JPS6243965B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides 1,2-benzisothiazoline-3
-one and 1,4-bis(bromoacetoxy)
-It relates to an industrial disinfectant characterized by containing 2-butene as an active ingredient. The industrial disinfectant of the present invention comprising the two components described above provides a stronger synergistic antibacterial effect while maintaining the antibacterial spectrum of each component. Almost all aqueous organic systems are prone to attack by microorganisms, which can lead to unpleasant odors and turbidity, decomposition of emulsions, coagulation of dispersions, decreases in viscosity, and changes in PH. This causes various damage such as the formation of slime and greatly reduces the commercial value of the product. 1,2-benzisothiazolin-3-one, one of the active ingredients of this invention, is well known as an active ingredient of non-metallic low toxicity industrial fungicides, and has the following properties. There is. (1) Has high antibacterial activity against a wide range of microorganisms. (2) They are active over a wide pH range, and their activity is less affected by the presence of bile or serum, for example. (3) Protect aqueous media against infection by microorganisms. Because of the above advantages, the formulation is used as an industrial disinfectant in various fields. For example, emulsion paints, latex, metalworking oils such as cutting oils, water-based adhesives,
It is widely used as a preservative in printing pastes and as a slime control agent. In addition, 1.4 which is another active ingredient of the present invention
-Bis(bromoacetoxy)-2-butene is a non-metallic compound and is generally known to have strong antibacterial activity against Gram-positive bacteria. Therefore, it is well known that its preparations are also used as various industrial disinfectants, mainly as slime control agents. The present inventors believe that by using these two components in combination, it can be expected to be effective against most objects to be sterilized, and that the sterilization effect is stronger than that of each of them alone. a fraction of the amount
The present inventors have discovered an industrially significant synergistic effect in which the same effect can be achieved with just the same amount, and have completed the present invention. That is, 1,2-benzisothiazoline-3
-one (hereinafter referred to as compound A) and 1,4-bis(bromoacetoxy)-2-butene (hereinafter referred to as compound B) preferably in a weight ratio of 16:1 to 1:64 (generally, especially It has been revealed that the growth of bacteria can be sufficiently inhibited by using a mixed drug mixture in a ratio of 8:2 to 2:8 (preferably 8:2 to 2:8) at a concentration of several ppm. Furthermore, since the two components exhibit a synergistic effect when used together, it is possible to significantly reduce the amount of drug used, and the cost is reduced accordingly, bringing great practical benefits. In actual use, the components of the present invention are dissolved in a hydrophilic organic solvent (dimethylformamide, ethylene glycol, methylcellosolve, etc.) and the solution is homogenized (in some cases, a surfactant is also added to make the solution uniform). It is possible to prevent the growth of microorganisms by adding them to the system after treatment. Next, the method for testing the synergistic effect of two components used to complete the present invention will be explained. Synergistic Effect Test Method The synergistic effect between two components is measured by the binary dilution method. Both components are diluted to a predetermined concentration, and a certain amount of each bouillon medium is added. Next, inoculate a certain amount of the pre-cultured bacterial solution into the medium and hold it at 37°C.
After culturing with shaking for 6.5 hours, the concentration of both components at which no increase in absorbance at 660 nm is observed is defined as the minimum inhibitory concentration (hereinafter referred to as TDMIC) determined by the binary dilution method. Figure 1 shows the minimum inhibitory concentration (hereinafter referred to as MIC) of each component using normal scale coordinates.
This is a graph where the values are placed equally on both axes. In this graph, the area above the curve (ie, the TDMIC curve) indicates the growth inhibition zone, and the area below the growth zone. Furthermore, when the diagonal line and the TDMIC curve match, it indicates an additive effect, when the TDMIC curve is above the diagonal line, it indicates an antagonistic effect, and when it is below the diagonal line, it indicates a synergistic effect. Next, the present invention will be explained by examples. Example 1 Synergistic effect against Pseudomonas aeruginosa Compound A and compound B were each administered at 100 μg/
After preparing the solution by diluting it several times more than ml, the synergistic effect was examined according to the test method described above. The results are shown in FIG. This TDMIC curve against Pseudomonas aeruginosa clearly shows synergism. For example, the synergistic effect of two components that completely suppressed the growth of bacteria is when the concentration of compound A is 3.2μg/ml and the concentration of compound B is 3.2μg/ml.
g/ml. That is, for compound A, this drug concentration is
This was approximately 1/16 of the MIC, and for Compound B, it was approximately 1/8 of the MIC of compound B alone, demonstrating that this drug has a strong synergistic effect. In addition, compound A that exhibits a synergistic effect,
Examples of combinations of B concentrations are shown in Table 1.

[Table] Note that FIG. 2 also shows the results of combinations not listed in Table 1. Example 2 Synergistic effect on Bacillus subtilis The results of the same test as in Example 1 are shown in FIG. 3 and Table 2.

[Table] Note that FIG. 3 also shows the results of combinations not listed in Table 2. Example 3 Synergistic effect on Aerobacter aerogenes The results of the test conducted in the same manner as in Example 1 are shown in FIG. 4 and Table 3.

[Table] Note that FIG. 4 also shows the results of combinations not listed in Table 3. In addition, no matter which bacteria in Examples 1 to 3 were used, the stability of the drug was good, and even if the shaking culture was continued for 24 hours,
Furthermore, a similar remarkable synergistic effect was exhibited. Example 4 Compound A and compound B were mixed at a mixing ratio of 10:
Mix to give a ratio of 0, 8:2, 6:4, 4:6, 2:8, and 0:10, and prepare a multiple dilution series for these. A certain amount of the mixture is added to a bouillon medium inoculated with a certain amount of inoculum, and cultured with shaking for 6.5 hours. The MIC of the bacteria was determined. Furthermore, shaking was continued for 24 hours to check the stability of the drug, but the results were similar. The results are shown in Figures 5-7. As is clear from the figure, a synergistic effect was observed in this example as well. Example 5 (Bactericidal effect) Similar to Example 4, compound A and compound B were mixed at a mixing ratio of 10:0 to 0:10,
1 ppm of each was added to a broth medium inoculated with a certain amount of Bacillus subtilis, and cultured with shaking for 1 hour. Thereafter, the number of viable bacteria in each mixed system was determined by the plate dilution method. The results are shown in Table 4.

[Table] As is clear from Table 4, the mixing ratio of compound A and compound B is 4:6.
A significant synergistic effect was observed when the ratio was 2:8. Example 6 At tunnel construction sites, underground water is contaminated by slime, the flow of water in drainage ditches becomes poor, and drainage ditches are even blocked.
At the same time, phenomena such as the release of a foul odor have also been observed, and similar phenomena have been observed in various places. The effectiveness of the mixture of the present invention was tested using slime from a drain in a certain tunnel that contained the causative bacteria. The results of the test according to Example 1 are shown in FIG. 8 and Table 5.

[Table] Note that FIG. 8 also shows the results of combinations not listed in Table 5. Example 7 Compound A and Compound B in emulsion paint base
A mixture of 4:6 was added in an amount of 5 ppm. Then, the sample and drug-free additives were heated to 30°C.
The paint base was left in a constant temperature chamber at 90% humidity and the state of decomposition of the paint base was examined over time. As a result, the product containing no chemical additives exhibited a rotting phenomenon after 7 days, but the product containing the substance of the present invention did not change in appearance even after 40 days. It was revealed that the addition of chemicals completely prevented spoilage. Example 8 For preservative use of machine oil (cutting oil) used for metal cutting, drilling, polishing, etc., a mixture of Compound A and Compound B at a ratio of 2:8 was added in an amount of 5 ppm.
Added to machine oil. Thereafter, it was placed under the same conditions as in Example 7, and the change in the number of viable bacteria in the cutting oil was tested over time. The results are shown in Table 6.

[Table] Example 9 In a certain paper mill, the mixture of the present invention was added to white water resulting from the manufacturing process. A mixture of Compound A and Compound B at a ratio of 4:6 was added in an amount of 5 ppm continuously to white water every 8 hours (by continuous addition method). Even after two weeks, the muddy slime and pink slime that used to adhere to mechanical parts did not appear. This proves that the substance of the present invention has sufficient value as a slime control agent.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the minimum inhibitory concentration curves obtained by the binary dilution method;
The figure shows Pseudomonas aeruginosa (2nd
Fig.), Bacillus subtilis (Fig. 3), Aerobacter aerogenes (Fig. 4), and slime-forming bacteria (Fig. 8) by the two-way dilution method of the minimum inhibitory concentration curves of the industrial fungicide of the present invention. This is a graph showing. Figures 5, 6 and 7 show the mixing ratio of two components of the industrial fungicide of the present invention against Pseudomonas aeruginosa (Figure 5), Bacillus subtilis (Figure 6) and Aerobacter aerogenes (Figure 7). This is a graph showing the relationship between MIC and MIC.

Claims (1)

[Claims] 1. An industrial fungicide characterized by containing 1,2-benzisothiazolin-3-one and 1,4-bis(bromoacetoxy)-2-butene as active ingredients.