DE2710469A1 - STABILIZED METAL SALT OF ETHYLENE-BIS-DITHIOCARBAMIC ACID, COMPOSITIONS OF THESE COMPOSITIONS AND METHOD OF STABILIZATION - Google Patents

Description

Dr. F. Zumstein Sr. - Or. C. Assmann - Dr. R. Koenigsberger Dipl.-Phys. R. Holzbauer - Dipl.-Ing. F. Klingseisen - Dr. F. Zumstein jun.

PATENT LAWYERS

8 MUNICH 2,

BRAUHAUSSTRASSE 4

TELEPHONE: COLLECTING NO. 22 53 41 TELEGRAMS: ZUMPAT TELEX 529979

Cas 1729 D

PROCIDA, Saint-Marcel, Marseille / France

Stabilized metal salts of ethylene-bis-dithiocarbamic acid, compositions containing these, stabilized compositions

Settlements and methods of stabilization

The present invention relates to stabilized metal salts of ethylene-bis-dithiocarbamic acid, these stabilized Compositions containing salts and a corresponding method for stabilization.

It is known that the metal salts have ethylene-bisdithiocarbamic acid fungicidal properties.

In particular, the manganese-bis-dlthiocarbamate (or Maneb) and the zinc ethylene bis-dithiocarbamate (or Zineb) have long been used extensively as fungicides in agriculture used.

Maneb and Zineb are prepared by adding a soluble salt of ethylene-bis-dithiocarbamic acid in an aqueous medium how an ammonium, calcium or sodium salt reacts with a soluble salt of manganese or zinc like sulphate. After The salts obtained are then precipitated and dried, with the necessary adjuvants added to a

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.6.

to obtain fungicidal composition.

It is also known that the maneb and the zineb are little are stable compounds that decompose easily under the action of heat, oxygen, and moisture.

This instability makes their industrial production and, in particular, their drying difficult.

If the drying is carried out under special precautions, i.e. at normal pressure and at a temperature of the order of magnitude from 80 to 110 ° C, one generally notices an extensive change in these zinc or manganese salts, which results in a change in color (for example, the color of the maneb changes from yellow to maroon and subsequently to black) and expresses itself in the formation of decomposition products with an unpleasant odor. The change can To such an extent that it leads to spontaneous ignition in the case of maneb, the Inflammation is likely related to a release of carbon disulfide.

Even when drying under milder conditions, for example is carried out successfully under reduced pressure at less high temperatures, which is more expensive, In general, the active ingredients are subject to later storage in the form of salts or in the form of containing these salts Compositions undergo considerable degradation, especially if storage is carried out under a humid and warm atmosphere will. This degradation manifests itself in a change in color, in the formation of compounds with an unpleasant odor and by a considerable decrease in titer (decrease in the analytical titer of CS «), which inevitably leads to a decrease in the fungicidal Activity. Moreover, decomposition processes of a complex nature lead to the formation of different ones Decomposition products which, in considerable quantities, can cause phytotoxicity to plants and to food

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create unwanted residues.

To counter these disadvantages, attempts were made to add various stabilizing compounds, such as Paraformaldehyde (French patent 1,344,342), o-, p- or m-phenylenediamine (French Patent Specification 1,374,622) or 1,8-3,6-diendomethylene-i, 3,6,8-tetraazacyclodecane (French patent specification 1,476,610) .

According to the invention it has now been found that the salts of ethylene bis-dithiocarbamic acid and in particular the zinc and manganese salts advantageously by adding cinnamaldehyde can be stabilized.

Thus, the present invention relates to the metal salts of Ethylene-bis-dithiocarbamic acid and compositions containing these salts, characterized in that these salts or these compositions by a sufficient amount of cinnamaldehyde or by converting this aldehyde resulting compound are stabilized.

Compounds that result from a conversion of cinnamaldehyde are understood as meaning the compounds that are starting from cinnamaldehyde in the presence of metal salts of ethylene-bis-dithiocarbamic acid or during the stabilization process form.

The invention relates in particular to the metal salts or the compositions as defined above, characterized in that the metal salt of ethylene-bsdithiocarbamic acid is manganese-ethylene-bis-dithiocarbamate or zinc-ethylene-bs-dithlocarbamate.

To ensure a good stabilization of the salts of ethylene-bis-dithlocarbamic acid and in particular to ensure of Maneb or Zineb or of compositions containing these salts,

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- * - 2710A69

it is preferable to use amounts of cinnamaldehyde between 0 * 1 and 10 Weight Ji (based on the weight of the stabilized salt) or from 0.1 to 20 wt .- ^ (based on the weight of the stabilized Composition).

The above mentioned cinnamaldehyde concentrations are preferred Concentrations that correspond to practical application.

It will be understood that the salts or compositions that contain lower: or higher amounts of stabilizing agents, do not depart from the scope of the invention.

The invention thus relates to the metal salts defined above, characterized in that the amount of cinnamaldehyde used to stabilize these salts is between 0.1 and 10% by weight, based on the weight of the stabilized metal salt, and the compositions defined above, characterized in that that the Zimtaldehydmenge used for the stabilization of these compositions between 0.1 and 20 wt -.% _y weight based on the weight of the stabilized composition.

The inventive stabilized compositions can be in the form of powders, wettable powders, granules, suspensions, emulsions and solutions containing the active ingredient and the stabilizing agent contained, for example, in a mixture with a carrier and / or an anionic, cationic or nonionic surfactant which, among other things, ensures a uniform dispersion of the substances of the composition. The carrier used can be a liquid such as water, alcohol, hydrocarbons or other organic solvents, a mineral oil, an animal or vegetable oil or a powder such as talc, clays, silicates or diatomaceous earth.

In practice the stabilized compositions of the invention will be used preferably either in the form of a wettable powder with 5 to 90 percent by weight of active ingredient or in the form of an aqueous suspension

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"• a"

pension with 10 to 70 wt .- # active ingredient.

The invention relates in particular to compositions, characterized in that this in the form of a V in / ater dispersible powder with 5 to 90 weight - of a metal salt of ethylene-bis-dithiocarbamic acid and 0.1 to 5 wt% -..% Cinnamic aldehyde, based on the weight of the stabilized composition, and compositions characterized in that they are in the form of an aqueous suspension containing 10 to 70 wt .- ^ of a metal salt of ethylene-bis-dlthiocarbamic acid and 0.1 to 15 wt .- ^ cinnamaldehyde, based on the weight of the stabilized composition.

The invention also relates to a method for stabilizing a metal salt of ethylene-bis-dithiocarbamic acid or a composition which contains this metal salt as an active ingredient, characterized in that during one or several synthesis stages and / or the formulation of this metal salt introduces a sufficient amount of cinnamaldehyde to ensure the stabilization of the salt or the composition containing it. The following is this Procedure denoted by the general procedure α.

More precisely, the invention relates to a method according to the general method α described above, in which the metal salt is manganese-ethylene-bls-dithiocarbamate or Zinc ethylene bis dithiocarbamate is.

According to the process according to the invention, an amount of cinnamaldehyde between 0.1 and 10% by weight is preferably used based on the weight of the stabilized salt and 0.1 to 20 wt .- # based on the weight of the stabilized composition.

The invention thus relates to a method for stabilizing a metal salt of ethylene-bis-dithiocarbamic acid the general method α, which is characterized

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^ o ·

is that the amount of cinnamaldehyde used to stabilize this salt is between 0.1 and 10 wt .- ^ based on the Weight of the stabilized salt and a method for stabilizing a composition according to the general Method cc, characterized in that that used for the stabilization of this composition Cinnamaldehyde amount is between 0.1 and 20 wt .- # based on the weight of the stabilized composition.

According to the invention, the cinnamaldehyde can be used during one or more stages of the chemical synthesis of the ethylene-bis-dithiocarbamic acid salt or introduced during the formation of this salt.

In particular, in the case of maneb or zineb, cinnamaldehyde can be used bring in:

either in the aqueous solution of the soluble salt of ethylene bis-dithioearbamic acid,

or in one of the aqueous solutions of the soluble manganese or zinc salt,

or during the precipitation of the manganese or zinc ethylene bis-dithiocarbamate simultaneously with the mixing of the aqueous solution of the ethylene-bis-dithiocarbamate salt and the aqueous Solutions of soluble manganese or zinc salt, or during suction of maneb or zineb, or while drying Maneb or Zineb, then adding the cinnamaldehyde either directly by pulverization can take place in liquid form or after prior introduction into an inert solid,

or during formulation, the incorporation preferably either by simply mixing the liquid cinnamaldehyde with classic adjuvants for the formulation, if the composition to be obtained is a liquid suspension, or by previously mixing the aldehyde with an inert powder in such a way that all components are homogeneously distributed the final mixing is ensured if one wishes to obtain a solid composition can be done.

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The invention thus relates to:

a method corresponding to the general method α described above, which is characterized in that the cinnamaldehyde is introduced during one or more chemical production stages of the ethylene-bis-dithiocarbamldic acid salt, in particular either in the solution of the soluble one Salt of ethylene-bis-dithiocarbamic acid or in the solution of the soluble metal salt or in the suspension of the Precipitation of the dithiocarbamic acid salt J a process corresponding to the general process α described above, which is characterized in that the cinnamaldehyde during the drying of the salt of ethylenebis-dithlocarbamic acid either by direct pulverization or in the form of a powder consisting of a mixture of Cinnamaldehyde and an inert filler is introduced; a method corresponding to the above-described general method α, which is used when the composition of the ethylene-bis-dithlocarbamic acid salt is a liquid A suspension which is characterized in that the cinnamaldehyde is incorporated into a mixture of various adjuvants for the formulation;

a method corresponding to the above-described general method α, which is used when the composition of the ethylene-bis-dithiocarbamic acid salt is a powder or a wettable powder, which is characterized in that the cinnamaldehyde in the final mixture according to the preceding Mixing with an inert powder is introduced in such a way that there is a homogeneous distribution of the stabilizing agent in the Composition ensures.

The interest in the stabilizing agent during various stages of the synthesis or formulation of Bringing maneb or zineb is due to the presence of the stabilizing agent during drying is required, but this also occurs during storage of the formulated or non-formulated product before or after the formulation is necessary. It is known that in particular,

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if the degradation processes to be combated have a considerable extent, the stabilizing agent introduced after it has played its part, is more or less chemically transformed. So it can be beneficial after drying add another amount of cinnamaldehyde again to ensure storage without change since the initial amount of Stabilizing agent may have decreased considerably during drying.

It should also be noted that due to the the above-mentioned type of phenomena in a Maneb or Zineb sample or in a sample of one of these products Composition of detectable amounts of cinnamaldehyde can be considerably lower than the doses of stabilizers that were originally introduced.

The invention also relates to compositions which contain a metal salt of ethylene-bis-dithiocarbamic acid and a sufficient one Amount of cinnamaldehyde or of a compound resulting from a * conversion of this aldehyde to this metal salt to stabilize, which are characterized in that they are obtained according to one of the processes described above and especially those of these compositions which are characterized in that the salt of ethylene bisdithiocarbamic acid Manganese ethylene-bis-dithiocarbamate or zinc-ethylene-bis-dithiocarbamate is.

The invention also relates to metal salts of ethylene-bis-dithiocarbamic acid, obtained by one of the processes described above, which are characterized in that they have a sufficient amount of cinnamaldehyde or a compound resulting from the conversion of this aldehyde, included to ensure the stabilization of these salts and in particular those of these salts that are characterized are that the salt-forming metal of ethylene-bis-dlthiocarbamic acid Is manganese or zinc.

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The stabilizing effect of cinnamaldehyde is used in the experimental Partly shown on the basis of comparative experiments with or without the addition of cinnamaldehyde.

These tests show in particular:

that during the drying of Maneb at 100 ^° C. the addition of cinnamaldehyde prevents the product from igniting, which spontaneously ignites without stabilization; that the addition of cinnamaldehyde to maneb either as a product in loose form or in the form of a product after formulation in the form of a wettable powder or an aqueous suspension considerably reduces the decomposition of maneb under the influence of heat and moisture; that the addition of cinnamaldehyde to maneb greatly reduces the amount of undesirable impurities such as ethylene thiourea which is formed under the influence of heat and moisture without the addition of the stabilizing agent; that the addition of cinnamaldehyde to an aqueous suspension of zineb considerably reduces the decomposition of the zineb under the influence of heat and moisture; that the zinc or manganese ethylene-bis-dithiocarbamates obtained in the presence of cinnamaldehyde are odorless or have hardly any odor and have a satisfactory color, which is not the case in the absence of the stabilizing agent.

The special advantages of the stabilization process according to the invention compared to processes according to the prior art are based in particular on

that the cinnamaldehyde, a liquid compound, easily dissolves in a satisfactorily homogeneous mixture with the salts of ethylene-bis-dithiocarbamic acid as such or in loose form or can be converted according to a formulation, the solid stabilizers especially in the case of aqueous suspensions tend to settle at the bottom of the recipients, that the cinnamaldehyde considerably that of the decomposition products of the salts of ethylene-bis-dithiocarbamic acid

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Odors (mercaptans, sulfur derivatives ...) reduce the fact that the cinnamaldehyde to a considerable extent the formation of Decreases ethylene thiourea, which tends to result from the salts of ethylene-bis-dithiocarbamic acid under the influence from heat and moisture to form.

The following examples illustrate the invention without restricting it.

example 1

Preparation of stabilized manganese-bis-dithiocarbamate 820 ecm of an aqueous ammonium-bis-dithiocarbamate solution (titer by weight 28.5 %) is introduced into 4800 ecm of water at 45 ° C., 1052 g of an aqueous manganese sulfate solution with a titer of 280 are added g / l added, stirred for 30 min., The precipitate formed was isolated by suction, washed with water, 520 g of moist maneb was obtained, which was mixed intimately with 8 g of cinnamaldehyde, dried in the open air at 100 ^° C. and obtained 408 g Maneb of yellow color, which is practically odorless and has a titer of 96 % .

Example 2

Preparation of stabilized manganese-bis-dithlocarbamate One brings 820 ecm of an aqueous ammonium-bis-dithiocarbamate solution (weight titre 28.5 %) into 4800 ecm of water at 45 ° C., at the same time adds 10 g of cinnamaldehyde and 1052 g of one with stirring aqueous manganese sulfate solution with a titer of 280 g / l, stir for 30 min. Isolate the precipitate formed by suction, wash it with water, obtain 532 g of moist maneb, which is ^{dried in the open air at 100 °} C. and obtained 407 g of yellow colored maneb which is practically odorless and has a titer of 96 % .

Example 3

Stabilized aqueous suspension based on maneb An aqueous suspension of maneb is obtained by mixing the following ingredients:

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stabilized maneb 30 g

Cinnamaldehyde 2 g Brecolane N.V.A. »1g Calcium lignosulfate 4 g

Carboxymethyl cellulose C 500 £ * 0.5 g

Ethylene glycol 10 g

Water 52.5 g fc sodium alkylnaphthalene sulfonate ♦♦ viscosity 300 cP

Example 4

Stabilized wettable powder based on Maneb A wettable powder is obtained by using the following

Components mixes:

stabilized maneb 86.5 g

Cinnamaldehyde 3 g Calcium lignosulfate 3 g Brecolane N.V.A. 1g Silicon dioxide 6.5 g

The cinnamaldehyde is first mixed with an equal weight of silicon dioxide , this mixture then being incorporated into the other components according to the usual methods .

example 5

Stabilized wettable powder based on Zlneb

A wettable powder from Zineb is obtained by adding the

mixes the following ingredients:

technical zineb 90 g

Cinnamaldehyde 2 g Calcium lignosulfate 3 g Brecolane N.V.A. 1g Silica 4 g Example 6

Comparative experiment in In terms of the stability of maneb with or without Addition of cinnamaldehyde

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1.) Influence of adding cinnamaldehyde at the time of drying maneb

Bringing into 1200 cc of water at 45 ⁰ C, 205 g of an aqueous Ammoniumäthylen-bis-dithiocarbamatlösung (with a weight titre of 28.5%) that adds 265 g of an aqueous manganese sulfate solution having a titer of 280 g / l, stir for 20 minutes, isolate the precipitate formed by suction, wash it with water and obtain 150 g of moist precipitate, which is divided into two equal parts:

The first part is dried in the open air in an oven at 100 ⁰ C. After a few minutes, a violent or spontaneous ignition of the product is observed, which turns black.

The second part is intimately mixed with 1 g of cinnamaldehyde and then dried under the same conditions as the first part. 51 g of yellow colored maneb with a titer of 96.5 %, which is practically odorless, are obtained. Conclusion;

During drying at 100 ^° C. in the open air, the addition of cinnamaldehyde prevents the maneb from igniting and enables a maneb with a very high titer to be achieved. 2) Study of the storage of maneb at 80 ° C and a relative humidity of 100 ⁰ C with or without the addition of cinnamaldehyde.

Maneb is prepared by using the same amounts of reactants as in paragraph 1 of Example 6. The precipitate obtained is ^{dried at 85 °} C. under a vacuum of 30 mm Hg. 100 g of maneb are obtained, which is divided into four equal parts: the first part is left as such and forms the comparative component (A);

0.25 g of cinnamaldehyde is added to the second part (B); the third part is mixed with 0.5 g of cinnamaldehyde (C); the fourth part is mixed with 0.75 g of cinnamaldehyde (D);

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5 g of each of the batches A, B, C and D are stored in open receptacles which are placed in an oven at 80 ° C. with a relative humidity of 100 % . After 8 hours of storage, the following observations can be made:

Approach A.

Maneb ^ titer

at the beginning after

8th; Hrs;

94%

4%

Color of the maneb

at the beginning "· after

: 8 hours

yellow- _; ,

: chestnuts · • brown / - ^. .: black

(Approach B

(ÄP-sentence C

93%

60%

yellow - ^: yellow

92%

yellow

^: yellow -

(Approach. D

J

91%

70%

ge Ib

Conclusion;

At a temperature of 80 ° C and a relative humidity of 100 % , normal maneb with a titer of approx. 94 % is completely decomposed after 8 hours, while samples of the same origin with different proportions of cinnamaldehyde still have 60 contain up to 70 % active ingredient.

J.) Investigation of the storage of maneb in the form of a wettable powder at 50 ° C and a relative humidity of 80 % with or without the addition of cinnamaldehyde: An intimate mixture of the following ingredients is prepared: a) a wettable powder (A), the comparative composition containing 86.5 grams of maneb, 3 grams of calcium lignosulfate, 1 gram of Brecolane NVA, and 9.5 grams of silicon dioxide;

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b) a wettable powder (B) containing 86.5 g of maneb, 2 g of cinnamaldehyde, 3 g of calcium lignosulfate, 1 g of Brecolane N.V.A. and Contains 7.5 g of silicon dioxide;

c) a wettable powder (C) containing 86.5 g of maneb, 3 g of cinnamaldehyde, 3 g of calcium lignosulfate, 1 g of Brecolane N.V.A and 6.5 g Contains silicon dioxide.

The three formulations are subjected to the following test: Two metal plates are placed in an oven with a volume of 200 l and dimensions 60 × 60 × 58 cm at a distance of 19 cm and 38 cm from the floor. 50 circles with a diameter of 32 mm are cut into each metal plate. 100 crucibles made of frit glass with a diameter of 30 mm and with a certain porosity are placed in these circles. 3 g of each of the batches A, B and C are placed in these crucibles, which are distributed randomly. The oven is set to 50 ^° C. and a relative humidity of 80 % .

The manebs are observed at intervals of 10 days, 20 days and 30 days. The crucibles corresponding to these observations are removed from the oven, homogenized and placed in a desiccator in the presence of phosphoric anhydride until the weight is constant (48 hours). The manbtiter (determined by measuring CS ₂ ) and the titre of ethylene thiourea (ETU) are then determined. The experimental results obtained are given in the following table:

( *
A ' Beginning •
:
O%: O, 25 4th
% 1
% - % % /
.) ί B ί •
•
2%: 0.18 I.
% %; % % I.
)
) (
(Approach, C: . Tifcer. Titer
ί CS ₂ : ETü. •
O%: 0.15 %: %: %: % )
)
) (A / isatz : to ίβ3, : 10 days : 20 days : 30 days ) (Approach ■
: 83, 83, : Titer, _titer;!
• fQ · T ** Φ Tl Titer: titer
ί CS ₂ : ETU : Titer.titer
: CS ₂ : ETU I ·
: 25.3% <: 3.9 •
»·
t
• 5.1%: 5.9 »·
»·
: .3,4%: _8/3 •
• 70%: 0.3 *
•
•
55%: 0.8 > ·
: 49%: 1.2 •
•
72%: O, 3
• •
. :
61%: O, 6
•
• ί 54%: 0.9

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Conclusion;

At a temperature of 5O ⁰ C and at a relative humidity of 80%, a Manebprobe in the form has passed almost completely decomposes a wettable powder for a month and the remaining product contains a content of Äthylenthioharnstoff in the order of 8%, while with cinnamaldehyde stabilized maneb samples still contain 50% active ingredient and the content of ethylene thiourea formed in these stabilized samples is of the order of 1 % .

4.) Investigation of the retention; von Maneb in the form of an aqueous suspension with or without the addition of cinnamaldehyde: An aqueous maneb suspension is prepared as indicated in Example 3 (suspension A) and an analogous aqueous suspension of the composition in which the cinnamaldehyde is replaced by water (suspension B).

After a 6-week storage at 5O ⁰ C, the suspension B was transferred into a heterogeneous mass, which makes use legendary impossible remained while the suspension A homogeneous and has only a loss of titer of 10%.

Conclusion;

A classic or conventional aqueous Manebsuspension, which is stored at 50 ⁰ C, after 6 weeks has symptoms of a precipitate and a transition into a mass, which leads to heterogeneity, which makes their use impossible, while in the presence of cinnamic aldehyde, the suspension remains homogeneous and shows only a slight loss of titer.

Example 7 Investigation of the storage of Zineb in the form of wettable Powder with or without the addition of cinnamaldehyde;

It is poured into water 5OOO ECM 536 g of an aqueous Ammonlumäthylen-bis-dlthiocarbamatlösung (titer 28.4 wt .- ^), and then brings slowly a solution of zinc sulfate 29Ο g (7 H ₃ O

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in 900 ecm of water, stir, isolate the precipitate formed by suction, wash it with water and dry it at 50 ⁰ C until a constant weight is achieved. 280 g of zineb are obtained, which are divided into two equal portions: starting from the first portion, a wettable powder is prepared which contains 90 g of zineb, 3 g of calcium lignosulfate, 1 g of Brecolane NVA and 6 g of silicon dioxide (batch A); Starting from the second part, a wettable powder is produced which contains 90 g of zineb, 2 g of cinnamaldehyde, 3 g of calcium lignosulfate, 1 g of Brecolane NVA and 4 g of silicon dioxide (batch B).

5 g of each of the batches A and B are stored in an oven at 70 ^° C. at a relative humidity of 100 %. After 15 hours of storage, the following results are found, which are given in the table below:

Zineb titer (determined by brass from CSg) .-. _ ^ r)

^: at the beginning .Jl ~ ^: after 15 hours ""' \

Approach A. ...: 83%: 35%)

Approach B s 83%: 65%)

Conclusion:

A wettable powder from Zineb stored for 15 hours at 70 ° C. and a relative humidity of 100 % appears to change its titer from 83 % to 35 % , while the titer of the same wettable powder which has been treated with cinnamaldehyde and has been stored under the same conditions, is 65 % after 15 hours.

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Claims (1)

Claims (1 .y Metal salts of ethylene-bis-dithiocarbamic acid and compositions containing these salts, characterized in that these salts or compositions have been stabilized by a sufficient amount of cinnamaldehyde or a compound resulting from the conversion of this aldehyde. 2.) Salts or compositions according to claim 1, characterized in that the metal salt of ethylene-bis-dithiocarbamic acid is manganese-ethylene-bis-dithiocarbamate or zinc-ethylene-bis-dithiocarbamate. 3.) Metal salts according to claim 1 or 2, characterized in that the amount of cinnamaldehyde used to stabilize these salts is between 0.1 and 10% by weight , based on the weight of the stabilized metal salt. 4.) Compositions genäß claim 1 or 2, characterized in that that the amount of cinnamaldehyde used to stabilize these compositions is between 0.1 and 20 wt .- ^ based on the weight of the stabilized composition. 5.) Compositions according to claim 1, 2 or 4, characterized characterized in that they are in the form of a water-dispersible powder containing 5 to 90 wt .- # of a metal salt of ethylene-bis-dithiocarbamic acid and 0.1 to 5 wt .- ^ Cinnamaldehyde based on the weight of the stabilized composition. 6.) Compositions according to claim 1, 2 or 4, characterized in that they are in the form of an aqueous suspension containing 10 to 70% by weight of a metal salt of ethylene-bis-dithiocarbamic acid and 0.1 to 15 wt .- ^ cinnamaldehyde based on the Weight of the stabilized composition. 709838/0765 ORIGINAL INSPECTED . 2710463 7.) Process for stabilizing a metal salt of ethylene-bis-dithiocarbamic acid or a composition, containing this metal salt as an active ingredient, characterized in that that one or more stages of the synthesis and / or the formulation of this metal salt a introduces sufficient amount of cinnamaldehyde to stabilize the salt or the composition containing it to ensure. 8.) Method according to claim 7 *, characterized in that this metal salt is manganese-ethylene-bis-dithiocarbamate or zinc-ethylene-bis-dithiocarbamate is. 9.) A method for stabilizing a metal salt of Äthylenbis-dithiocarbamic acid according to claim J, characterized in that the amount of cinnamaldehyde used for stabilizing this salt is between 0.1 and 10% by weight , based on the weight of the stabilized salt. 10.) A method for stabilizing a composition according to claim 7 »characterized in that the stabilization This composition used amount of cinnamaldehyde between 0.1 and 20 wt .- ^ based on the weight of the stabilized Composition amounts. 11.) The method according to claim 7 »characterized in that d & ß the cinnamaldehyde during one or more stages of the chemical production of the salt of ethylene-bis-dithiocarbamic acid either in the solution of the soluble salt of ethylene bisdithiocarbamic acid or in the solution of the soluble metal salt or in the suspension of the precipitate of the salt the dithiocarbamic acid is introduced. 12.) The method according to claim 7 »characterized in that the cinnamaldehyde at the time of drying the salt of Xthylenbis-dithiocarbamic acid either by direct pulverization or in the form of a powder consisting of a mixture of 709838/0785 Cinnamaldehyde and an inert filler is introduced. 15 ·) Method according to claim 7 «applied in the case« in the the composition of the salt of ethylene-bls-dithlocarbamic acid is a liquid suspension, characterized in that the cinnamaldehyde is incorporated into the mixture of the various adjuvants for the formulation. 14.) The method according to claim 7, used in the case at dsm the composition of the salt of ethylene-bis-dithiocarbamic acid is a powder or a wettable powder, characterized in that the cinnamaldehyde is introduced into the final mixture, after it has previously been admixed with an inert powder in such a way that a homogeneous distribution of the stabilizing agent is ensured in the composition. 15.) Compositions containing a metal salt of ethylene bis-dithiocarbamic acid and a sufficient amount of cinnamaldehyde or a compound resulting from the conversion this aldehyde, to stabilize this metal salt, characterized in that it according to one of the processes according to the Claims 7 # 8, 10, 13 or 14 can be obtained. 16.) Compositions according to claim 15, characterized in that the salt of ethylene-bis-dithiocarbamic acid is manganese-ethylene-bis-dithiocarbamate or zinc-ethylene-bisdithiocarbamate. 17 ·) Metal salts of ethylene-bis-dithiocarbamic acid obtained according to one of the methods of claims 7, 8, 9, 11 or 12, characterized in that they contain a sufficient amount of Cinnamaldehyde or a compound resulting from the conversion of this aldehyde contained in order to stabilize these salts to ensure. 709838/0765 18.) Metal salts of ethylene-bis-dithiocarbamic acid according to Claim 17 * characterized in that the salt-forming metal of the ethylene-bis-dithlocarbamic acid is manganese or zinc. 709838 / 07B5