|Title of Invention||
AN ESSENTIALLY ANHYDROUS DITHIOCARBANTATE LIQUID FORMULATION
|Abstract||The invention relates to dithiocarbamate liquid formulations which are essentially devoid of water, comprising: a) 10 - 70 wt. % of at least one active substance from the class of dithiocarbamates b) 10 - 89 wt. % of a substantially water-free oil phase, c) 1 -40 wt. % of a polyhydroxy stearic acid or a derivative thereof and/or an alkyl or alkenyl glycerine etherethoxylate. d) 0 -40 wt. % of at least one anionic surfactant.|
The invention relates to an essentially anhydrous dithiocarbamate liquid formulation, in particular comprising metiram. "Essentially anhydrous" 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 l%.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
in particular 8 to 22, carbon atoms, which can be straight-chain or branched and can exist with or without double bonds, with epichiorohydrin 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 (ED), propylene oxide (P0), 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 Ci2-\$ 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-Bs 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 preferably 0.5 to 20% 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.
1. An essentially anhydrous dithiocarbantate liquid formulation comprising
a) 10 to 70% by weight of at least one active ingredient from the class of the dithiocarbamates
b) 10 to 89% by weight of an essentially anhydrous oil phase,
c) 1 to 40% by weight of polyhydroxystearic acid or a derivative thereof and/or an alkyl or alkenyl polyol ether alkoxylate,
d) 0 to 40% by weight of at least one anionic surfactant.
2. The liquid formulation as claimed in claim 1, wherein the dithiocarbamate is
selected from the group consisting of ziram, thiram, nabam, metham and the
compounds of the formula II hereinbelow
Me is a mono- or divalent agriculturally utilizable metal ion, 1 depending on the valence of Me, is 1 or 2.
3. The liquid formulation as claimed in claim 1 or 2, wherein the active ingredient is
selected from mancozeb and metiram.
4. The liquid formulation as claimed in any of the preceding claims, wherein
component b) comprises at least one of the following components:
u) a C8 to C30-hydrocarbon of the n- or iso-alkane series or a mixture thereof,
v) an aromatic or cycloaliphatic C7. to C18hydrocarbon or a mixture thereof, bc) an aliphatic ester.
5. The liquid formulation as claimed in claim 4, wherein component
bb) is selected from the group consisting of mono-, di-, trialkylbenzenes, mono-, di-, trialkyl-substituted tetralins and mono-, di-, trialkyl-substituted naphthalenes.
6. The liquid formulation as claimed in claim 4, wherein component
be) is selected from the group consisting of methyl oleate, dioctyl adipate, octyl laurate, 2-ethylthexyl 2-ethylhexanoate and benzoic esters.
7. The liquid formulation as claimed in any of the preceding claims, wherein the
hydroxystearic acid derivative is a reaction product of polyhydroxystearic acid with a
polyethylene-imine or a mono- or di-Ci-C4-alkyleneamine or a Ci-C4-alkyl-
quaternized product thereof
8. The liquid formulation as claimed in any of the preceding claims, wherein the
anionic surfactant d) is selected from
oo) the group consisting of alkyl sulfates, alkylsulfonates, alkylbenzene sulfates, alkylarylsulfonates, alkyl polyethoxysulfates, alkylphenol polyethoxysulfates and a-olefinsulfonates, the cation being an agriculturally utilizable mono- or divalent cation,
pp) compounds of the group of the mono- and/or di-C6-C30-alkyl ester sulfosuccinates, the cation being an agriculturally utilizable mono- or divalent cation,
in which M is an agriculturally utilizable mono or divalent cation, g is 0 or 1, n is an integer in the range 0
9. The liquid formulation as claimed in claim 8, wherein the anionic surfactant is an
alkylarylsulfonate or an anionic polymer cc) as claimed in claim 8.
10. The liquid formulation as claimed in any of the preceding claims comprising
where Me = Zn, 1 b) 10 to 89% by weight of a Cg-Cso-hydrocarbon or a mixture thereof,
c) 1 to 40% by weight of polyhydroxystearic acid and/or a reaction product of polyhydroxystearic acid with a polyethyleneimine or a mono- or di-C i -C4-alkyleneamine or a CrC4-alkyl-quaternized product thereof, and
d) 0.5 to 20% by weight of an alkylarylsulfonate or an anionic polymer dc) as claimed
in claim 8.
in which Me = Zn, 1 b) 10 to 85% by weight of an essentially anhydrous oil phase, and
c) 5 to 40% by weight of at least one anionic surfactant, where the anionic sufactant c)
is selected from
ca) the group consisting of alkyl sulfates, alkylsulfonates, alkylbenzene sulfates,
alkylarylsulfonates, alkyl polyethoxysulfates, alkylphenol polyethoxysulfates and a-
olefinsulfonates, the cation being an agriculturally utilizable mono- or divatent cation,
cb) compounds of the group of the mono- and/or di-C6-C3o-alkyl ester sulfosuccinates,
the cation being an agriculturally utilizable mono- or divalent cation,
in which M is an agriculturally utilizable mono- or divalent cation, g is 0 or 1, n is an integer in the range 0
12. A liquid formulation as claimed in claim 11, where 3 13. A crop protection product suitable for aerial application which comprises a
formulation as claimed in any of claims 1 to 12.
|Indian Patent Application Number||IN/PCT/2001/1668/CHE|
|PG Journal Number||26/2007|
|Date of Filing||28-Nov-2001|
|Name of Patentee||BASF AKTIENGESELLSCHAFT|
|Applicant Address||D-67056 Ludwigshafen (DE)|
|PCT International Classification Number||A01N47/26|
|PCT International Application Number||PCT/EP00/04887|
|PCT International Filing date||2000-05-29|