DE2607033C3 - Microbicidal agent - Google Patents

Description

wherein

R ^{1 is} an alkyl radical having 1 to 4 carbon atoms, which is optionally substituted ^{by the radical —OR 3,}

where R ^{3 is} an alkyl radical having 1 to 4 carbon atoms or the phenyl radical, and

R ² denotes hydrogen, an alkyl radical with 1 to 4 carbon atoms, halogen or the nitro group,

and dichloro-fluoro-methyl-thiophthalimide.

2. Microbicidal agent according to claim 1, characterized in that in the active ingredient combination to 1 part by weight of 2-benzimidazolyl alkyl carbamate 1 to 25 parts by weight of dichloro-fluoro-methyl-thiophthalimide omitted.

3. Use of active ingredient combinations according to claim 1 and 2 for the protection of technical materials against microwave degradation.

4. Use of active ingredient combinations according to claim 1 to 3 for adhesive and Paper preservation.

The present invention relates to new synergistic combinations of active ingredients from benzimidazolyl alkyl carbamates and dichloro-fluoro-methyl-thiophthalimide.

It is known to use benzimidazolyl alkyl carbamates as fungicidal agents for controlling a wide variety use of fungal diseases in plants without damaging the host (DE-OS 16 20 175). Likewise is known that halomethyl thiophthalimides such as trichloromethyl thiophthalimide and dichlorofluoromethyl thiophthalimide (paint + varnish 77, 888 to 890 [197!]) have a microbicidal effect.

However, these compounds are unsatisfactory in the individual application against microorganisms, since you The spectrum of activity is incomplete. A combination of active ingredients has already been selected to solve this problem Benzimidazolyl methyl carbamate and 3,5-dimethyl-tetrahydiO-1,3,5-thiadiazine-2-thione known (DE-AS 2t 50 219). Disadvantages of this known combination of active ingredients is that the 3,5-dimethyl-tetrahydro-1,3,5-Ihiailia / .in 2-ihion as a formaldehyde depot only moderately resistant isl and therefore light under environmental influences is dismantled.

It has been found that new combinations of active ingredients from beiizimidazolylalkylcarbamates of the formula

wherein

R ^{1 is} an alkyl radical having 1 to 4 carbon atoms which is optionally ^{substituted by the radical —OR J} , where R ^{3 is} an alkyl radical having 1 to 4 carbon atoms or the phenyl radical, and

R ² denotes hydrogen, an alkyl radical with 1 to 4 carbon atoms, halogen or the nitro group,

and dichloro-fluoro-methyl-thiophthalimide especially one have high microbicidal effectiveness.

Surprisingly, the microbicidal, in particular the fungicidal, effectiveness is that of the invention Active ingredient combination much higher than the sum of the effects of the individual active ingredients. So it lies a real synergistic effect and the active ingredient combinations represent a valuable enrichment of the Technology.

The synergistic effect of the active ingredient combination according to the invention is surprisingly greater than that of the mixture known from DE-OS 22 26 945 of benzimidazolylmethyl carbamate and N-trichloromethylthio-phthalimide.

κι alkyl radicals R ¹ —R ² can be straight-chain or branched hydrocarbon radicals such as. B. the methyl, ethyl, propyl, iso-propyl, butyl or iso-butyl radical, especially the methyl radical, be.

Halogens R ² can be fluorine, chlorine, bromine or iodine, especially chlorine.

For example, the following are benzimidazolyl alkyl carbamates called:

Benzimidazolyl methyl carbamate,
4-methyl-beiizimidazolylmethylcarbamate,
M) 5-methyl-benzimidazolylmethylcarbamate,
Benzimidazolyl ethyl carbamate,
4-methylbenzimidazolylethyl carbamate,
5-ethylbenzimidazolyethylcarbamate,
Benzimidazolyl iso-propyl carbamate,
Ί5 4-ethylbenzimidazolyl-iso-propyl-

carbamate,
5-methyl-benzimidazolyI-iso-propyl-

carbamate,

4-propyl-benzimidazolyl-iso-propylcarbamate,

4-butyl-benzimidazolyl-iso-propyl-

carbamate,
4-ibo-butyl-benzimidazolyI-iso-propyl-

carbamate,

Benzimidazolyl methoxy ethyl carbamate,

4-methyl-benzimidazolyl-methoxy-ethyl-

carbamate,
5-methyl-benzidmidazolyl-methoxy-ethyl-

carbamate,

bo benzimidazolyl-ethoxy-ethyl-carbamate,

Benzimidazolyl-propoxy-ethyl-carbamate,
Benzimidazolyl-phenoxy-ethyl-carbamate,
4-methyl-benzimidazolyl-phenoxy-ethyl-

carbamate,
M 5-methyl-benzimidazolyl-phenoxy-ethyl-

ciirbamat.

The preferred benzimidazolyl alkyl carbamate is benzimidazolyl methyl carbamate.

It is always possible to use mixtures of different Use Benzimidazolylalkylcarbamaie.

The preparation of the benzimidazolylalkyl carbamates is already known (US Pat. No. 3,010,968).

The production of dichloro-fluoro-methyl-thiophthalimide can be done according to US-PS 32 85 929.

The weight ratios of the active ingredient groups in the active ingredient combinations can be relatively large Areas fluctuate. In general there are 1 to 25 per part by weight of benzimidazolyl alkyl carbamate Parts by weight, preferably 2 to 12 parts by weight, dichloro-fluoro-methyl-thiophthalimide

The particle size of the active ingredients according to the invention can be varied within wide limits. In general active ingredients with a particle size of 100 to 350 microns, preferably 150 to 300 microns, used.

Combinations of 1 part by weight of benziniidazolyl methyl carbamate and 2 to are particularly effective 10 parts by weight of dichloro-fluoro-methyl-thiophthalimide.

The active ingredient combinations according to the invention have a strong effect on microorganisms. Fungi, yeast and algae may be mentioned as microorganisms, for example.

Examples of fungi and yeasts that may be mentioned are: Penicillium glaucum, Rhizopus nigricans, Asperigillus niger, Pullularia pullulans, Alternaria tennis, Torula utilis, Candida crusei, and Candida albicans.

Examples of algae are: Phaeodactylum tricornutum Bohlin, Euglena gracilis Klebs, Oscillatoria geminata Meneghini Stichococcus bacillaris Naegili.

The invention relates to an active ingredient combination for protecting industrial materials against microbial degradation. Technical materials are e.g. B. adhesives, glues, papers and cannons, textiles, Leather, HoU, paint, plaster and container contents that are damaged by microbial effects or can be destroyed. The active ingredient mixture according to the invention is particularly useful for adhesive, textile and paper conservation.

The new active ingredient combinations can be converted into the usual formulations, such as. B. Solutions, suspensions, pastes and powders.

The new active ingredient combinations can be used as such in the form of their formulations and that of them prepared application forms are used. It is used in the usual way, for. B. by homogeneous distribution in the material to be protected, by impregnation. Coating or spraying technical materials.

The amount of active ingredient combinations used depends on the type and occurrence of the microorganisms, the number of germs and depending on the medium. The optimal amount can be used in the application can be determined in each case by test series. In general, however, it is sufficient to add 0.1 to 1.0 parts of the Use active ingredient mixture.

The active ingredient combinations according to the invention preferably have a broad spectrum of activity. The concentrations of the substances according to the invention occurring in wastewater when used properly Combinations of active ingredients do not interfere with the biological clarification.

The active ingredient combinations according to the invention advantageously enable those previously available to replace microbicidal agents with more effective ones and those necessary to combat microorganisms Reduce the amount of biocide.

Examples 1 and 2
Testing for mold resistance of paints

The test is based on Report 219 of Defense Standards Laboratories Maribyrnong / Australia Carried out as follows: A smooth cardboard box is coated on both sides with the product to be tested and

κι 8 days at room temperature, dried to aging is a part of the painting soaked for 24 hours in running water of 24 ° or ventilated 8 days fresh air of 40 to 60 ⁰ C or exposed to 110 hours in a dry Xenon test. Of the so prepared

If samples are taken, sections of 5 χ 5 cm are individually in Petri dishes are placed on a dextrose medium and filled with a spore suspension of the following Fungi contaminated: Aspergillus niger, Pullularia pullulans, Alternaria speciales, Penicillium citrinum,

Stachybotrys atra, Paecilomyces varioti, Cladosporium herbarum, Aspergillus ustus and Aspergillus flavus.

The contaminated dishes are stored at 28 to 3O ⁰ C and 90 to 95% RH and evaluated after 3 weeks. Paintings are considered

mold-resistant if the samples remain free of fungi after these tests.

example 1

According to the test method given above, such a commercially available paint based on alkyd resin is applied Mold resistance tested. To demonstrate the synergistic effect of the active ingredient mixture according to the invention the paint color (a) with 0.075% benzimidazolylmethyl carbamate (hereinafter called BCM), and j-> (b) with 0.198% dichlorofluoromethyl thiophthalimide (hereinafter referred to as DCFP) and (c) with 0.273% des according to the invention (consisting of 0.075% BCM and 0.198% DCFP) added (each based on film weight). The individual active ingredients are previously • κι test solved in the paint.

The following assessment results after the test:

BCM

DCFP

BCM + DCFP

Assessment of fungal infestation Fungal infestation no fungal infestation

The result of the test is independent of the individual exposure to aging of the paintwork.

The paint requires, based on the film weight, an addition of 1.5% dichlorofluoromethyl-ihiopluhalimid, if fungus formation of the paint film is to be prevented. If only benzimidazolyl methyl carbamate is added as the active ingredient of the paint, you need 0.8% benzimidazolylmethylcarbamate, based on the solids content to avoid fungus growth.

From these figures, for the inventive Combination of active ingredients to determine a synergism. According to KuIl (Applied Microbiology 9, 538 to 541 [196I]) the following relationship applies:

Qa ,

Qa

Qn

= X

X = 1 means additivity
X => 1 means antagonism
X = <1 means synergism

0.8 = Q, 1.5 = Whether 0.075 - Qa

0.198 = Qb

Concentration of BCM that provides a mold-resistant coating.
Concentration of DCFP that provides a mold-resistant coating.
Amount of BCM in the mixture according to Example I ₁ dis provides a mold-resistant paint
Amount of DCFP in the mixture according to Example 1, which provides a mold-resistant paint.

This results in X
Synergism).

0.23 (that means

Example 2 (comparative example) _{] 3}

According to the above test method, a commercially available paint based on alkyd resin is applied Mold resistance tested. To demonstrate the synergistic effect of the active ingredient mixture according to the invention the paint (a) with 0.15% Benzimidazoiylmethylcarbamat (hereinafter referred to as BCM), (b) with 0.396% trichloromethyl thiophthalimide (hereinafter Called TCP) and (c) with 0.546% of the active ingredient mixture according to the invention (consisting of 0.15% BCM and 0.396% TCP), based on the solid gel age, added. The individual active ingredients are in the Paint color solved.

The test gives the following assessment:

BCiM

TCl '

BCM + TCl '

30th

Assessment of fungal infestation Fungal infestation no fungal infestation

The paint requires the addition of 2% trichloromethyl thiophthalimide if the fungus causes the Paint film should be prevented.

For the active substance mixture used in Example 2, a synergism of only X = 0.39 is calculated in an analogous manner.

Example 3

In a paper pulp (consistency 1%, pH value 4.8) of the following composition:

39.9% bleached sulphite pulp "5

39.9% bleached birch sulphate pulp

0.2% of a commercially available brightener
2% of a commercially available resin glue
15% clay
3% alum

based on paper weight (90 to 100 g / m ² ) 0.4% BCM / DCFP - 1/6 are homogeneously distributed. The paper made from this pulp is extremely mold-resistant; the pulp control system remains slime-free during papermaking, so that the use of other slime control agents is unnecessary.

The mold resistance of the paper is checked as follows: Round paper specimens (diameter 4 cm) are placed in Petri dishes on a nutrient medium that has previously been infected with the test fungi (Trichoderma viride, Chaetomium globosum Kunze, Aspergillus niger, Alte.-naria tenuis). After 8 to 14 days storage at 30 ⁰ C and 90 to 95% relative humidity active substance-free paper is completely overgrown with the test fungi, while the paper prepared as mentioned above is free from fungi even under these extreme conditions.

On the other hand, adding 1% BCM or 1% DCFP (based on the weight of the paper) does not result in paper that is resistant to mold. According to KuIl (see Example 1), a synergism is calculated as X = 0.40.

Example 4

Commercially available wallpaper base paper is coated with a starch glue which, based on dry glue, contains 0.25% BCM / DCFP = 1/9. Paper weight 80 g / m ² . Adhesive layer 8 g / m * (after drying). The self-adhesive wallpaper base paper produced in this way is - as the following test shows - mold-resistant.

Test specimens (diameter 4.5 cm) are placed on agar culture media in Petri dishes, which are previously infected with molds (including Trichoderma viride, Chaetoniium globosum Kunze, Aspergillus niger, Alternaria tenuis) isolated from moldy and spoiled wallpaper. After one-week storage at 30 ⁰ C and 90 to 95% relative humidity the test specimens are still free from fungi. Kin wallpaper base paper with an active ingredient-free adhesive layer is completely overgrown by the test fungi under the same conditions during this time.

Claims (1)

Patent claims: 1- Benzimidazolylalkyl carbamate-based microbicidal agent and rialogenmethyl-thiophthali- ί miden, characterized by a salary on a combination of active ingredients consisting of a benzimidazolyl alkyl carbamate of the formula