NO130713B - - Google Patents

Description

Poly-chloro-benzimidazoles for use as microbicide agents against material-damaging micro-

organisms.

The present invention relates to new, microbicidal agents for combating microorganisms that damage or decompose organic materials and objects of use when using these agents, respectively the active substances or mixtures of active substances contained therein, as well as the materials and objects of use protected by treatment with these active substances and agents . In particular, the invention relates to microbicidal agents for combating microorganisms that damage or decompose cellulose and cellulose-containing materials as well as damage of any kind.

For the protection of organic materials, a number of microbicides Cfr. at 38h-2/01 active substances have become known, of which a large amount does not completely satisfy the requirements. Thus, e.g. those for combating fungal species that damage or decompose cellulose and cellulose-containing materials are mostly phenols, especially pentachlorophenol, or trialkyltin oxides, especially tributyltin oxide, only of limited use due to their properties, such as e.g. the high vapor pressure, their unpleasant odor, the lack of lightfastness, etc. These active substances do indeed have a broad spectrum of effects, but the duration of their effects is not satisfactory. Benzimidazoles substituted in the benzene nucleus with one or more chlorine atoms have so far been described as herbicidal active substances, as pesticidal active substances and as active substances for combating keratin-eating insects (see Swiss patent no. V+3,777).

Surprisingly, it has now been found that agents which as active ingredient contain at least twice chlorinated 2-chloro-benzimidazole in the benzene nucleus or mixtures of such polychloro-benzimidazoles are excellently suitable for combating microorganisms that decompose or damage organic materials and objects of use. The active substances and/or mixtures of active substances contained in the new agents inhibit and prevent the growth of bacteria, fungi and yeast species, especially, however, of fungi and bacteria that decompose and damage cellulose and cellulose-containing materials and infections of all kinds. These polychlorobenzimidazoles have a broad effective spectrum, are largely stable against humidity and exposure to light, have a very good affinity for the materials mentioned and a long-lasting effect. Due to these properties as well as their low vapor pressure associated with the good light stability and their lack of smell, these new agents are particularly suitable as microbicidal additives for paint colors of all kinds, such as colors on the most diverse bases, varnishes, varnishes, wallpapers , wood and wood materials and textiles of all kinds.

The poly-chloro-benzimidazoles that are used as active substances for the protection of cellulose-based and cellulose-containing materials and wooden objects of use against attack by material-damaging microorganisms are. 2,5,6-trichloro-henzinidazole-, 2,-4,0,6-tetrachloro-benzimidazole, 2,4 , o,6,7-pentachloro-ber.zir;andazole or combinations thereof.

By a preferred. according to the invention, these are preferably used in the following special composition:

A. h2', 6% 2, 5,6-trichloro-benzimidazole

29.7% 2,<>>+,5,6-tetrachloro-benzimidazole 27.7% 2,U,5,6,7-pentachloro-benzimidazole;

B. 61.8% 2,!+, 5,6,7-pentachloro-benzimidazole

33.8% 2,^,5,6-tetrachlorobenzimidazole

h, h% 2,5,6-trichloro-benzimidazole.

The preparation of these compounds is known from the Swiss patent No. ^U-3,777. Likewise, the preparation of the individual components as well as of mixture A by chlorination of 2-mercapto-benzimidazole in water is described there. According to an improved method, mixtures A and B are obtained by chlorinating 2,5-dichlorobenzimidazole in the presence of ferric chloride in glacial acetic acid with the addition of a base. When carrying out the method, the addition of chlorine is interrupted several times and the acidity of the reaction mixture is reduced by adding a base, such as sodium acetate. The chlorination practically remains at the stage for mixtures A and B. With fractional crystallization, the two mixtures can be separated from each other. The mixtures have uniformly good melting points and their composition has been determined using gas chromatograms.

When using the new agents, the treated materials receive an excellent microbicidal device. As the active substances are odorless, they are particularly suitable for treating materials that are in closed spaces, such as wood, paper, stains of any kind, etc. Treated materials, such as paper, showed no discoloration after prolonged exposure . The polychlorobenzimidazoles are practically non-volatile towards tributyltin oxide. At 90°C and 16 days of storage, the weight loss for tributyltin oxide amounts to approx. 3^+%? while the weight loss for polychlorobenzimidazole mixture A, on the other hand, only amounts to 0.w%.

The agents according to the invention are suitably concentrates of active substances, which are either liquid (solutions, emulsifiable concentrates) or paste-like. The concentrates can be diluted to the required concentration shortly before use. As the active substances are soluble in organic solvents, they are suitable for non-aqueous applications. The polychlorobenzimidazoles form salts with alkali metal ions and can therefore also be applied from aqueous dispersions or solutions. The treatment of wood and wood materials with the new means is thereby significantly simplified.

In order to determine the bactericidal and fungicidal effect of the polychlorobenzimidazoles used according to the invention, the following experiments were carried out:

1. Width of effect.

The solution of active substance is mixed with the still warm nutrient agar. The agar is then solidified into plates and, after solidification, the test cells are added.

The following microorganisms were used:

A. Bacteria

Escherichia coli, Bacillus pumilus, Sarcina ureae, Bacillus subtilis, Sarcina lutea, Streptococcus faecalis, Staph saproph., Staph.. aureus, Corynebact. diphtheroides 17, Brevibact. am.monia-genes, Salmonella pullorum, Proteus valgåris HXL, Proteus vul-garis ox 1°, Proteus mirabilis.

B. Mushrooms.

let. Aspergillus niger, Penicillium italicum, Fusarium oxysporum,

Candida albicans, Stemphylium botryosum.

lb. Cellulose decomposer: Chaetomium globosum, Trichoderma viride,

Metarrhizium glutinosum, Stachybotrys atra.

2. Yeast species: Saccharomyces cerevisiae, Torula utilis, Monilia nigra. 3. Dermatophytes: Trichopyton gypseum, Ctenomyces Spee, Keta-tin-omyces ajelloi,- Epidermophyton flossosum. <1>+. U bicuitary saprophytes: Rhizopus nigricans, Paeeilomyces varioti, Penicillium citrinum, Aspergillus oryzae, Aspergillus clavatus, Aspergillus flavus. 5. Fungi imperfecti: Scopulariopsis brevicaulis, Alternaria tenuis, Acro-stalagmus cinnabarinus. 6. House rot: Coniophora cerebella, Poria vaporaria, Poria incarnata. 7. Stock rot: Polystitus versicolor, Daedalea quericina, Lenzites tes abietina, Lentinus lepideus.

8. Parasites: Fornes annosus.

9. Tree miscolours: Scopularia phycomyces, Pullularia pullulans.

In the following compilation, the nutrient base, incubation temperature and time as well as the concentrations of active substance used for the various organisms are reproduced:

B judgment:

The limit concentration that inhibits the growth of the various microorganisms is determined.

In the following table 1, the bacteriostatic effect and in table 2 the fungistatic effect of the polychlorobenzimidazoles against some of the microorganisms listed above are listed.

(The numerical values mean the limit concentrations in ppm.).

As active substance was used:

1. 2,556-Trichloro-benzimidazole

2. 2, h,5,6,7-pentachloro-benzimidazole

3. mixture A: ^2.6% 2,5,6-trichloro-benzimidazole 29.7% 2,h,5,6-tetrachloro-benzimidazole and

27.7% 2,14-, 5,6,7-pentachloro-benzimidazole.

h. 2, h,5,6-tetrachloro-benzimidazole

5. mixture B: 61.8% 2,*f, 5,6,7-pentachloro-benzimidazole

33.8% 2,*+,5,6-tetrachloro-benzimidazole and

<l>+,<1>f% 2, 5,6-trichloro-benzimidazole.

6. 2-oxy-3' j 5' ,6-tetrachloro-2-phenyl-benzimidazole (known from DP 888 032)

2. Inhibition zone prdve.

In the extraction or Foulard method, active substances from solutions with different contents of active substance are applied to paper discs. Ethylene glycol monomethyl ether was used as the solvent here. So-called 2-layer agar plates are used as nutrient agar. These consist of a layer of bacto-agar and a layer of the agar suitable for the corresponding test organisms. This second plate is inoculated in advance with the seeds. The discs diluted with active substance are then placed on these plates and cultured for 2<*>4 hours at 37°C. The growth of the fungal organisms on and under the rondels is then assessed."

The following organisms were used as test organisms:

Bacteria: Staphylpcoecus aureus SG 511 (nutritional agar +

potassium tellurite) Eschericia coli (nutrient agar

Fungi: Aspergillus niger (redtter agar)

Candida albicans (redtter agar)

In the table means:

inactive = vegetation equivalent to the control

+•+ weakly active = 25-30% of the control's vegetation + totally active = no vegetation.

3. Disinfection sample.

In the extraction method (Foulard), the active substances from solutions with different contents of active substance are applied to paper discs. These test bodies are then inoculated with suspensions (physiological saline solution with 10% broth content) of the various test organisms. The rondels are then cultured in a moist chamber for 2 hours at 37°C and then washed out in 20 cw} of physiological sodium chloride solution (containing for blocking the active substance polyoxyethylene sorbite mono-oleate). Aliquot portions are taken from this solution and distributed on suitable nutrient bases. The nutrient bases are then cultured for 2 hours at 37°C. As test organisms, those mentioned under 2 were used. The number of live germs was then determined in comparison with the control.

In the following table means:

inactive = vegetation equivalent to the control

++ weakly active = 25-30% of the control's vegetation

•r++ total effective no vegetation.

h. Effect of urea-degrading microorganisms.

A paper disc is inserted into one of two interconnected powder bottles and inoculated with a germ suspension consisting of liquid urea nutrient medium and urea-decomposing bacteria. 0.1 N hydrochloric acid is introduced into the second bottle. The bottles are then cultured for 3 days at 28°C on a rolling device. The quantity of ammonia produced by the breakdown of urea is then determined on the basis of the pH shift. The following test organisms were used:

Brevibacterium ammoniagenes

Proteus 0X 19.

The polychlorobenzimidazoles according to the invention prevent the growth of such bacteria in concentrations of 0.05 and 0.1%. No change in the pH value for 0.1 N hydrochloric acid with absorbed ammonia could be determined.

5. Cane stain sample

On a sterile Wort-agar plate, paper discs are placed on which, by the Foulard method, the active solutions were applied and inoculated with a germ suspension of test organisms. The rondelles are then grown for 3 days at 28°C and 75-85% relative humidity. The growth on and under the test pieces is then determined.

The following organisms were used as test organisms:

Penicillium expansum

Aspergillus niger

Alternaria tenuis.

The following table shows the fungicidal activity at different concentrations of active substance:

- inactive = vegetation corresponding to the control

++ weakly active = 25-30% of the control's vegetation

+++ totally active = no vegetation.

+Width of influence-for sdk

6. Microbiocidal effect in affected areas

X parts of active substance are first dissolved in 5 parts of a 1:1 mixture of dimethylformamide and ethylene glycol monomethyl ether and spread homogeneously with (90-x) parts of a commercially available dispersion paint based on polyvinyl acetate-ethyl acrylate copolymer and 5 parts water to a ready-to-iron colour. Filter paper, e.g. Whatmann 3 MM, is supplied with a coating, which is left at room temperature for 3 days. The test pieces are then aired for S days in a ventilation duct at 65°C and 80-90% relative humidity. The test pieces are cut then up and placed on inoculated agar plates (fungi layer upwards, bacteria layer downwards).

As active substance, mixture A was:

^2.6% 2,5,f1-trichloro-benzimidazole

29.7% 2,<*>f, 5,6-tetrachloro-benzimidazole

27.7% 2,'4,5,6,7-pentachlorobenzimidazole

used.

The plates were then cultured:

Fungi: 7 days at 28°C and .70-80% relative humidity. Bacteria:. 2k hours at 37°C and 60% relative humidity.

In the following table, the concentration of active substance that inhibits the growth of the microorganisms before and after aeration is shown:

Against this, the tributyltin oxide even in a concentration of 6% shows only a partial effect.

7. Protective effect against mold and rot inducers. To determine their dry weight, beech wood blocks and pine surface wood (200 x 10 x 5 mm) were dried for 1h hours at 105°C and then weighed. The wood samples were then impregnated for 2 hours at room temperature and normal pressure with a 2.5 and 1% acetone solution of active substance and then stored for 1 week at room temperature under normal pressure. The wooden samples were then with 2/3

of its length dug into the ground. The remaining 1/3 stuck up above the soil. The buried beech trees were then allowed to remain for 3 months, the pine trees for 6 months in the soil, which had a water content of 23-35% and at 28°C and 70-80% relative humidity . The wood samples were then washed under running water with a soft brush, and then dried for 1h hours at 105°C, after which the wood samples were weighed. Opposite the too advanced location found weighing

had the sample lost weight. The size of the weight loss shows the extent to which the wood is protected by the active substances against mold-rot-inducing microorganisms (cellulose- and lignin-degrading microorganisms).

The following table shows the percentage weight loss of wood products treated with the active substance.

From the values listed in the table, it will be seen that the mixture of chlorinated benzimidazoles protects beech and pine against mold-rot agents (cellulose- and lignin-degrading fungi) better than pentachlorophenol, which in a concentration of 2.5% was ineffective on pine after 6 months, by book only partially effective after 3 months.

8. House rot.

Samples of different tree species were dried for determination of

tdr weight 16 to 20 hours at 105°C The sample is then impregnated using a vacuum with acetone solutions of active substance in different concentrations. By repeated weighing, the amount of absorbed active substance is determined.

Furthermore, powder bottles were half-filled with quartz sand and 15 cm^ of a nutrient solution, glucose, peptone dissolved in phosphate buffer, malt extract. A piece of wood of a species suitable for the growth of the fungus is inserted into the quartz sand, inoculated with the mushroom culture and cultivated for 3 weeks.

The pieces of wood impregnated with the active substance are placed on the achieved, even layer of fungus. The device is then kept for 2 months at 2h°C. The mushroom growth and the quality of the wood are then assessed. The sample is then stored for h weeks in a wind tunnel at 65°C with fresh air and once again subjected to a bed of fungal growth.

The following were used as test organisms and tree species:

Coniophora cerebella on pine (Pinus silvestris)

Coriulus versicolor on beech (Fagus silvatica)

Poria incarnata on linden (Tilia spee).

The following table shows the concentration of active substance that inhibits the growth of fungi:

To determine the volatility of these substances, the powdered mixture A was compared with liquid, technical bis-tributyltin oxide and powdered, technical triphenyltin hydroxide.

Volatility for these substances is defined as the weight loss in percentage that occurs when a gram of preparation is stored in a Petri dish in the laboratory. thorium at approx. 20-25°C and in a drying cabinet at 90°C.

The following example describes the preparation of polychlorobenzimidazole mixtures. The temperatures are indicated in °C.

Example.

708 g of 2,5-dichlorobenzimidazole and 2.5 g of iron-III chloride are slurried in 5800 ml of glacial acetic acid. The reaction mixture is heated to U0°C, cooled off and then at 20°C 380 g of chlorine gas are introduced into the mixture, then heated to <1>+0-50°C and 390 g of sodium acetate are added. After the exothermic reaction has ceased, a further 380 g of chlorine gas are introduced, then heated again to <>>+5-50°C, after cooling, 589 g of sodium acetate are added and 500 g of chlorine gas are introduced into the reaction mixture again. After 1 hour's rest, the mixture is poured onto 30 kg of ice and 1500 ml of 30% aqueous sodium hydroxide solution is added, so that the mixture has a pH value of h. The precipitated grains are separated, boiled in boiling methanol and filtered. From the filtrate the mixture A crystallizes out, consisting of h- 2, 6% 2, 5,6-trichloro-benzimidazole, 29.7% 2, h, 5,6-tetrachloro-benzimidazole and 27.7% 2, h, 5,6,7-pentachlorobenzimidazole with a melting point of 212 to 2lk C and a chlorine content of 5<*>+%. The filter residue is boiled again in 1000 ml of methanol and filtered immediately. Mixture B, consisting of h, h% 2,5,c-trichloro-benzimidazole, 33.8% 2,^4-, 5,6-tetrachloro-benzimidazole and 61.8% 2,V,5,6, 7-pentachloro-benzimidazole has a melting point of 280°C during decomposition. This mixture has a chlorine content of 59.12%.

For the material - and particularly for wood protection - the new agents are used in the form of solutions or emulsions. Wood and wood materials are impregnated, applied, wetted or sprayed with such liquid agents. The treatment can take place externally or according to the technical methods known for wood impregnation.

For the preparation of the solutions, organic solvents are used in particular, which are practically odorless and non-volatile, such as e.g. mineral oil fractions, tar oil, high-boiling, aliphatic and aromatic hydrocarbons as well as their chlorinated derivatives - alone or as a mixture. To improve penetration, these solvents may contain additives of lower boiling, aliphatic hydrocarbons and their derivatives. It is preferable to use solvents which in turn have an insecticidal effect.

For the production of emulsion concentrates, organic solvents, dispersants and water are used. As sources of information, e.g. alcohols, aromatic hydrocarbons as well as the solvents listed above. The following substances can serve as dispersants: Polyethylene glycol ethers of mono- and dialkylphenols with 5-15 ethylene oxide residues per molecule and 8-9 carbon atoms in alkyre stone [e.g. those under the trade names "Triton" (Fa. Rohm und Haas, Philadelphia), "Tergitol"

(Union Carbide Chemicals Co., New York) and "Igepal" (General Anilin + Film Corp., Antara Chemicals Div., New York) commercial products], fatty alcohol polyethylene glycol ethers with 5-20 ethylene oxide residues per molecule and 8 to 18 carbon atoms in the fatty alcohol part [e.g. those under the trade names "Genapol"

(Hoechst, Frankfurt a.M.) commercially available products], condensation products of ethylene oxide/propylene oxide [e.g. those products commercially available under the trade names "Pluronics" (manufactured by Wyandotte Chemical Corp., Industrial Chemical Div., Wyandotte, Mich.)], polyvinylpyrrolidones, condensation products of urea-formaldehyde, condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde [f .ex. the product commercially available under the trade name "Sellasol" (manufactured by J.R. Geigy A.G., Basel)], condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde [e.g. those under the trade name "Irgatan"

(manufactured by J.R. Geigy A.G., Basel) commercially available products], further alkylaryl sulfonates, alkali and alkaline earth salts of dibutylnaphthalene sulfonic acid, fatty alcohol sulfates, such as salts of sulfated hexadecanols, heptadecanols, octadecanols,

octadecenols and salts of sulfated fatty alcohol polyglycol ethers [e.g. those commercially available under the trade name "Eriopon" (manufactured by J.R. Geigy.A.G., Basel)], araino-fatty alcohol sulfates [e.g. those under the trade name "Duponol"

(manufactured by DuPont, Wilmington, Del.) commercial products], the sodium salt of oleoylmethyl tauride [those under the trade name "Arkopon" (manufactured by Hoechst, Frankfurt a.M.) commercially available products], ditertiary acetylene glycols [e.g. those under the trade name "Surfynol" (manufactured by Air Reduction'Chemical Company, New York) commercially available products], dialkyldilaurylammonium chloride [that under the trade name "Aliquat" (manufactured by General Mills Inc., Karikakee, Illinois)

commercially available product].

The solutions and emulsion concentrates contain the active substance in a concentration between 1 and 80%. The content of active substance in the solutions used is preferably between h and 10%. Such solutions can be used directly for impregnation, application or application of wood and wood materials. The emulsion concentrates are diluted for use with water to form emulsions with an active substance content of The described agent according to the invention can be mixed into further other • biocide active substances. Thus, the new agents for the polychlorobenzimidazoles can e.g. contain insecticides, such as DDT-active substances, other fungicides, bactericides, fungicides and bacteriostatics to create a wider spectrum of action. Optionally, these agents may also contain water-repellent substances.

The following examples illustrate the production of some typical delivery forms for the agent according to the invention. Parts here means parts by weight.

Emulsion concentrate.

The following substances are used to produce an 8% elution concentrate:

8 parts mixture A, which consists of:

h- 2, hfa 2, 5,'6-trichloro-benzimidazole 29.7% 2,!+, 5,6-tetrachloro-benzimidazole

and 27.7% 2,*+, 5,6,7-pentachloro-benzimidazole,

7 parts DDT active substance (dichlorodiphenyl-trichloroethane),

80 parts xylol and

5 parts of a combination emulsifier of nonylphenol polyethylene glycol ether and dodecylbenzenesulfonic acid calcium salt.

The active substance is intimately mixed with the DDT active substance and dissolved while adding the combination emulsifier in xylol. You get an emulsion concentrate, which can be diluted with water to any desired concentration. If wood or wooden materials, particularly wooden building materials, are coated, impregnated or sprayed with such aqueous emulsions, the treated material is protected against attack by destructive microorganisms and insects.

- Solutions

For the preparation of a h%* solution, the following substances are used:

h shares mixture A, which consists of

<*>f2.6% 2, 5,6-trichloro-benzimidazole 29.7% 2,!+, 5,6-tetrachloro-benzimidazole

and 27.7% 2,1f,5,6",7-pentachlorobenzimidazole

<3> shares DDT active substance

93 parts solvent with 93% content of aromatic substances, boiling point 212-273°C, specific gravity 0.930.

The active substance is dissolved together with DDT-active substance. The solution obtained is used directly for impregnation, coating or sprinkling of wood, etc. and wood materials, whereby the material receives a microbiocidal and insecticidal effect.

Claims (2)

1. Use of 2, 5, 6-trichloro-benzimidazole, 2,4,:j>,6-tetrachloro-benzimidazole, 2,4,5,6,7-pentachloro-benzimidazole or combinations of these as active substances for protection of cellulose-based or cellulose-containing materials and wooden articles of use against attack by food-damaging microorganisms. 2. Use according to claim 1 of a mixture consisting of 4.4 to 42.6 wt% 2,5,6-trichlorobenzimidazole, 29.7 to 33.8 wt% 2,4,o,6-tetrachloro henzimidazole and 27.7 to 61.8 wt/% 2,4,5,6,7-pentachlorobenzimidazole.