Fungicidal composition with synergistic activity

There is described a fungicidal composition which comprises a synergistic amount of PA1 (a) propyl 3-(dimethylamino)propylcarbamate or an acid addition salt thereof, and PA1 (b) a compound selected from the group consisting of zinc propylenebis(dithiocarbamate) polymer (propineb), zinc ethylenebis(dithiocarbamate) polymer (zineb), manganese ethylenebis(dithiocarbamate) polymer (maneb), zinc ammoniate ethylenebis(dithiocarbamate)-poly(ethylenethiuramdisulphide) (metiram), tetrachloroisophthalonitrile (chlorothalonil) and copper(I)oxide, as well as carriers and/or other additives, the ratio of component A to component B being preferably from about 1:0.1-3.

This invention relates to a fungicidal composition with synergistic 
activity. 
The composition contains, as essential ingredients, two components that 
mutually affect each other when used together and display a biological 
activity that is greater than the sum of the activities when used alone, 
an effect which is designated as synergism. This synergism leads to an 
increased protective activity when treating plants against a large number 
of fungi. 
Thus these fungicidal compositions can be used in plant protection for 
combating Deuteromycetes, Zygomycetes, Basidiomycetes, Plasmodiophoraceae, 
Ascomycetes, Domycetes and Chytridiomycetes. 
Compositions with fungicidal activity are already known and are the subject 
of Patents such as for example DE OS No. 6 05 551. Mixtures of fungicides 
that show a synergisitic activity are known (EP No. 106558 and 40007). 
However, there is still a considerable need and in even greater amounts 
for further compositions in this area with increased activity in order 
especially to meet the increased demands for protection of the environment 
and to overcome resistance. 
The object of the present invention is thus to provide a fungicidal 
composition with synergistic activity. This object is provided according 
to the invention, by a composition that is characterised by a content of 
(a) propyl 3-(dimethylamino)propylcarbamate or an acid addition salt 
thereof, and 
(b) a compound selected from the group consisting of zinc 
propylenebis(dithiocarbamate) polymer (propineb), zinc 
ethylenebis(dithiocarbamate) polymer (zineb). manganese 
ethylenebis(dithiocarbamate) polymer (maneb), zinc ammoniate 
ethylenebis(dithiocarbamate) poly(ethylenethiuramdisulphide) (metiram), 
tetrachloro isophthalonitrile (chlorothalonil) and copper(I)oxide, as well 
as carriers an other additives. 
the ratio of component A to component B being preferably from about 
1:0.1-3. 
Component A can be used in the form of an acid addition salt as well as its 
free base. The salts can be derived from inorganic or organic acids, such 
as mineral acids. mono or polycarboxylic acids or sulphonic acids for 
example: hydrochloric acid, sulphuric acid, formic acid, propionic acid, 
valeric acid, oxalic acid, malonic acid, succinic acid, cyanoacetic acid, 
chloroacetic acid, dichloroacetic acid, trifluoroacetic acid, benzoic 
acid, furan-2-carboxylic acid, p-toluenesulphonic acid, methanesulphonic 
acid, thioglycolic acid and citric acid. 
The compositions of the invention show a surprising fungicidal activity 
that exceeds the sum of the activities of the individual components when 
used alone. This synergistic activity could not be envisaged from the 
present state of knowledge. 
The synergistic activity of the composition of the invention is 
significantly displayed in a mixture ratio of 1 part by weight of 
component A to 0.1 to 3 parts by weight of component B, although these 
limits can be exceeded by greater or smaller amounts by weight. The 
composition of the invention shows increased activity in comparison to the 
additive activity of the individual components if one part by weight of 
propamocarb (component A) is used in the mixture with: 
0.5-1.5 parts by weight propineb 
1.0-3.0 parts by weight zineb 
0.5-1.5 parts by weight maneb 
0.5-2.0 parts by weight metiram 
0.5-2.0 parts by weight chlorothalonil 
or 1.0-3.0 parts by weight copper(I)oxide 
as component B. 
However, the weight ratio of component A and B depends on the sensitivity 
and resistance of the plants, the time of application the climatic 
conditions and the soil conditions. 
The composition of the invention shows a wide fungicidal activity against 
fungi of various systematic types, such as: Aphanomyces; Bremia; 
Peronospora: Phytophthora; e.g. Phytophthora infestans; Pseudoperonospora, 
e.g. Pseudoperonospora humuli; Pythium and Plasmopara e.g. Plasmopara 
viticola. 
In treating parts of the plant above the ground, protection is given 
against wind-borne diseases. In order to protect against seed-borne 
diseases the compounds of the invention can be used as a seed treatment. 
Besides they also act systemically, that means they are taken up by the 
roots of the plant, for example after sowing, are transported into the 
parts of the plant above the earth and protect against these diseases 
Because of the broad spectrum of activity that has been found, the 
compositions are suitable not only for protection of crops, but also for 
protection of materials and for combating microbes which are Pathogenic to 
humans and animals from which wide-ranging possibilities of use arise. 
The rate of use lies as a rule from 500 to 9000 g of the mixture 
(components A and B)/ha, preferably 1700 to 3500 g mixture/ha. 
The composition can be applied in conventional manner, for example with 
water as carrier in spray amounts of about 100 to 2000 liters per hectare. 
Application of the composition by so-called "low-volume" or "ultra-low 
volume" methods is also possible. 
The composition of the invention can be used also in mixture with each 
other active ingredients, for example growth regulants. Plant nutrients, 
soil-structure improvers, defoliants, plant-protection agents or 
pesticides, depending on the desired result. 
An improvement in the intensity and speed of action can be obtained, for 
example, by addition of suitable adjuvants, such as organic solvents, 
wetting agents and oils. Such additives may allow a decrease in the dose. 
The compositions of the invention can suitably be used as powders, dusts, 
granules, solutions, emulsions or suspensions, with the addition of liquid 
and/or solid carriers and/or diluents and, optionally, binding, wetting, 
emulsifying and/or dispersing adjuvants. 
Suitable liquid carriers are, for example water, aliphatic and aromatic 
hydrocarbons such as benzene, toluene and xylene, cyclohexanone, 
isophorone, dimethyl sulphoxide, dimethylformamide and other mineral-oil 
fractions. 
Suitable solid carriers include mineral earths, e.g. tonsil, silica gel, 
talcum, kaolin, attapulgite, limestone, silicic acid and plant products. 
e.g. flours. 
As surface-active agents there can be used for example calcium 
lignosulphonate. Polyoxyethylenealkylphenyl ether, naphthalenesulphonic 
acids and their salts, phenolsulphonic acids and their salts, formaldehyde 
condensates, fatty alcohol sulphates, as well as substituted 
benzenesulphonic acids and their salts. 
The amount of the mixture (components A and B) in the composition of the 
invention in the various preparations can vary over a wide range. For 
example the compostion can contain around 10 to 80 weight percent of the 
mixture, around 90 to 20 weight percent of liquid or solid carriers, as 
well as optionally up to 20 weight percent of surfactant. 
Formulations can be prepared, for example, from the following ingredients. 
(a) 90% mixture (components A+B) 
7% kaolin 
3% surfactant based on the sodium salt of N-methyl-N-oleyltaurine and 
calcium lignosulphonate 
(b) 
50% mixture (components A+B) 
35% colloidal silicic acid 
10% calcium lignosulphonate 
5% ammonium tetraethyleneglycolnonyl phenyl monosulphate 
(c) 
30% mixture (components A+B) 
2% colloidal silicic acid 
6% water 
(d) 
20% mixture (components A+B) 
70% tonsil 
8% cell pitch 
2% wetting agent based on fatty acid condensation products 
(e) 
5% mixture (components A+B) 
80% tonsilite 
10 cell pitch 
5% wetting agent based on fatty acid condensation products 
The preparation of the composition of the invention can be carried out by 
mixing the individual components in a suitable apparatus for this purpose. 
The following examples illustrate the possibility of use of the 
compositions of the invention. 
The examples contain data on components A and B, their rates of use, the 
percentage fungicidal acitivity achieved and the percentage inhibition 
obtained with the combination of A and B according to the method described 
by S. R. Colby, in which the existence of additive activity would be 
expected (S. R. Colby "Calculating Synergistic and Antagonistic Respones 
of Herbicide Combinations" Weeds 15/1 (1967) P 22-22). 
The calculation was carried out according to the following equation: 
##EQU1## 
in which X=the percentage of fungicidal activity with substance A at P kg 
active ingredient/ha 
Y=the percentage of fungicidal activity with substance B at g kg active 
ingredient/ha 
E=expected fungicidal activity by A+B at P+q kg/ha. 
If the observed value is higher than the value E calculated according to 
Colby, the combination has a synergistic activity.