JPH0635369B2 - Industrial sterilizer / algicides - Google Patents

Description

TECHNICAL FIELD The present invention relates to an industrial bactericidal / algicidal agent. More specifically, papermaking process water in the pulp and paper industry, cooling water for various industries, metalworking oils, fiber oils, water-based paints, paper coating liquids,
It is useful for antiseptic and sterilization of lattex, sizing agent, etc.
In addition, the present invention relates to an industrial bactericidal / algicidal agent which is useful for preventing damage caused by algae in various water and wastewater systems.

(B) Conventional technology In the papermaking process in the pulp and paper industry and in cooling water systems in various industries, slime caused by bacteria and fungi may occur, resulting in loss of product quality and production efficiency. Are known. In many industrial products such as metalworking oils, fiber oils, water-based paints, paper coating liquids, various latices, and pastes, bacterial spoilage and fungal contamination cause a great deal of damage. In addition, many obstacles occur due to the generation of algae in various types of wastewater systems.

Many fungicides and algaecides have been used to prevent damage by these microorganisms. In the old days, organic mercury compounds such as ethyl mercury phosphate and phenyl mercury acetate, and chlorinated phenol compounds such as pentachlorophenol and trichlorophenol were used. The use of these drugs is regulated because they are highly toxic to humans and seafood and cause environmental pollution.

(C) Problems to be Solved by the Invention The present invention is intended to provide a novel bactericidal / algicidal agent that can replace the conventional bactericidal agents and algicidal agents described above.
In particular, it aims to provide an effective drug at a lower concentration from the viewpoint of environmental pollution.

In this regard, the present inventors have previously conducted diligent research focusing on nitroalcohol derivatives in order to solve the microbial disorders of the early stage, and as a result, among many of these derivatives,
We have found that 1,1-dibromo-1-nitro-propanol-2 and its acetoxy compounds exhibit selective and excellent bactericidal and algicidal effects.

The present invention has been made by further developing this finding, and in particular, when the above 1,1-dibromo-1-nitro-propanol-2 and its acetoxy compound and methylenebisthiocyanate are used in combination, It is based on the fact that an excellent synergistic effect is obtained.

(D) Means and Actions for Solving the Problems Thus, according to the present invention, the following formula (I): (Wherein R represents a hydrogen atom or an acetyl group) and a methylenebisthiocyanate represented by the following formula (II): CH ₂ (SCN) ₂ (II) as active ingredients. An industrial bactericidal / algicidal agent containing the same is provided.

The industrial bactericidal / algicidal agent of the present invention is based on a specific aliphatic nitroalcohol derivative having an excellent effect as described above and is combined with methylenebisthiocyanate which exerts a synergistic effect. Therefore, the intended sterilization / algaidic treatment can be performed at a low concentration.

The aliphatic nitroalcohol derivative of the formula (1) used in the present invention includes 1,1-dibromo-1-nitro-propanol-2.
And 1,1-dibromo-1-nitro-2-acetoxypropane.

These compounds are prepared, for example, by reacting nitromethane with acetaldehyde to prepare 1-nitro-propanol-2, which is contacted with bromine under alkaline conditions to cause bromine addition, and if necessary, contacted with acetic anhydride to obtain acetyl. Can be obtained. At this time, in addition to the above-mentioned dibromide, a monobromide is formed as a by-product, but these may be used in a mixed state as they are without being particularly separated.

The aliphatic nitroalcohol derivative of the above formula (1) and the above formula (I
The use ratio of methylenebisthiocyanate of I is preferably such that the weight ratio of the former to the latter is 99: 1 to 1:99, and particularly 25: 1 to 1:20 in terms of synergistic effect,
It is more preferable that the ratio is from 6: 1 to 1: 6.

The above-mentioned compounds are usually used by formulating them in the form of the same liquid agent, but not limited thereto, and may be used in the form of powder or the like depending on the intended use. Also,
The above compounds may be added separately as separate formulations. Therefore, the present invention provides an aliphatic nitroalcohol derivative represented by the formula (I) in a system for sterilization / algaidization,
It also provides an industrial sterilization / algicidal method comprising adding a trace amount of methylenebisthiocyanate represented by the formula (II). In the case of liquid preparations, glycol-based solvents such as ethylene glycol and diethylene glycol monomethyl ether, amides such as dimethylformamide or alcohols having up to 8 carbon atoms, and various surfactants can be used for preparation.

The addition amount of the industrial bactericidal / algicidal agent of the present invention is, for example, 1 to 100 ppm, preferably 5 to 50 ppm, for white water in a paper mill, and 5 to 50 ppm for industrial cooling water.
0.1 to 100 ppm, preferably 1 to 50 ppm, and 10 to 20000 ppm, preferably 100 to 200 ppm for industrial chemicals and industrial products such as metalworking oils, fiber oils, paints, adhesives, pastes and the like.

Incidentally, in the industrial bactericidal / algicidal agent of the present invention, other known bactericidal agents, third components such as algicidal agents and additives are further added unless the effects of the combination of the present invention are impaired. May be. Examples of the third component include 4,5-dichloro-1,2-dithiol-3-one, dibromonitrilepropionamide, bis (tribromomethyl) sulfone, bisbromoacetoxyethane, and 1,4-bis (bilomoacetoxy). ) Bromoacetates such as 2-butene, 2-methyl-3-isothiazolone, 5-chloro-2
And isothiazolones such as -methyl-3-isothiazolone.

(E) Examples Hereinafter, the present invention will be described in detail with reference to Examples.

An example of the synergistic effect test of the two components used to complete the present invention will be described. The synergy between the two components is measured by the binary dilution method. After diluting both components to the specified concentrations, inoculating a certain amount into broth medium and culturing with shaking at 37 ° C for 7 hours, no increase in absorbance at 660 nm was observed. Inhibitory concentration (hereinafter TD
MIC). FIG. 1 is a graph in which the minimum inhibitory concentration of each component is made to be equal on both axes using normal scale coordinates. The curve of this graph or TDMI
The area above the C curve represents the growth inhibition zone, and the area below the C curve represents the growth zone. In addition, when the diagonal line and the TDMIC curve match, an additive action appears, and when there is a curve above the diagonal line, an antagonistic action appears below the diagonal line, and a synergistic action appears.

Next, the results obtained by the method described above and other examples using representative strains of gram-negative bacteria and bacterium-positive bacteria isolated from slime, which are genus Cydomonas and Bacillus, will be described.

Example 1 1. Test method Methylenebisthiocyanate (hereinafter referred to as compound A)
For 1,1-dibromo-1-nitro-2-propanol (hereinafter referred to as compound B), a multiple dilution series was adjusted so that the addition amount to the medium was 100 μ / 10 ml. The synergistic effect was examined according to the test example. As a test bacterium, the genus C. sudomonas was used.

2. Test Results As shown in FIG. 2, T against this genus C.
The DMIC curve clearly means that there is a remarkable synergistic effect. The synergistic effect of the two components that completely suppressed the growth of the bacterium is, for example, that the concentration of compound A is 0.25 μg / ml and the concentration of compound B is 0.4 μg. Appeared when it was / ml. Compound A alone is 1 μg / ml, Compound B alone is 3.2 μg
Since the growth of bacteria is suppressed at a concentration of 1 / ml, the agent of the present invention has a considerably strong synergistic effect with the amount of about 1/4 when compound A is used alone and about 1/8 when compound B is used alone. It was shown to have. Further, the drug of the present invention has a compound A concentration of 0.13 μg / ml and a compound B concentration of 0.8.
Even in the case of μg / ml, a remarkable synergistic effect is exhibited, and in this case, 1/8 amount of the compound A alone is used, and 1/4 amount of the compound B is used to show the same efficacy. Other combinations of the concentrations of the compounds A and B exhibiting a synergistic effect are as shown in Table 1, for example.

Example 2 1. Test method Compound A and 1,1-dibromo-1 were prepared in the same manner as in Example 1.
The synergistic effect of -nitro-2-acetoxypropane (hereinafter referred to as compound C) was examined. As a test bacterium, the genus C. sudomonas was used.

2. Test Results As shown in FIG. 3, a significant synergistic effect was similarly obtained with the combination of Compound A and Compound C. For example, the concentration of Compound A is 0.25 μg / ml and the concentration of Compound C is 0.4 μg
Appeared when it was / ml. Compound A alone is 1 μg /
Since ml and compound C alone inhibit the growth of bacteria at a concentration of 3.2 μg / ml, the agent of the present invention is about 1/4 the amount when compound A is used alone and about 1/8 when compound C is used alone.
It was shown that it has a considerably strong synergistic effect.
Table 2 shows examples of combinations of the concentrations of the compounds A and C showing other synergistic effects.

Example 3 1. Test method Similar to Examples 1 and 2, the synergistic effect was examined for compound A and compound B and for compound A and compound C. Bacillus was used as the test bacterium.

2. Test results As shown in FIGS. 4 and 5, a remarkable synergistic effect was exhibited also against Bacillus. For example, if the concentration of compound A is
0.75 μg / ml, concentration of compound B and compound C is 0.4 μg
A significant synergistic effect appeared when it was / ml. Compound A
3 μg / ml alone, compound B and compound C alone
Since the growth of the bacteria is suppressed at a concentration of 3.2 μg / ml, the agent of the present invention is about 1/4 the amount when compound A is used alone.
Equivalent potency is shown at about 1/8 the amount when compound B and compound C are used alone. Compounds A and B that show other synergistic effects
Table 3 shows examples of combinations of the concentrations of the compounds A and C.

Example 4 When white water was collected from a certain paper mill and the viable cell count was measured, it was 5.4 ×.
It was 10 ⁶ cells / ml. This white water was dispensed into an L-shaped tube, and the drug was added to the mixture so as to have a predetermined concentration. 1 at white water temperature (37 ℃)
After shaking for a period of time, the viable cell count was measured. The results are shown in Table 4.

As a result, compound A and compound B or compound A and compound C
The combination of the above shows a bactericidal effect that cannot be achieved by single use.

Example 5 A 30% cornstarch slurry was prepared, 1% of 30% rotted cornstarch (viable cell count: 1.0 × 10 ⁷ ) was added, and a drug was added so as to have a predetermined concentration. It was stored at 37 ° C and the viable cell count was measured daily. In addition, 1% of the rotted slurry was added again after the measurement of the number of bacteria on the third day. The results are shown in Table 5.

Thus, the combined use of the compound A and the compound B or the compound A and the compound C exhibits a bactericidal effect which cannot be achieved by single use.

Example 6 1 ml of the already spoiled cutting oil (5.4 × 10 ⁷ viable cells / ml) and 9 ml of 30-fold diluted cutting oil (pH 8.6) collected in a certain metalworking improvement were put in an L-shaped tube, and the medicine was prescribed. The cells were added so as to have a concentration and shaken at 37 ° C., and the number of cells after 1 hour was measured. The results are shown in Table 6. According to it, the combined use of the compound A and the compound B or the compound C shows a bactericidal effect which cannot be achieved by single use.

Example 7 Spoilage lignin solution was added to the lignin solution (viable cell count, bacteria 1.6 × 10 ⁶
Cells / ml, filamentous fungus 1.1 × 10 ³ , yeast 7.4 × 10 ⁴ ) 10% added, drug added and placed in an Einhorn tube, cultured in an egg incubator at 30 ° C., gas generation and viable cell count after 30 days Measured. The results are shown in Table 7.

As a result, the combination of the compound A and the compound B, or the combination of the compound A and the compound C did not generate gas or mold, and the number of bacteria was suppressed low.

Example 8 1. Test method Similar to Examples 1, 2, and 3, the synergistic effect was examined for the compound A and the compound B and the compound A and the compound C. The test method was carried out by dispensing the genus Glorrella, which had been separated and cultivated from the algae generated in the cooling tower in advance, into an L-shaped tube and adding it with the dilution solution of the above-mentioned multiple dilution series. Turbidity was measured by culturing with shaking at 27 ° C. under irradiation of light, and the effective concentration was determined as the concentration at which no increase in turbidity was observed after 7 days.

2. Test results As shown in FIGS. 6 and 7, a clear synergistic effect appeared even in the case of algae. For example, the concentration of compound A is 7.5 μg / m
1, the concentration of compound B was 1.6 μg / ml, the concentration of compound A was 3.8 μg / ml, and the concentration of compound B was 3.1 μg / ml, a remarkable synergistic effect was exhibited. Similar results were obtained with Compound A and Compound C.

Compound A alone at 30 μg / ml, Compound B or C alone
Since the growth of bacteria is suppressed at a concentration of 12.5 μg / ml, the drug of the present invention is used in combination with Compounds A, B and C alone.
Equivalent potency is shown with an amount of 1/4 to 1/8.

The combinations of the concentrations of Compounds A and B or C showing the synergistic effect are as follows.

Example 9 A formulation example of the industrial bactericidal / algicidal agent of the present invention is shown below.

(Formulation Example 1) Methylenebisthiocyanate 10 parts by weight 1,1-dibromo-1-nitro-2-propanol 5 parts by weight Diethylene glycol monomethyl ether 83 parts by weight Myristyldimethylbenzyl ammonium chloride 2 parts by weight as a cationic surfactant Parts (Formulation Example 2) methylenebisthiocyanate 5 parts by weight 1,1-dibromo-1-nitro-2-acetoxypropane 10 parts by weight diethylene glycol monomethyl ether 82 parts by weight N, N, N ', N'-polyoxyethylene-poly Oxypropyleneethylenediamine-based nonionic surfactant 3 parts by weight (c) Effect As described above, the industrial bactericidal / algicidal agent of the present invention has excellent bactericidal / algicidal effects and is intended at a low concentration. Since it can be sterilized and algae killed, it is extremely useful in terms of environmental pollution and economy. Than it is.

[Brief description of drawings]

FIG. 1 is a graph for explaining the synergistic effect determination standard in the embodiment of the present invention, and FIGS. 2 to 7 are graphs for explaining the synergistic effect in the embodiment of the present invention.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area A01N 37:12)

Claims (3)

[Claims] 1. The following formula (I): (Wherein R represents a hydrogen atom or an acetyl group) and an methylenebisthiocyanate represented by the following formula (II): CH ₂ (SCN) ₂ (II) as an active ingredient. Industrial sterilizing and algaecide containing. 2. The compounding ratio of the aliphatic nitroalcohol derivative of formula (I) and the methylenebisthiocyanate of formula (II) is
The industrial bactericidal / algicidal agent according to claim 1, which has a weight ratio of 25: 1 to 1:20. 3. The compounding ratio of the aliphatic nitroalcohol derivative of formula (I) and the methylenebisthiocyanate of formula (II) is
The industrial bactericidal / algicidal agent according to claim 1, which has a ratio of 6: 1 to 1: 6 (weight ratio).