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Патент USA US2848304

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United States Patent 0
,.
ICC
2,848,297.
Patented Aug. 19, 1958
1
2
The metal- ethylenebisdithiocarbamate-containing fun~~
2,848,297
gicidal composition employed in practicing» the methods
MANGANESE E'IHYLENEBISDITHIOCARBAMATE
STABHJIZED BY DESICCANT; METHOD AND
of the invention- can- be unformulated metal ethylenebis
dithiocarbamate‘ or‘ formulated material. For example,
manganous~ ethylenebisdithiocarbamate or‘ other metal
ethylenebisdithiocarbamate can be admixed with ad
juvants, carriers or other biologically active materials as
desired as is disclosed1 in»
S. Patent‘ 2,504,404.
PACKAGE
Sanford J. Hill, Wilmington, DeL, assignor to E. I. du,
Pont de Nemours and Company, Wilmington, DeL, a
corporation of Delaware
No Drawing. Application October '12, 1953
Serial ‘No. 385,687
3 Claims. (Cl. 21-4)
In practicing‘ the‘ processes of' the invention, the desic
10 cant is included within the container for the metal ethyl
enebisdithiocarbama-te fungicidal composition in any’ con
venient manner;
This invention relates to fungicidal compositions com
prising a metal salt of ethylenebisdithiocarbamic acid.
More particularly, it relates to methods for protecting
such compositionsv from oxidation in closed containers
andv to the resulting packaged compositions so protected.
Metal ethylenebisdithiocarbamates have in general
fungicidal properties. Two members of the class,
namely‘ manganous ethylenebisdithiocarbamate- and zinc
One relatively simplemanner involves
placing one or more small porous paper or fabric bags
containing the desiccant within the) container for the
fungicidal composition». Instead of-‘plaeihg the desiccant
in a small bag, it can be placed‘ in any’ other convenient
receptacle adaptedI for avoiding direct contact of the
metal ethylenebisdithiocarbamate composition‘ without
20
ethylenebisdithiocarbamate, are currently marketed com
mercially and used effectively for the control of a wide
variety of plant attacking fungi. Manganous ethylene
preventing vapor‘ passage; if multi-wall bags are used
for- packaging the fungicidal’ composition, the desiccant
can, for example, be placed between the walls of the
multi-wall bag.
Alternatively if care is taken to avoid the use of a
bisdithiocarbamate and fungicidal compositions contain
desiccant which is reactive with the metal ethylenebis
ing it are described and claimed in U. S. Patent 2,504,404. 25 dithiocarbamate or other components of the fungicidal
Unfortunately, metal ethylenebisdithiocarbamates are
composition, the desiccant can be directly admixed with
relatively unstable on storage. Thus a serious problem
the fungicidal composition prior to packaging or it
has existed heretofore in marketing manganous ethyl
enebisdithiocarbamate fungicidal compositions, and to
a signi?cant though lesser extent in marketing zinc 30
ethylenebisdithiocarbamate fungicidal compositions, be
35
_
It has been found, for example, that commercial
formulations containing initially about 70% by weight
of manganous ethylenebisdithiocarbamate packaged and
closed for shipment in containers such as mentioned above
lose from 10 to 50% by weight of the manganous
ethylenebisdithiocarbamate content over a six-month
period (February-July) under normal storage conditions,
with losses in the higher part of the range occurring in
relatively Warm areas such as the Gulf Coast of the
United States, and lesser losses for example in the New 45
York City area.
It has now been found according to this invention
that metal ethylenebisdithiocarbamate fungicidal com
positions can be protected against decomposition in
closed containers by including within the container a
minor amount of a desiccant.
composition.
The amount of desiccant employed in the methods
and packaged materials of the invention can be varied
rather widely depending upon the relative action of the
cause these compounds tend to decompose relatively
rapidly on storage in conventional shipping containers
such as multi~wall bags, ?ber drums, glass bottles, and
the like.
can be introduced loosely in the packaging container
before, during, or after introduction of the fungicidal
The mechanism of the
desiccant used and the period and temperature of storage
for which protection is to be required. In general,
the desiccant will amount to from about 2 to 15% by
weight based on the weight of the composition which
is packaged.
In order that the invention may be better understood,
the following examples are given in addition to the
examples already given above.
Commercial manganous ethylenebisdithiocarbamic
fungicidal compositions were placed in various kinds
of contained as shown in the tabulation below and
stored in a warehouse for six months. Finely divided
anhydrous cupric sulfate was included as the desiccant
in each container in which compositions were packaged
according to this invention. The cupric sulfate was
contained within a cloth pack which was enclosed in the
container, the amount of cupric sulfate used being shown
in the table as “percent desiccant” and said percentage
being based on the amount of packaged manganous
protective action provided by the desiccant is not under
stood. The result is unexpected since available evidence
ethylenebisdithiocarbamate fungicidal composition in the
shows that the decomposition in packaged material not
container. In each case there was _a control, that is,
55
containing a desiccant is relatively independent of the
a like packaged composition in which the cupric sulfate
“breathing” properties of the package and thus the
was omitted.
humidity in the air surrounding the package, and since
it has also been found that there is relatively little change
in the free-moisture content of stored packaged material
whether or not it is protected by a desiccant according 60
to this invention.
The term “desiccant” as used herein with reference to
Example
Container
bromide, calcium chloride, anhydrous copper sulfate,
anhydrous sodium sulfate, low temperature ?red alumina,
and silica gel. These and other desiccants which will
be apparent to those skilled in the art can be used in
preparing the packaged compositions of the invention.
Desic
cant
the protective agent is employed in the conventional
sense to describe a material that will pick up water if
exposed to humid conditions. Such materials are also 65
sometimes called hygroscopic materials or agents. Illus
trative of such materials are calcium bromide, zinc
Percent
Percent Man
ganous Ethyl
enebisdithio
earbamate
As
After
Packed Six
Months
50 1b., 5 ply multiwall paper
bag with asphalt vapor bar-
5.5
None
74.7
74. 7
68.7
58.2
rier.
251b. ?bre drum with asphalt
vapor barrier.
2.1
None
75.1
74. 7
68. 7
60. 2
3 1b., 2 ply paper bag with
vapor barrier.
3 1b., 2 ply paper bag with 5
mil. polyethylene liner.
13.2
None
13.2
None
74.7
74.7
74.7
74. 7
68.2
56. 5
68.7
60.6
2,848,297
4
3
It will be seen from the above examples that the
decomposition rate in packages not containing the
I claim:
1. A method for protecting manganese ethylenebis
desiccant was from two to three times as great as the
dithiocarbamate from decomposition on storage in a
decomposition rate in compositions packaged according
closed container which comprises including Within the
to this invention. The analyses for manganous ethylene
container a minor amount of a desiccant, su?icient to
stabilize the dithiocarbamate.
bisdithiocarbamate given in the above table were deter
mined according to the carbon disul?de evolution method
2. A package comprising a closed container, man
ganese ethylenebisdithiocarbamate disposed within said
as described by W. K. Lowen, Journal of the Association of
container and a minor amount of a desiccant, sut?cient
O?icial Agricultural Chemists, May 1953, page 484 et seq.
The invention has been illustrated in the detailed 10 to stabilize the dithiocarbamate.
examples with speci?c reference to manganous ethylene
3. A package comprising a closed container, man
bisdithiocarbamate because the decomposition problem
ganese ethylenebisdithiocarbamate disposed within said
is acute with that material, and with reference to cupric
sulfate as the desiccant in all such examples so that the
manganese ethylenebisdithiocarbamate
results would be on a comparable basis.
container and from 2 to 15% by weight base on the
It will be 15
of anhydrous
cupric sulphate.
understood, however, that other metal ethylenebisdithio
carbamates and desiccants can be used in place of those
shown in the examples. Thus any departure from the
References Cited in the ?le of this patent
foregoing detailed description which conforms to the
principle of the invention, namely, to the utilization of 20
a desiccant to prevent decomposition of metal ethylene
bisdithiocarbamates on storage in closed containers, is
intended to be included within the scope of the claims
below.
25
UNITED STATES PATENTS
789,176
1,631,903
2,283,867
2,428,861
2,531,114
2,665,285
Smith _______________ __ May 9,
Van Der Lande ________ __ June 7,
Flosdorf ____________ __ May 19,
Waring et al. ________ __ Oct. 14,
Deitz _______________ __ Nov. 21,
Johnson ______________ __ Jan. 5,
1905
1927
1942
1947
1950
1954
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 2, 848,297
August 19, 1958
Sanford J. Hill
It above
is hereby
of the
numb certified that error appears in the printed specification
requiring
Patent should readered
as patent
corrected
below. correction and that the said Letters
Column 2, line 28, for "in" read as into v‘m; hine 44, for _' "contained"
read -- container -; column 4, line 13,. for "base-""read -— based --V.
Signed and sealed this 28th day of October 1958.
(SEAL)
Attest:
KARL Ho . AXLINE
Attesting O?icer
ROBERT C. WATSON
Commissioner of Patents
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