypropylene oxide, polyethylene oxide, maleic anhydride/isobutene copolymers, vinylpyrrolidone/vinyl acetate copolymers.
The alkyl chains of the abovementioned auxiliaries can be linear or branched. The alkyl chain lengths are, in general, between 8 and 22 carbon atoms.
Frequently, mixtures of the surfactants are particularly suitable. The auxiliaries mentioned can be added before or after grinding to the aqueous dithiocarbamate or EBDC SC intermediate product or to the oil SC batch to be formulated.
To widen the spectrum of action and to achieve synergistic effects, liquid formulations may be applied in accordance with the invention as a mixture with a large number of representatives of other groups of fungicidal active ingredients, and, accordingly, also jointly. Suitable components in mixtures are, for example: morpholine compounds such as tridemorph, fenpropimorph, fenpropidin and spiroxamin; strobilurins such as azoxystrobin, kresoxim methyl; triazoles such as tebuconazole, flusilazole, propiconazole, fenbuconazole; epoxiconazole; benzimidazoles such as carbendazim, benomyl; valinamides such as sprovalicarb or KIF 230 by Kumiai; thiophanates, such as thiophanate-methyl, and also chlorothalonil. These active ingredients can be incorporated into the formulations according to the invention or added to the spray mixture.
The formulation of the first aspect of the invention can also be mixed with the other active ingredients, which are encompassed by the formulation of the second aspect of the invention.
Also of interest is the miscibility with mineral salt solutions which are employed for remedying nutritional and trace element deficiencies. Nonphytotoxic oils and oil concentrates and antidrift reagents may also be added.
The formulations according to the invention are preferably prepared in a method in which a highly-concentrated (approx. 30 to 60% by weight active ingredient), aqueous microparticulate dispersion of the active ingredient, for example of the active ingredient metiram, is first prepared by grinding in the presence of at least one nonionic or anionic surfactant (for example component d) of the first aspect or component c) of the second aspect) and subsequently spray-dried. If the grinding step involves an anionic surfactant d) or c), all or some of the intended quantity can be employed during the grinding step.
To prepare the formulation of the first aspect of the invention, the powder or granules obtained after spray-drying is or are ground or processed with the oil component b), the component c) and, if appropriate, the rest or all of the anionic surfactant and, if appropriate, other auxiliaries and/or additives.
To prepare the formulation of the second aspect of the invention, the powder or granules is or are ground or processed in a similar manner with the oil component b) and the remainder or all of the anionic surfactant c) and, if appropriate other auxiliaries and/or additives.
The measures and apparatus required for the preparation are known to those skilled in the art.
It is particularly advantageous to stabilize the formulations according to the invention. This is effected by adding 1 to 5% by weight of a stabilizer (based on the active ingredient content) to an aqueous, technical-grade preconcentrate of the active ingredient prior to spray-drying.
The stabilizer is either added during the preparation of the aqueous SCs, i.e. while the technical-grade active ingredient is ground, or after grinding, but before the step in which the material is spray-dried to give the DF (dry flowable) intermediate product.
Preferred stabilizers are formaldehyde, paraformaldehyde or urotropin.
The additional stabilization with formaldehyde is carried out essentially in agreement with the known prior art, see DE-A 33 38 979.
Other stabilizers which are suitable arexe2x80x94as has already been mentioned above in some casesxe2x80x94HMS, calcium salts, for example calcium oxide or calcium carbonate, see EP-A-568 378 and 460 612.
Thickeners which the oil SC formulations according to the invention may furthermore comprise are mineral constituents such as, for example, bentonites, talcites or hectorites, by means of which the physical properties of the formulations with regard to less serum formation or less sedimentation can generally be improved.
Furthermore, such additions can also suppress chemical processes which take place in the formulations upon storage, in most cases as a consequence of an increased viscosity, which may lead to an improved stability of the active ingredient. Other organic thickeners which may be suitable are, for example, castor oil derivatives.
The liquid formulations according to the invention constitute a concentrate which comprises the active ingredient with a medium particle size in the range of 0.1 to 10 xcexcm, preferably 0.5 to 5 xcexcm. For use as crop protection product in agriculture (in particular for banana and coffee plantations), the concentrate is converted into a form which is suitable for application by diluting it in the customary manner prior to use. In particular, the use in the form of a spray mixture preparation is particularly preferred.
The fact that a virtually anhydrous oil-based formulation is present also allows application by the ULV method (ultra-low volume), for example by aerial application.
For a customary tankmix spray mixture, 0.5 to 10, preferably 1 to 5, l/ha of the formulation according to the invention are diluted with water to 5 to 2,000 l. For a ULV tankmix spray mixture, 0.5 to 10 l, preferably 1 to 5 l/ha of the formulation according to the invention are diluted to 5 to 50 l with an oil phase, preferably an oil of component b), or with water or a mixture of water and oil in a ratio of approximately 2:1 to 4:1 by volume. If appropriate, 0.1% to 5% by weight (based on the spray mixture) of other anionic, cationic or nonionic surfactants, auxiliaries, polymers and/or of the abovementioned other fungicidal active ingredients are added to the tankmix mixture. Substances which are examples of such, surfactants and other auxiliaries have already been described above. Substances which must be mentioned in particular are starch and starch derivatives, for example a starch comprising carboxyl and sulfonyl groups (Nu-Film by Union Carbide Corp.) and spreaders and extenders such as Vapor Guard by Miller Chemical and Fertilizer Corp.