DE1060660B - Process to increase the duration of action of pest control agents based on dithiocarbamates - Google Patents

Description

GERMAN

B44291IVa / 451

ANHELO DAY: APRIL 13, 1957

NOTICE THE REGISTRATION AND ISSUE OF THE EDITORIAL:

2nd JUH 1959

It is known compounds of the general formula

ncsr ₃

where R ₁ and R ₂ each represent an aliphatic or aromatic radical or two members of a ring, Rj a metal, an amine, a carbamate radical or the radical

R ₄

Procedure ,

to increase the duration of action of pesticides based on dithiocarbamates

Applicant:

Joh. A. öenckiser G.m.b.H.,

Chemical factory,
Ludwigshafen / Rhein, Frankenthaler Str. 3

represents, where R ₄ and R _{5 have} the meaning of R ₁ and R ₂ and their substitution products, to be used as fungicides and / or bactericides. If these compounds are used individually as such or in a mixture or in mixtures with other fungicides and / or bactericides with aqueous media, e.g. B. dispersions, suspensions, emulsions and the like. Used or if they come into contact with such aqueous media after impregnation, it is found that the mentioned dithiocarbaminates and / or thiurams and their derivatives decrease in their biological effectiveness and this even completely can lose.

Surprisingly, it has now been found that the biological effectiveness of such fungicides and Bactericidal or combinations containing them very largely and in favorable cases even in full increased in the treatment and preparation with aqueous media in this itself in a manner not previously known can be if the active ingredients with orthophosphates and / or salts of condensed phosphoric acids or salt-like compounds with inorganic or organic groups, such as. B. hydrazine, hydroxylamine, Oxyquinoline, amines and others, individually or in a mixture together with water glass or in general with soluble or solubilized silicates of various types and / or other silicon compounds, such as silica, kieselguhr, colloidal silicas, silicones, esters of silicas and other derivatives of silicon.

It is of course also possible to add inert fillers, dispersants to the combination according to the invention and / or to add emulsifying agents.

The invention is intended to be based on the following examples, without restricting the scope of protection sought, explained:

Example t

100 g Cakiumoarbonat, 12Q ml water, 3 g cellulose egg, 0.3 g of graham salt, 0.1 g of dry sodium silicate and 0.1 g of TetHunethylthiuramdisulfid (TMTD) were added mixed and painted with this mixture test plates.

The fungicidal test of the above paint showed compared to comparative experiments! those with water glass and phosphates, but without TMTD and

»5 such identical paints with phosphates and TMTD, but carried out without silicate, have a significant preservation of the fungicidal effect of the according to the invention combination on the moist test plate during a week.

Table 1 summarizes the test and comparison results: '

Table 1
(Mean values of ten plates)

Age of

Paint

in hours

hours

hours

hours

Type of paint,
Composition in%

Cellulose glue paint
+ 0.4% phosphates
+ 0.1% sodium silicate
(without TMTD)

Cellulose glue paint
+ 0.4 "/" phosphates
- (- 0.1 »/" TMTD
(without silicate)

Cellulose glue paint
+ 0.3% phosphates
- (- 0.1 · /, Na-silicate
4-0.1% TMTD

Fungicides

stated fa

mmj distance

from, edge of

Test disc

j no effect

~> 12 mm

H W. rom

909 559/422

Another test consisted of using paints according to Example 1 in the same composition - with and without water glass additive - in the ready-to-use state before painting 30 days at normal Stored at room temperature.

The paints made afterwards were tested for their fungicidal effect and showed excellent results Wise the superiority of the additives according to the invention, as can be seen from Table 2.

Table 2
(Mean values of ten plates)

Age of
Paint

in days
before painting

Type of paint, composition in ° / "

Fungicides

Effect,

given in

mm distance

from the edge of the

Test disc

4 to 8 mm

20 to 22 mm

30. ■ Cellulose glue paint 0.4% phosphates 0.1% TMTD

30 cellulose glue paint

+ 0.3% phosphates + 0.1% sodium _{silicate + 0.1 o / o TMTD}

Example 2

An additive for soap, impregnation agent for textiles, bandages, packaging material, paper, wallpaper, Pulp and the like were prepared as follows: 250 mg sodium tripolyphosphate, 190 mg tetramethylthiuram disulfide and 25 mg of powdered sodium silicate were dry-mixed, then suspended with 50 ml of water and soaked paper foils with this solution.

The above means can also be used in the manufacture of paper, plastic, glue, leather and in manufacture are incorporated into them by other products. "A test of identically manufactured agents according to the example 2 - with and without the addition of water glass - showed after various storage times before the order that the Agents without added waterglass no longer had a fungicidal effect after 82 days, while that according to the invention compound agents still exhibited excellent fungicidal properties. Table 3 summarizes the results of these tests:

Table 3

Age of the ready to use

Means before
the use

ITag

5 days

21 days

30 days

82 days

250 mg phosphate mixture + 190 mg TMTD

Effective area in

mm distance from

Edge of the test disc

17.9
19.3

9.25
10.0

0.0

17.5

19.15

16.6

17.3

11.25

as occurs when sand (= SiO ₂ ) is fused with sodium carbonate, and 83.5 kg of sodium tripolyphosphate are ground together to form a powdery homogeneous product.

The above agent can be used in a wide variety of preparations, e.g. B. Soaps, detergents and dishwashing detergents, as a stabilized fungicidal and. bactericidal additive

be incorporated. - ^

It is particularly advantageous that even if

ίο traces of heavy metals, e.g. B. Kup * ft * f *% ei of the selected Compilation discoloration cannot occur, so that also a stabilization of the tetramethylthiuram disulfide is ensured against discoloration.

Paper or fiber pulp or other preparations to be protected against infestation by small organisms, Sludge and the like add 0.05 to 3% of the above agent.

250 mg phosphate mixture + 190 mg TMTD + 25 mg

Na silicate in

mm distance from

Edge of the test disc

ao

Example 4

97 kg of tetramethylthiuram disulfide are processed into a homogeneous paste with 3 kg of blood plasma powder and 201 of water. This slurry is preferably ^{dried under 30 °} C. in a vacuum.

The dry product obtained is first crushed and then with 10 kg of a phosphate glass melt, which has approximately the following composition: 50 parts of sodium pyrophosphate, 58 parts of sodium tripolyphosphate, 42 parts of a sodium polyphosphate mixture, the average composition of which corresponds to a sodium heptapolyphosphate, and 5 kg of a water glass melt product, such as this occurs when sand (SiO ₂ ) is fused with sodium carbonate and is ground together to form a powdery product.

The above ground product is very well suited to z. B. in soaps, detergents and dishwashing detergents, in paper pulps or other pulp slurries, pigments, sizes and other preparations, the stabilized thiuram finely dispersed and incorporated in a form that can be easily wetted with water.

45

Claims (3)

Patent claims: 1. Process for increasing the fungicidal and / or bactericidal action of compounds of the general formula : n - c-s - R, in which R ₁ and R ₂ each represent an aliphatic or aromatic radical or two members of a common ring and R _{3 is} a MetaU, an amine, a carbamate radical or a dithiocarbamate radical of the general formula ^: _S —C —N, Example 3 3.0 kg of tetramethylthiuram disulfide, 3.0 kg of dimethyldithiocarbamic acid tin, 0.5 kg of sodium tin (II) pyrophosphate, 10 kg of a water glass melt product, in which R ₄ and R _{6 represent} the meanings of R ₁ and R ₂ and their substitution products, characterized in that these compounds or their mixtures are orthophosphates and / 5 6 or salts of condensed phosphoric acids, as well as silicones and esters of silicic acids are added Adds derivatives of silicon. will. 2. The method according to claim 1, characterized 3. The method according to claim 1, characterized in that that the derivatives of silicon are water-soluble, that the mixtures contain suspending agents and / Silicates and / or kieselguhr, colloidal silicas, 5 or emulsifiers can be added. β 909 559/422 6.59