DE3604791A1 - Microbicidal composition - Google Patents

Abstract

Microorganisms can be controlled using individual active substances or combinations of active substances. Combinations of active substances are more effective if the joint use of the individual components shows synergism. Combinations of benzimidazolyl alkyl carbamates with substituted chloroacetamides show a synergistic effect in the control of microorganisms, in particular fungi and yeasts. They are specially suitable for the protection of industrial materials.

Description

The invention relates to a microbicidal agent, which contains a mixture of several active substances, and the use of this remedy.

It is known that N-phenyl-2-chloroacetamides are used as fungicides to protect industrial material such as paper, Wood, paint, rubber and plastic are used; these Fungicides are undiluted or together with an inert one organic solvents used (European Registration publication 01 37 729).

It is also known that combinations of active ingredients of benzimidazolylalkylcarbamates with different ones too Microbicidal substances for the protection of technical Anti-microbial materials are used; suitable substances are, for example, N-dimethyl-N'- phenyl (N'-fluorodichloromethyl-thio) sulfamide (German Laid-open specification 26 07 031 = British patent specification 15 42 829), tetramethylthiuramide sulfide (German Offenlegungsschrift 26 07 032 = British patent specification 15 39 706) and halomethylthiophthalimide (German Laid-open specification 26 07 033 = British patent specification 15 42 829). These drug combinations have the disadvantage that their stability with changes in pH is insufficient or that they are undesirable in colors Cause discoloration; they are therefore not unlimited applicable.

The object of the invention is to provide a microbicidal By means of a combination of active ingredients, which is a broad, especially compared to mushrooms and yeasts, has a balanced spectrum of activity and to protect technical materials against the influence of microorganisms suitable is.  

The invention relates to a microbicidal agent which is characterized by a content of an active ingredient combination consisting of (A) a benzimidazolyl-alkyl carbamate of the formula (1) in which R represents an alkyl radical with 1 to 4 carbon atoms, which is optionally substituted by the radical -OR ¹ , in which R ^{1 represents} an alkyl radical with 1 to 4 carbon atoms or a phenyl radical, and (B) a substituted chloroacetamide of the formula (2 ) in which X and Y are the same or different and each represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl radical with 1 to 4 carbon atoms or an alkoxy radical with 1 to 4 carbon atoms.

The weight ratio of active ingredients (A): (B) is preferably 1: 0.1 to 1:20 and in particular 1: 0.5 to 1:10.

The microbicidal agent according to the invention contains a benzimidazolyl alkyl carbamate of the formula (1) as active ingredient (A) in which R represents an alkyl radical with 1 to 4 carbon atoms, which is optionally substituted by the radical -OR ¹ , in which R ^{1 represents} an alkyl radical with 1 to 4 carbon atoms or a phenyl radical. Particularly suitable compounds are the lower alkyl esters of benzimidazolylcarbamic acid, namely the methyl, ethyl, isopropyl, n-propyl and n-butyl esters, and substituted benzimidazolylethylcarbamates, namely 2-methoxy, 2-ethoxy, 2 -Isopropoxy and 2-phenoxy ethyl esters. The active ingredients (A) are used either individually or in groups.

The benzimidazolyl alkyl carbamate is optionally used in the form of a sulfonic acid salt. The acid used for this has an ionization constant of more than 1.5 × 10 ^-5 ; alkanesulfonic acids having 12 to 18 carbon atoms, for. B. dodecanesulfonic acid, and alkylbenzenesulfonic acids having 12 to 18 carbon atoms in the alkyl radical, for. B. dodecylbenzenesulfonic acid. Benzimidazolylmethylcarbamate dodecylbenzenesulfonate is preferably suitable.

The active ingredient (B) in the microbicidal agent according to the invention is a substituted chloroacetamide of the formula (2) in which X and Y are the same or different and each represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl radical with 1 to 4 carbon atoms or an alkoxy radical with 1 to 4 carbon atoms. Suitable compounds are, for example, N-phenyl-2-chloroacetamide, N- (3,4-dichlorophenyl) -2-chloroacetamide, N- (2-chloro-5-methylphenyl) -2-chloroacetamide and preferably N- (4-bromo-acetamide 2-methylphenyl) -2-chloroacetamide.

The active ingredients (B) are either individually or in groups used.

The microbicidal agent is used in the usual way as a powder, Formulated solution or paste. The wording contains the microbicidal agent generally in an amount of 1 to 98 percent by weight, preferably 10 to 95 percent by weight, the remainder of the formulation being made up usual formulation aids, e.g. B. dispersants, Solvents, anti-caking agents, thickeners, Fillers and carriers.

A powdery formulation is made, for example, by grinding of the microbicidal agent with an inorganic Carrier manufactured. Particularly suitable as a carrier Aluminum silicate, clay, chalk, synthetic Silica and kaolin. The active ingredients (A) and (B) are here in the form of solid particles with diameters up to a maximum of 0.2 mm, preferably up to a maximum of 0.06 mm.

A solution is, for example, by dissolving an active ingredient (A) in the form of a sulfonic acid salt and an active ingredient (B) obtained in an alcohol ether as a solvent. Monoethers, in particular, the glycol suitable, e.g. B. ethylene glycol monomethyl ether, -monoethyl ether and -monoisopropyl ether.

A paste is made, for example, by dispersing the microbicidal agent in water with the addition of a dispersant produced. This serves as a dispersant especially hydroxyethyl cellulose, sodium hexametaphosphate and the ammonium salt of a low molecular weight polyacrylic acid.

The microbicidal agent according to the invention is extremely suitable to protect technical materials against the  Influence of microorganisms, especially fungi like Ulocladium consortiale, Aureobasidium pullulans, Aspergillus niger, Penicillium funiculosum, Chaetomium globosum, Cladosporium herbarum, Mucor spec., Paecilomyces varioti, Trichoderma viride, Verticillium glaucum and Sclerophoma pityophila and yeasts such as Torula utilis and Candida albicans.

The microbicidal effectiveness is determined by determining the minimal inhibitor concentration (MIC value) determined. The MIC value gives the lowest concentration of one Active ingredient or combination of active ingredients in which the growth of the test germ is still completely inhibited. For this purpose, graduated amounts of active ingredient are dissolved incorporated into culture media and the culture media become infected and then incubated. Within the scope of the invention will use a modified method of determining bacteriostatic Effect applied with the help of the dilution test (see guidelines for testing chemical disinfectants, Gustav Fischer Verlag, Stuttgart, 2nd edition, 1969, pages 5 and 6). A liquid serves as a breeding ground Malzagar-N medium, the homogeneous incorporation takes place at a temperature of 50 ° C, and the incubation is 2 weeks long at a temperature of 29 ° C. A comparison the MIC values of the active compound combinations according to the invention with those of the individual components results in one Synergism, calculated using the method of Kull (Applied Microbiology 9, 538-541) (1961)).

The following examples serve to explain the Invention. Percentages refer to the Weight.  

example 1

A mixture of 3 g benzimidazolylmethyl carbamate (BCM) and 7 g of N- (4-bromo-2-methylphenyl) -2-chloroacetamide (BPCA) were added dissolved in 990 g of dimethyl sulfoxide. The so received Formulation was used to determine the MIC value for various Test mushrooms used. For comparison, in the MIC values of the individual components BCM and BPCA determined.

The values are shown in Table 1 below.

Table 1

The existence of a synergism was calculated from the formula

QA means the MIC value for BCM in the combination, Qa the MIC value for BCM as a single active substance, QB the MIC value for BPCA in the combination and Qb the MIC value for BPCA as a single active substance. (There is synergism if X is less than 1.) The following values resulted:

X = 0.74 (Aspergillus niger)
X = 0.70 (Mucor spec.)
X = 0.70 (Ulocladium consortiale)

Example 2

A mixture of 20 g benzimidazolylmethyl carbamate dodecylbenzenesulfonate (BCMDBS) and 80 g BPCA were mixed in 900 g Dissolved ethyl glycol. The formulation so obtained was to determine the MIC value for various test mushrooms used. For comparison, the MIC Values of the individual components BCMDBS and BPCA determined.

The values are shown in Table 2 below.

Table 2

According to Example 1, the presence of a synergism calculated. The following values resulted:

X = 0.40 (Mucor spec.)
X = 0.44 (Ulocladium consortiale)

Example 3

A mixture of 333 g BPCA and 83 g BCM was mixed with 584 g Grind kaolin to a powder. The drug particles then showed diameters up to a maximum of 0.04 mm. The formulation thus obtained was in an amount of (a) 0.1%, (b) 0.5% and (c) 1% in three samples of one commercially available emulsion paint incorporated. For comparison were four more samples (d-g) of the emulsion paint in the same way with different amounts of pure BCM or pure BPCA.

250 g each of the samples obtained were placed on round filter papers deleted, and the coated filter papers were  Dried for 72 hours at a temperature of 20 ° C. The dried filter papers were placed on Malzagar-N media, previously with a culture of Ulocladium consortiale had been inoculated. After an incubation period of 14 days at a temperature of 29 ° C the degree of growth on the paint coats visually assessed.

The evaluation is shown in Table 3 below.

Table 3

Example 4

Example 3 was repeated with the modification that the Filter papers for 48 hours before placing on the culture media long leached in running water.

The evaluation is shown in Table 4 below.

Table 4

Example 5

10 g of hydroxyethyl cellulose were at a temperature of 75 ° C stirred in 478 g of water, and in the obtained homogeneous suspension were 10 g of sodium methhexaphosphate and 5 g of ammonium polyacrylate dissolved. In this suspension were 97 g in succession after cooling to room temperature finely ground benzimidazolyl (2-isopropoxy) ethyl carbamate (Particle diameter up to a maximum of 0.04 mm) and 400 g fine ground N- (3,4-dichlorophenyl) -2-chloroacetamide (particle diameter up to a maximum of 0.04 mm). The mixture was then stirred for a further 30 minutes, and it became one Get homogeneous, easy-flowing paste.

Claims (5)

1. Microbicidal agent, characterized by a content of an active ingredient combination consisting of (A) a benzimidazolyl alkyl carbamate of the formula (1) in which R represents an alkyl radical with 1 to 4 carbon atoms, which is optionally substituted by the radical -OR ¹ , in which R ^{1 represents} an alkyl radical with 1 to 4 carbon atoms or a phenyl radical, and (B) a substituted chloroacetamide of the formula (2 ) in which X and Y are the same or different and each represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl radical with 1 to 4 carbon atoms or an alkoxy radical with 1 to 4 carbon atoms. 2. Composition according to claim 1, characterized in that the Weight ratio (A) to (B) is 1: 0.1 to 1:20. 3. Means according to claim 1, characterized in that the Active ingredients (A) and (B) each in the form of solid particles with diameters in the range of 0.01 to 0.2 mm. 4. Use of the agent according to claim 1 for the protection of technical materials against the influence of microorganisms. 5. Process for combating microorganisms, thereby characterized in that an agent according to claim 1 in a effective amount applied to the materials to be protected becomes.