Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Reexamination Certificate
1999-08-06
2002-04-16
Pryor, Alton (Department: 1616)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Having -c-, wherein x is chalcogen, bonded directly to...
Reexamination Certificate
active
06372771
ABSTRACT:
The present invention relates to new, in particular aqueous and optionally organic solvent- and emulsifier-free microbicidal active compound combinations comprising known azole fungicides and quaternary ammonium fungicides.
It is known that imidazole fungicides or triazole fungicides, such as, for example, &agr;-[2-(4-chlorophenyl)-ethyl]-&agr;-(1,1-dimethylethyl)-1-H-1,2,4-triazole-1-ethanol (tebuconazole), 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1,2,3-triazol-1-yl)-propan-2-ol and 1-[[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl]-methyl]-1-H-1,2,4-triazole (propiconazole), can be used as such or in the form of their salts for protecting plants and seeds (compare, for example, EP-A 0,040,345 and EP-A 0,052,424).
It is furthermore known that these compounds are also suitable for use in the preservation of materials for combating microbes which destroy materials or discolour materials (compare, for example, DE-OS (German Published Specification) 3,621,494 and U.S. Pat. No. 4,079,062).
However, the azole fungicides, such as the tebuconazole mentioned, have gaps in their action on some germs relevant to the preservation of materials, such as, for example, Trichoderma spec.
Because of the often low water-solubility of azoles, their use in some fields of application, such as, for example, leather, water-based wood preservatives, disinfection, cooling water treatment, paper industry, metal processing and industrial preservation of water-containing products, is furthermore limited or impossible.
Quaternary ammonium salts have been known for a long time as microbicides having a broad action and are used, for example, in disinfection and preservation of textiles.
Although these active compounds are usually readily water-soluble, they tend to foam severely at the use concentrations, which causes trouble in many fields of use. Furthermore, because of their cationic properties, they can react with anionic components, such as soaps, surfactants and the like. This can adversely influence their profile of properties, or they may become deactivated. It is furthermore known that quaternary ammonium salts can easily be deactivated by the presence of protein and dirt.
For many uses in the practice of preservation of materials, it is desirable to employ the active compounds in liquid formulations which are free from organic solvents or in which the corresponding solvent content is drastically reduced.
Water-insoluble solvents are incompatible with aqueous products such as leather liquors, emulsion paints, cooling and process water and disinfectants.
The users are often also not equipped to handle products in the form of solutions in organic solvents, since particular devices, associated with high investment costs, are necessary for application from the solvent and for recovery thereof, which is essential to avoid ecological problems.
Water-soluble solvents would in principle be suitable as solubilising agents in aqueous systems. However, if they enter the waste water, they can cause ecological problems. Furthermore, solvents can manifest themselves adversely in the products to be preserved.
Another possibility of solubilisation for the preparation of water-based active compound formulations is to use emulsifiers. In the case of highly water-insoluble compounds, such as azoles, large amounts of emulsifier are as a rule needed for this, which is to be avoided for ecological reasons. The activity of the microbicidal active compound can likewise be severely impaired by the use of emulsifiers. The usefulness for certain systems may also be limited.
The object of the invention was therefore to provide new, preferably water-based, solvent- and emulsifier-free microbicidal active compound formulations based on azole fungicides, which can be diluted easily with water and then give storage-stable solutions for use.
It has now been found, surprisingly, that stable aqueous solutions or emulsions which have a particularly high microbicidal activity can be prepared by combination of at least one azole fungicide in the form of the free base, preferably
1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazo-1-yl)-2-butanones (triadimefon)
&bgr;-(4-chlorophenoxy)-&agr;-(1,1-dimethyl-ethyl)-1H-1,2,4-triazole-1-ethanol (triadimnenol)
±&agr;-[2-(4-chlorophenyl)-ethyl]-&agr;-(1,1-dimethyl-ethyl)-1H-1,2,4-triazole-1-ethanol (tebuconazole)
(RS)-2-(2,4-dichorophenyl-1-(1H-1,2,4-triazol-1-yl)-hexan-2-ol (hexaconazole)
1-(N-propyl-N-(2-(2,4,6-(trichlorophenoxy)-ethyl)-carbamoyl)-imidazole (prochloraz),
2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol
1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolon-2-yl]-methyl]-1H-1,2,4-triazole (propionazole)
1-[2-(2,4-dichlorophenyl)-1,3-dioxolon-2-yl-methyl]-1H-1,2,4-triazole (azaconazole)
the isomers and isomer mixtures of the most diverse compositions also being included in the cases where the compounds have asymmetric carbon atoms;
especially preferably ±&agr;-[2-(4-chlorophenyl)-ethyl]-&agr;-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol (tebuconazole)
and at least one quaternary ammonium fungicide, preferably of the formula (II)
in which
R
1
, R
2
, R
3
and R
4
are identical or different and in each case represent unsubstituted or substituted, straight-chain or branched, saturated or unsaturated alkyl groups having 1-20 carbon atoms, alkylaryl and aralkyl groups having 5-10 carbon atoms in the aryl part and 1-20 carbon atoms in the alkyl part or aryl groups having 5-10 carbon atoms, and optionally mono-or polyalkoxylated derivatives hereof; possible substituents being halogen, C
1
-C
4
-alkyl and C
1
-C
4
-alkoxy; and wherein 2 or 3 radicals R
1
to R
4
on the quaternary centre, optionally with further hetero atoms, can form a saturated or unsaturated 5-, 6- or 7-membered (hetercyclic) ring and
x represents an anion which promotes water-solubility, such as, for example, halide, sulphate, alkylsulphonate or optionally substituted arylsulphonate.
Such aqueous formulations avoid the abovementioned ecological and use-related disadvantages of solvent-based or emulsifier-mediated formulations and in this respect are a useful enrichment of the prior art.
Quaternary ammonium compounds which may be mentioned as preferred are ammonium salts such as
C
12
-C
14
-alkyl-benzyl-dimethylammonium chloride
trimethyl-coconut-ammonium chloride
didecyldimethylammonium chloride.
C
12
-C
14
-Alkyl-benzyl-dimethylammonium chloride is particularly preferred.
As already mentioned, the azole fungicides are in the form of their free base.
A combination of tebuconazoles and C
12
-C
14
-alkyl-benzyl-dimethylammonium chloride is especially preferred.
The weight ratios of the active compounds in the active compound combinations can be varied within relatively wide ranges.
They depend in general on the field of use and on the particular azole and guaternary ammonium fungicides employed. However, these weight ratios can easily be determined in test series by simply mixing the components.
The weight ratio of azole fungicide to quaternary ammonium fungicide is preferably 1:99 to 99:1, in particular 1:40 to 9:1, particularly preferably 1:20 at 1:1 and especially preferably 1:10 to 1:2. To prepare aqueous formulations, the active compounds are incorporated individually or as an active compound combination, for example in the form of powders, granules, pastes or concentrated solutions, suspensions or emulsions, into water by simple mixing, and are then present in the form of an aqueous suspension, solution or emulsion.
The aqueous solutions or emulsions preferably contain more than 20% by weight, in particular more than 40% by weight of water and can be diluted with water as desired to the use concentration. It is of course also possible for the active compounds or active compound combination in the form of concentrates, solutions, suspensions, emulsions, powders, granules or pastes to be incorporated directly in the amounts required for use, for example by stirring into the agent
Büchel Karl-Heinz
Exner Otto
Holmwood Graham
Ludwig Georg-Wilhelm
Bayer Aktiengesellschaft
Norris & McLaughlin & Marcus
Pryor Alton
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