DE2607030A1 - Antimicrobials for paints, paper and adhesives - contg. benzimidazole carbamate, tetramethyl-thiuram disulphide and (1)-methylol-(2)-thiono-(1,2)-dihydro-benzthiazole - Google Patents

Abstract

New microbicidal agents contain a combination of (a) a benzimidazole deriv. of formula (I): (where R' is 1-4C alkyl opt. substd. by a residue OR3, R3 being 1-4C alkyl or phenyl; and R2 is H, 1-4C alkyl, halogen or NO2); (b) tetramethylthiuram disulphide (II); and (c) 1-methylol-2-thiono-1,2-dihydro-benzothiazole (III). New combinations have high microbicidal activity which, esp. fungicidal activity, is substantially higher than the sum of the activities of the individual components. The combinations are active against e.g. bacteria, fungi, yeasts and algae. Compsn. pref. contains 5-15 wt. parts (II) and 0.5-5 wt. parts (III) per weight part (I). The pref. compound (I) is methyl 2-benzimidazolecarbamate.

Description

Microbicidal agent

The present invention relates to new synergistic combinations of active ingredients from benzimidazolylalkyl carbamates, tetramethylthiuram disulfide and 1-methylol-2-thiono-1 , 2-dihydrobenzthiazole.

It is known to use benzimidazolyl alkyl carbamates as fungicidal agents to combat a wide variety of fungal diseases in plants without damage of the host (DOS 16 20 175). Tetramethylthiuram disulfide is also known to be used as a means of combating microorganisms (Federal Health Gazette 14, No. 6/7, pages 83 to 86 (1971) and Verfkronik 47, pages 98 and 99 (1974)). The use of 1-methylol-2-thiono-1, 2-dihydrobenzthiazole as a microbicide is from DT-OS 22 01 457 known.

However, these compounds are used individually against microorganisms unsatisfactory, as their spectrum of activity is incomplete. To solve this problem is already an active ingredient combination of benzimidazolyl methyl carbamate and 3,5 dimethyl tetrahydro-I 3, 5-thiadiazin-2-thione known (DAS 21 50 219). Disadvantage of this known The combination of active ingredients is that the 3,5-dimethyl-tetrahydro-1,3,5-thiadiazin-2-thione is only moderately stable as a formaldehyde depot and is therefore subject to environmental influences is easily degraded.

It has been found that new combinations of active ingredients from benzimidazolylalkyl carbamates of the formula wherein R1 is an alkyl radical having 1 to 4 carbon atoms, which is optionally substituted by the radical -oR3, where R3 is an alkyl radical having 1 to 4 carbon atoms or the phenyl radical, and R2 is hydrogen, an alkyl radical having 1 to 4 carbon atoms, halogen or the Nitro group mean, tetramethylthiuram disulfide and 1-methylol-2-thiono-1,2-dihydrobenzthiazole have a particularly high microbicidal activity.

Surprisingly, the microbicidal, especially the fungicidal, Effectiveness of the active ingredient combinations according to the invention is significantly higher than that Sum of the effects of the individual active ingredients. So there is a real synergistic one Effect before. The active ingredient combinations represent a valuable addition to the technology represent.

Alkyl radicals R1, R2 and R3 can be straight-chain or branched hydrocarbon radicals such as the methyl, ethyl, propyl, iso-propyl, butyl or isobutyl radical, in particular the methyl radical.

Halogens R2 can be fluorine, chlorine, bromine or iodine, especially chlorine, be.

The following benzimidazolylalkyl carbamates may be mentioned as examples: Benzimidazolylmethylcarbamate, 4-methylbenzimidazolylmethylcarbamate, 5-methylbenzimidazolylmethylcarbamate, Benzimidazolyl ethyl carbamate, 4-methyl benzimidazolyl ethyl carbamate, 5-ethyl benzimidazolyl ethyl carbamate, Benzimidazolyl iso-propyl carbamate, 4-ethyl benzimidazolyl iso-propyl carbamate, 5-methyl-benzimidazolyl iso-propyl carbamate, 4-propyl-benzimidazolyl-iso-propylcarbamate, 4-butyl-benzimidaoly1-iso-propylcarbamate, 4-iso-butyl-benzimidazolyl-iso-propylcarbamate, benzimidazolyl-ethyl methoxy-carbamate, 4-methyl-benzimidazolyl-ethyl methoxy-carbamate, 5-methyl-benzimidazolyl-ethyl methoxy-carbamate, Benzimidazolyl ethyl ethoxy carbamate, benzimidazolyl ethyl propoxy carbamate, benzimidazolyl ethyl phenoxy carbamate, 4-methyl-benzimidazolyl-ethylphenoxy-carbamate, 5-methzimldazolylphenoxy-carbamate.

The preferred benzimidazolyl alkyl carbamate is benzimidazolyl methyl carbamate.

It is also possible to use mixtures of different benzimidazolyl alkyl carbamates to use.

The preparation of the benzimidazolylalkyl carbamates is already known (U.S. Patent 3,010,968).

The active ingredient tetramethylthiuram disulfide can according to Ber. German

chem. Ges. 35, 820 (1902).

The production of the active ingredient ti -Methylol-2-thiono-1,2-dihydro-bEhiazole is from J.Chem.Soc. London 1948, known 1717.

The weight ratios of the active ingredient groups in the active ingredient combinations can fluctuate in relatively large areas.

In general, there are one part by weight of benzimidazolyl alkyl carbamate 5 to 15 parts by weight, preferably 6 to 12 parts by weight, of tetramethylthiuram disulfide and 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight of 1-methylol-2-thiono-1 , 2-dihydrobenzthiazole.

Combinations of 1 part by weight of benzimidazolyl methyl carbamate are particularly effective, 8 to 10 parts by weight of tetramethylthiuram disulfide and 2 to 5 parts by weight of 1-methylol-2-thiono-1,2-dihydrobenzene.

The particle size of the active ingredients according to the invention is within wide limits variable. In general, active ingredients with a particle size of 100 to 350 are used Microns, preferably from 150 to 300 microns.

The active ingredient combinations according to the invention have a strong killing effect or inhibitory to microorganisms. Examples of microorganisms are bacteria, Called mushrooms, yeasts and algae.

Examples of bacteria that may be mentioned are: Bacterium coli, Bacterium fluorescens, Bacterium subtillis, Bacterium punctatum, Bacterium proteus vulgare, Pseudomonas aeruginosa, Bacterium mycoides, Aerobacter aerogenes.

Examples of fungi and yeasts include: Penicillium glaucum, Rhizopus nigricans, Aspergillus niger, Pullularia pullulans, Alternaria tenius, Torula utilis, Candida crusei, Candida albicans.

Examples of algae are: Phaeodactylum tricornotum Bohlin, Euglena gracilis Klebs, Oscillatoria geminata Meneghini and Stichococcus Bacillaris Naegili.

The invention relates to an active ingredient combination for the protection of technical Materials against microbial degradation. Technical materials are e.g. adhesives, Glues, paper and cardboard, textiles, leather, wood, paint materials, plasters and aqueous formulations susceptible to microbial degradation.

The active ingredient mixture according to the invention is particularly suitable for painting, Suitable for adhesive and paper preservation.

The new active ingredient combinations can be used in the usual formulations such as solutions, suspensions, pastes and powders.

The new active ingredient combinations can be used as such or in the form of their Formulations and the application form prepared therefrom are used. the It is used in the usual way, e.g. through homogeneous distribution in the area to be protected Material, by impregnating or coating or spraying technical materials.

The amount of the active ingredient combination used depends on the type and the occurrence of the microorganisms, the number of germs and the medium. the The optimum amount used can be determined in each case by means of a series of tests will. In general, however, it is sufficient from 0.05 to 1.5% of the active ingredient mixture to use. The active ingredient combinations according to the invention advantageously have a broad spectrum of activity.

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

Examples 1 and 2 Testing for Mold Resistance of Paints The Testing is based on Report 219 of Defense Standards Laboratories Maribyrnong / Australia Carried out as follows: A smooth cardboard box is placed on both sides with the one to be tested Painted product and dried for 8 days at room temperature.

Part of the paintwork is exposed to fluid for 24 hours in order to age Watered with water at 240C or aerated with fresh air from 50 to 60 ° C for 8 days or Subjected to a dry xenon test for 110 hours. From the samples prepared in this way sections of 5 x 5 cm are placed individually in Petri dishes on a dextrose agar culture medium and contaminated with a spore suspension of the following fungi: Aspergillus niger, Pullularia pullulans, Alternaria speciales, Penicillium citrinum, Stachybotrys atra, Paecilomyces varioti, Cladosporium herbarum, Aspergillus ustus and Aspergillus flavus.

The contaminated dishes are at 28 to 300C and 90 to 95 96 relative humidity and evaluated after 3 weeks. Coatings apply as mold-resistant if the samples remain free of fungi after these tests.

Example 1 Following the test method given above, a commercially available Emulsion paint tested for mold resistance. To demonstrate the synergistic Effect of the active ingredient mixture according to the invention is the emulsion paint (a) with 0.17% benzimidazolyl methyl carbamate (hereinafter called BCM), (b) with 1.0496 Tetramethylthiuram disulfide (hereinafter referred to as TMTD), (c) with 0.17% 1-methylol-2-thiono-1 , 2-dihydrobenzene (hereinafter called MTBT) and (d) with 1.38 96 of the invention Mixture of active ingredients (consisting of 0.17% BCM, 1.04 5 'TMTD and 0.17% MTBT) added (each based on total solids content). The individual active ingredients are with rubbed into the emulsion paint.

The following assessment results after the test: BCM 1 TMTD i T | BCM + TMTDsMTgT Assessment 1 fungal infestation 1 fungal infestation 1 fungal infestation ß no fungal infestation The result of the test is independent of the individual exposure to aging of the emulsion paint coatings.

Example 2 The above test method is a commercially available Emulsion paint tested for mold resistance. To demonstrate the synergistic Effect of the active ingredient mixture according to the invention is the emulsion paint (a) with 0.095% BCM, (b) with 1.06% TMTD, (c) with 0.19% MTBT and (d) with 1.35% des Active ingredient mixture according to the invention (consisting of p, C95% BCM, 1.06% TMTD and 0.19% MTBT) based on the solids content.

The individual active ingredients are rubbed in with the emulsion paint.

The test gives the following assessment: BCM I TMTD r MTBT BCM + TMTD + MTBT Assessment of fungal infestation Fungal infestation 1 Fungal infestation no fungal infestation Example 3 Calculation of the synergism A commercially available emulsion paint requires an addition of 3% TMTD or 4.5% BCM or 5% MTBT, based on the total solids content, if it is to provide paint films whose mold resistance is comparable to that of the paint films produced using the active ingredient combinations according to the invention according to Example 1 or 2 reaches. A synergism for the active ingredient combinations according to the invention can be determined from these figures. According to Kull (Applied Microbiology 9, 538 to 541 (1961) the following relationship applies: QA QB QC - + - + - = X Qa Qb Qc X = 1 means additivity X => 1 means antagonism X = <1 means synergism = a Qa = Concentration of BCM that provides a mold-resistant coating.

3 = Qb = concentration of TMTD that makes a mold-resistant paint supplies.

5 = Qc = concentration of MTBT, which is a mold-resistant paint supplies.

0.17 = QA = amount of BCM in the mixture according to Example 1, the one Mold-resistant paint supplies.

1.06 = QB = amount of TMTD in the mixture according to the example, the one Mold-resistant paint supplies.

0.17 = QC = amount of MTBT in the mixture according to Example 1, the one Mold-resistant paint supplies.

This results in X = 0.42 (that means synergism).

For the active substance mixture used in Example 2, the calculation is made in an analogous way a synergism of X = 0.41.

Example 4 In a paper pulp (consistency 1 5 ', pH 4.8) the following composition: 39.9% bleached sulphite pulp 39.9% bleached Birch sulphate pulp 0.2% commercial brightener 2% commercial resin glue 15 96 Clay 3% alum is based on paper weight (90 to 100 g / m2) 0.5% BCM / TMTD / MTBT = 1/10/5 homogeneously distributed. The one made from this pulp Paper is mold resistant; the pulp guidance system remains during the papermaking process Mucus-free, so that the use of other mucus 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, who previously used the test mushrooms (Trichoderma viride, Chaetomium globosum Kunze, Aspergillus niger, Alternaria tenuis) becomes infected. After 8 to 14 days Storage at 30 ° C and 90 to 95% relative humidity does not contain any active ingredients Paper completely overgrown by the test fungi, while the one prepared as stated above Paper remains fungus-free even under these extreme conditions.

Example 5 A commercial wallpaper base paper is made with a starch glue coated, which, based on the dry glue, 0.3% of an active ingredient mixture consisting of BCM. Contains TMTD and MTBT in a ratio of 1: 9: 1. Paper weight 80 g / m2. Adhesive layer 8 g / m2 (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 that have previously been filled with mold (Trichoderma viride, Chaetomium globosum Kunze, Aspergillus niger and Alternaria tenuis) isolated from moldy wallpaper. After a week The test items are still stored at 300C and 90 to 95 96 relative humidity fungus free. A wallpaper base paper with an active ingredient-free adhesive layer is used under under the same conditions during this time completely overgrown by the test fungi.

Claims (4)

Patent claims: 1. Microbicidal agent, characterized by a content of an active ingredient combination consisting of 2-benzimidazolyl-alkyl carbamate of the formula wherein R1 is an alkyl radical with 1 to 4 carbon atoms, which is optionally substituted by the radical -OR3, where R3 stands for an alkyl radical with 1 to 4 carbon atoms or the phenyl radical, and R2 is hydrogen in the alkyl radical with 1 to 4 carbon atoms, halogen or the nitro group mean tetramethylthiuram disulfide and 1-methylol-2-thiono-1,2-dihydrobenzthiazole. 2. microbicidal agent according to claim 1, characterized in that in the active ingredient combination to one part by weight of 2-benzimidazolyl alkyl carbamate 5 to 15 parts by weight of tetramethylthiurand disulfide and 0.5 to 5 parts by weight of 1-methylol-2-thiono-1,2 no dihydrobenzthiazole. 3. Use of active ingredient combinations according to claim 1 and 2 for Protection of technical materials against microbial degradation. 4. Use of active ingredient combinations according to claim 1 to 3, for Paint, glue and paper preservation.