Note: Descriptions are shown in the official language in which they were submitted.
HOE 73/F ~7
1037~65
The present invention relates to fungicidal dispersions
of 2-benzimidazole methylcarbamate (BCM) of the formula
~ / -?~ CO~c~{3
1 :
It is known from British Patent Spec.: 1,190,614 that
BCM has excellent properties as a systemic plant fungicide.
Because of its complete insolutility in lipoids, however, it 10 does not penetrate easily through the plant surface into the
interior of the plant where it can display its systemic activity.
As a consequence, much of the material remains on the outer
plant surface where it acts as a prophylactic fungicide only
and is subject to the deteriorating influence of the weather.
The British patent describes a number of ways by which
the penetrating capacity of BCM and hence its systemic activity
~ may be improved, such as grinding it to a very fine particle
-- size (below 5 microns) or adding larger-than-usual amounts of
so-called "penetrants", i.e. compounds that facilitate the
penetration of BCM into the plant interior. However, while
. , .
these measures remove the drawbacks described above, they
create others. For instance, dry milling to a very fine ~ -
particle size requires special types of mills and expensive
filtering apparatus, and the addition of large amounts of
penetrants may cause toxicity hazards in the treated plants.
Especially, it has nlot been possible to produce useful dis-
persions of BCM by the ways described in the British patent.
Such dispersions have a number of advantages over usual -
29 formulations such as dusts and wettable powders.
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Since for making dispersions the active compounds are ground
in the wet state as slurries they do not require expensive
filtering devices. Furthermore, dispersions are more easily
dosable and do not dust while handling, thus reducing the
hazards of toxicity to humans.
The preparation of stable dispersions is difficult.
In order to prevent premature sedimentation the active com-
pounds have to be ground very finely. In this state, however,
strong Van der Waal's attraction forces appear between the ;
dispersed particles causing aggregation and flocculation of
the particles. To prevent this a surface active agent is
usually added which concentrates at the solid-liquid interface
and forms a solvating envelope around the individual particles
carrying uniform electric charges and thus preventing agglo-
meration. Even so, however, the solvating envelope may break
down partially e.g. if the dispersion is kept at higher
temperatures over prolonged periods of time,which results in
increasing viscosity, flocculation and irreversible sedimen-
tation.
It is an ob~ect of the present invention to provide stable
disperslons of BCM.
It is a further ob~ect of the invention to provide dis-
persions of BCM which have an improved systemic fungicidal
! activity as compared with previously described BCM-formulations
and which are equal to the most active standard plant fungi-
cides such as Benomy~ n-butylcarbamoyl-2-methoxy-carbonyl_
amino-benzimidazol).
The fungicidal dispersions of the invention are charac-
29 terized by a content of
-- 3 --
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;
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HOE 73/F ~2?_
103786S
a) about 5 to 30 % by weight of 2-benzimidazole-methyl-
carbamate
-I~H-COOC~3
H
b) about 60 to 85 % by weight of liquid esters of
- (C1 ~ C12) monoalcohols and (C2 - C10) carboxylic acids,
the esters containing at least 8 and, in the case of
- 10 esters of monobasic acids, a maximum of 12 and, in the
case of esters of dibasic acids, a maximum of 32 carbon
atoms.
c) about 2 to 10 % by weight of a combination of a
(C8 ~ C12)-monoalkylphenol polyglycol ether and castor
oil polyglycol ether and -~
d) about 0.1 to 5 % by weight of Ca-(C8 - C15)-monoalkyl-
benzene sulfonate.
Within these limits the components and percentages may be
; varied to a large degree. It will be appreciated however that~
if high percentages of active ingredient are desired, esters
of low viscosity among those as claimed are used in order to
en8ure easy mobility of the dispersion obtained. Conversely,
with smaller percentages of active ingredient esters of higher
viscosity may be used.
Suitable esters are for example those of aliphatic (C6-C10)-
carboxylic acids such as caprolc, capric, caprylic and per-
- largonic acid or esters of aromatic carboxylic acids such as
benzoic, toluic, salicylic and phthalic acid. Suitable alcohol
29 components of these esters are, for example, butanol, n-octanol,
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HO~ 7~/F 327
10378~jS
i-octanol, dodecanol, cyclopentanol, cyclohexanol, cycloocta-
nol or benzyl alcohol. Examples of suitable esters are benzyl
acetate, caproic acid ethyl ester, perlargonic acid ethyl
ester, benzoic acid methyl or ethyl ester, salicylic acid
methyl, propyl or butyl ester. Especially preferred are di-
esters of phthalic acid with aliphatic or alicyclic (C1-C12)-
alcohols, such as phthalic acid dimethyl ~Er , dibutyl ester,
diisooctyl ester, didodecyl ester, dicyclopentyl ester, di-
cyclohexyl ester or dicyclooctyl ester.
The combination of monoalkylphenol polyglycol ether and
castor oil polyglycol ether acts as surface active agent in
the composition according to the invention.
Suitable monoalkylphenol polyglycol ethers are especially
those having 8 to 9 carbon atoms in the alkyl moiety and a
variable degree of ethoxylation, preferably 5 to 14 ethylene
oxide (AeO) units and, especially 8 to 12 AeO units. Examples
of such compounds are the types commercially available under
the trade name "Triton(R)" for example Triton X-45, X-114
and X-207. Their proportion in the total formulation is ad-
vantageously from 3 to 4 % by weight. The castor oil poly-
glycol ethers which are also requir0d have a degree of ethoxy-
lation preferably in the range of from 30 to 50 and especially
of from 36 to 40 AeO units. They are for in8tance commercially
available under the trade name "Emulsogen EL(R)", their pro-
portion is advantageously in the range of from 1.5 to 3 % by
weight. The calcium salts of higher monoalkyl benzene sulfonic
; acids may be used as additives to the dispersions owing to
their solubility in organic solvents. Calcium salts of
29 (C10-C12)-monoalkyl benzene sulfonic acids, especially of
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~, . ..
~ HOE 7~/F 327
10;~7~S
dodecyl benzene sulfonic acid, are preferably used. Their
content is preferably 0.5 to 5 %, especially 2 to 4 % by weight.
The Ca-alkylbenzene sulfonates may be added in the solid
state or, preferably, in alcoholic solution, for example in
isopropanol or isobutanol.
The dispersionsof the invention are prepared in known
manner, for example by grinding the starting material in ~all
mills by means of quartz pearls having a diameter of from 1 to
2 mm. The active ingredient in the dispersions obtained has ~ -
a particle size of less than 10, preferably of less than
; 5 microns.
; The composition of the emulsifier is critical for the
properties of the formulation. Comparative tests have shown
that commonly used emulsifiers such as polyglycol esters of
oleic acid, stearic acid or palmitic acid, polyglycol deri-
vatives of dodecylmercaptan, of oleylamines or stearylamines
do not form storable dispersions with BCM. The same applies
to polyglycol ethers of oleyl, stearyl and technical coconut ~ ~
fat alcohols and of dodecylalcohol, of varying degrees of poly- ~ -
merization. Alkylphenol polyglycol ethers used alone were
likewise unsuitable.
The dispersions according to the lnvention on the other
hand are distinguished by an excellent activity and a high
storability. In this respect they are considerably superior
to the dispersions known from British Patent Specification
No. 1,190,614 (examplle 5). Their efficiency is also superior
to known wettable powder formulations of BCM and to Benomyl
formulations, as the follow~ng examples illustrate.
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103786S
E X A M P L E 1 (Comparative agent 1)
According to example 5 of British Patent Specification
No. 1,190,614 a dispersion was prepared
containing 26 % by weight of BCM
38.57 % by weight of indene resin (Piccolyte
resin S-10)
26.43 % by weight of low boiling isoparaffin oil
(Soltrol 130(R))
9 % by weight of lauryl alcohol polyglycol
ether.
A 115.71 g (38.57 %) of Piccolyte resin S-10 were dissolved
in 79.29 g (26.43 %) of Soltrol 130 and introduced into the
stirring compartment of a ball mill. Then 78 g (26 %) of BCM,
27 g (9 %) of laurylalcohol polyglycol ether ha~ing a poly-
merization degree of 10 and 500 g of 1 mm quartz pearls were
- added and the whole was ground for 6 hours. Thereafter the
BCM had a particle size of less than 5 microns. The quartz
pearls were then separated by sie~ing.
After a storage life of 37nonths the dispersion was
viscous, the cediment could not be redispersed in the container
and di~perBed in water only with great difficulty.
E X A M P L E 2
.;
A BCM dispersion according to the invention and
containing 20.00 % by weight of BCM
' 25 4.00 % by weight of Ca-dodecylbenzene sulfonate
(in the form of a 70 % solution in i-butanol)
2.66 % by weight of castor oil polyglycol ether
'~ ("Emulsogen EL 400(R)")
, ,
! 2g 3.34 ~ by weight of octylphenol polyglycol ether ~ ~
.
- ~ Tr~e ~.K - 7 ~
~ HOE 73/F 327
~0 37 ~ ~ S
("Triton X-207(R)")
70.00 % by weight of phthalic acid diisooctyl ester
("Genomoll 100(R)")
was prepared in the same manner.
E X A M P L E 3:
Another dispersion had the following contents:
15 % by weight of BCM
3 % by weight of Ca-dodecylbenzene sulfonate
2.7 % .by weight of castor oil polyglycol e.ther
103.3 % by weight of octylphenol polyglycol ether
(Triton X-207)
76 % by weight of phthalic acid diisononyl ester
(Genomoll 150)
E X A M P L E 4:
5Another dispersion had the following contents:
25 ~ by weight of BCM
4.2 % by weight of Ca-dodecylbenzene
2.48 ~ by weight of castor oil polyglycol ether
(Emulsogen EL 400(R))
202.00 % by weight of octylphenol polyglycol ether
(Triton X-207(R))
1.32 % by weight of octylphenol polyglycol ether . ::
(Triton X-117(R))
65 % by weight of phthalic acid diisobutylester
(Genomoll 140(R))
A commercial Blenomyl powder was used as a further com-
parative agent (comparative agent 3). : .
,
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HOE 73/F 327
1~)37~5
E X A M P L E 5:
Cucumber plants were cut off above the first two true
leaves. As soon as these were completely grown, the cotelydons
situated below were also removed and the lower parts of the
leaves were sprayed to the drip off with aqueous preparations
of the composition of example 2 by means of a microapplicator.
Care was taken to insure that the upper surface of the
leaves and other parts of the plant as well as the soil were
not contaminated by active ingredient.
The comparative preparation of example 1 was used as
comparative agent.
The compositions of the test preparations and of the
comparative agents were applied in concentrations of 1000,
500, 250, 125, 60 and 30 mg each of active ingredient per liter
of spraying liquid.
3 After drying, the upper surface of the leaves was infected
with conidia of cucumber mildew (Erysiphe cichoracearum).
The plants were then placed in a green house at a relative
humidity of 80 to 90 % and a temperature of from 2~ to 25C.
- 20 After an incubation time of 14 days the plants were examined
visually as to the degree of damage by cucumber mildew.
The degree of damage was expressed in percent of attacked
surface of the leaves compared to infected untreated control8.
From the result indicated in table 1 it is seen that the
activity of the dispersion prepared according to British
Patent Specificatioln No. 1,190,614 was considerably lower than
that of the dispersion according to the invention. The latter
dispersion was also by far superior to the commercial formu-
29 lation of Benomyl.
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HOE 7~/F 327
E X A M P L E 6: 1~78~5
Apple seedllngs in the 8-leaf-state were defoliated,
except for the 4 youngest unfilded leaves, strongly infected
with conidia of apple scab (Venturia inaequalis) and placed
dripping wet in a climatic chamber having a relative humidity
of 100 % and a temperature of 20C.
; After 2 days the plants were put in a green-house ad-
~usted to a temperature of 18C and a relative humidity of 90
to 95 %.
After 3 days the lower surfaces of the leaves were sprayed
to the drip off with aqueous preparations of the dispersions
prepared according to example 2 using the same precautions as
- in Example 3.
: A dispersion prepared according to example 1 (comparative
agent 1) and a dispersion of Benomyl (comparative agent 2) were
applied as comparative agents in an analogous manner. The
applied concentrations were 1000, 500, 250, 60 and 30 mg each
of active ingredient per liter of spraying liquid.
After drying the plants were replaced in the green-house
and examined visually as to the degree of damage by apple scap
after an incubation time of 21 days. The degree of damage was
expressed in percent of attacked surface of the leaves calcu-
lated on infected untreated controls.
From the test result indicated in table 2 it is seen that
the activity of the formulation according to the invention was
considerably higher than that of the comparative agent 1.
The formulation according to the invention was also ~uperior
!:
~ to the comparative agent 2.
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