JPH10109907A - Microvicidal and bacteriostatic agent for industrial purpose and process therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject agent which exhibits synergistic microbicidal effect against a wide range of microorganisms by combining α- chlorobenzaldoxim, a specific bromine-containing aliphatic compound, and methylene-bis-thiocyanate. SOLUTION: This agent contains (a) α-chlorobenzaldoxime, (b) a bromine- containing aliphatic compound selected from 2,2-dibromo-3-nitro-propionamide, 1,4-bis(bromoacetoxy)-2-butene, 1,2-bis(bromacetoxy)-propane, 1,2,3-tris(bromoacetoxy) propane and the like and (c) methylene-bis-thiocyanate. As for the proportions of individual active ingredients, the weight ratio of A/B is 1/(0.1-20) and the weight ratio of (A+B)/C is 1/(0.02-1). This microbial and bacteriostatic agent is increased in the persistency of its effect and can prolong the proliferation-inhibiting time, particularly no deterioration of these effects even in reductive environments. This microbicidal and bacteriostatic agent is desirably applied to the object system by 0.01-200mg/l.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an industrial bactericidal / bacteriostatic agent and an industrial bactericidal / bacteriostatic method. More specifically, the present invention relates to papermaking process water and pulp slurry in the paper and pulp industry, cooling water and washing water for various industries, as well as coating colors, cutting oils, latexes, emulsions of synthetic resins, starch slurries, calcium carbonate Industrial bactericidal and bacteriostatic agents useful for preserving, disinfecting and bacteriostatic agents for slurries, muddy polymers, heavy oil sludge, metalworking oil agents, fiber oil agents, paints, antifouling paints, paper coating liquids, etc. It relates to sterilization and bacteriostatic methods.

[0002]

2. Description of the Related Art Conventionally, slime due to bacteria and fungi is generated in the paper making process water in the paper and pulp industry and in the cooling water system in various industries, resulting in deterioration of the quality of products and production efficiency. It is known that there is an obstacle such as a decrease in the number of patients. For example, coating color,
In industrial products such as cutting oils, latexes, emulsions of synthetic resins, starch slurries, calcium carbonate slurries, muddy water polymers, heavy oil sludge, metalworking oils, textile oils, paints, antifouling paints, paper coating fluids, etc. Bacterial and fungal spoilage and contamination occur, causing the product to foul and reduce its value.

[0003] Many fungicides have been used to prevent these microbial disorders. In the past, organic mercury compounds and chlorinated phenol compounds were used, but these drugs are highly toxic to the human body and seafood,
Use is regulated to cause environmental pollution. Therefore, recently, nitrogen-containing organic compounds represented by relatively low toxicity methylene bisthiocyanate, 2,2-dibromo-2-nitroethanol, and 5-chloro-2-methyl-4-isothiazolin-3-one, and bromine-containing compounds Organic compounds,
In addition, compounds such as sulfur-containing organic compounds typified by 4,5-dichloro-1,2-dithiol-3-one are widely used as industrial fungicides (issued by the Japan Society of Antifungals and Fungi in 1986). See "Encyclopedia of Bacterial and Fungicides"

[0004] Industrial fungicides using two of the above low-toxic compounds are also known. For example, JP-A-50-1
No. 17933, JP-A-57-114502,
JP-A-2-42007, JP-A-2-53703 and JP-A-6-65006 disclose two kinds of compounds selected from a bromine-containing aliphatic compound and methylenebisthiocyanate which are active ingredients of the present invention. An industrial germicide which is used in combination is described. Further, JP-A-5-70
Japanese Patent Publication No. 306 describes an industrial germicide in which α-chlorobenzaldoxime, which is an active ingredient of the present invention, and a bromine-containing aliphatic compound are used in combination.

However, the above-mentioned one- or two-component low-toxicity bactericide is not suitable for industrial sterilization / bacteriostatic systems in a reducing environment, for example, in an environment in which a reducing substance of 5 mg / l or more is present as sulfite ion. However, there was a disadvantage that the sterilizing / bacteriostatic efficacy was reduced. In addition, although it has low toxicity, it has been desired to reduce the amount of use as much as possible from the viewpoints of pollution, environment, and sterilization treatment cost.

[0006]

SUMMARY OF THE INVENTION From this viewpoint, the inventor of the present invention has proposed the combination of α-chlorobenzaldoxime, a specific bromine-containing aliphatic compound and methylenebisthiocyanate to form a two-component combination. In comparison, we found a surprising fact that so-called synergistic enhancement of the bactericidal effect, improvement of the sustainability of the effect, and prolongation of the growth inhibition time are exerted on a wide variety of microorganisms, and the effect is particularly reduced. Toxic environment, eg 5mg /
The inventors have found that it does not decrease even in an environment where a reducing substance of more than 1 liter is present, and have completed the present invention.

Thus, according to the present invention, (a) α-
Chlorobenzaldoxime (hereinafter abbreviated as CBA);
(B) 2,2-dibromo-3-nitrilopropionamide (hereinafter abbreviated as DBNPA), 1,4-bis (bromoacetoxy) -2-butene (hereinafter abbreviated as BBAB),
1,2-bis (bromoacetoxy) ethane (hereinafter referred to as BB
AE), 1,2-bis (bromoacetoxy) propane (hereinafter abbreviated as BBAP), 1,2,3-tris (bromoacetoxy) propane (hereinafter abbreviated as TBAP), 2-bromo-2-nitro (C) one or more bromine-containing aliphatic compounds selected from -1,3-diacetoxypropane (hereinafter abbreviated as MAC) and 2,2-dibromo-2-nitroethanol (hereinafter abbreviated as DBNE); An industrial bactericidal / bacteriostatic agent characterized by containing methylene bisthiocyanate (hereinafter abbreviated as MBTC) as an active ingredient in a proportion exhibiting a synergistic effect.

Further, according to the present invention, the above-mentioned industrial bacteriostatic / bacteriostatic agent is added to the target system for industrial bactericidal / bacteriostatic at the same time or separately so as to have a total concentration of 0.01 to 200 mg / liter. An industrial sterilization and bacteriostatic method is provided.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS CBA, D used in the present invention
BNPA, BBAB, BBAE, BBAP, TBAP,
MAC, DBNE and MBTC are all known fungicides, and commercially available ones can be used.

The combination ratio of each active ingredient of the present invention varies depending on the kind and combination of the active ingredients. CBA and DB
The combination ratio (as a weight ratio) with a bromine-containing aliphatic compound selected from one or more of NPA, BBAB, BBAE, BBAP, and TBAP is 1: 0.1 to 20, preferably 1: 0.2 to 10. And the combined ratio (as a weight ratio) of the total amount of CBA and the bromine-containing aliphatic compound to MBTC is 1: 0.01 to 1.5, preferably 1: 1.
0.02 to 1.

The combined ratio (as a weight ratio) of CBA and MAC is 1: 0.05 to 10, preferably 1: 5.
0.1 to 5, and the total amount of CBA and MAC and M
The combination ratio (as a weight ratio) with BTC is 1: 0.01
１．５1.5, preferably 1: 0.02-1.

Further, the combination ratio (by weight) of CBA and DBNE is 1: 0.1 to 10, preferably 1: 1.
0.2 to 5, and the combined amount (as a weight ratio) of the total amount of CBA and DBNE and MBTC is 1: 0.0
It is 1-1.5, preferably 1: 0.02-1.

The active ingredient of the bactericidal / bacteriostatic agent of the present invention must be contained in the target system in the form of at least three components (a), (b) and (c) at the time of use. Here, the component (b) combined with the components (a) and (c)
DBNPA, BBAB, BBAE, BBAP, TBA
P, MAC and DBNE are one or more selected from bromine-containing aliphatic compounds, wherein two and three combinations are:
The following are mentioned.

The combination of the two components (b) includes:
DBNPA and BBAB, DBNPA and BBAE, DBN
PA and BBAP, DBNPA and TBAP, DBNPA and MAC, DBNPA and DBNE, BBAB and BBAE,
BBAB and BBAP, BBAB and TBAP, BBAB and MAC, BBAB and DBNE, BBAE and BBAP, B
BAE and TBAP, BBAE and MAC, BBAE and DB
NE, BBAP and TBAP, BBAP and MAC, BBA
P and DBNE, TBAP and MAC, TBAP and DBN
E, MAC and DBNE are mentioned, and among them, DBNPA and BBAB, DBNPA and MAC, and BBAB and MAC are preferable.

The three types of component (b) are DBNPA, BBAB, and BBAE, DBNPA, BBAB, and BBAP, DBNPA, BBAB, and TBA.
P, DBNPA and BBAB and MAC, DBNPA and BB
AB and DBNE, DBNPA and BBAE and BBAP, D
BNPA, BBAE and TBAP, DBNPA and BBAE
, MAC, DBNPA, BBAE, DBNE, DBNP
A, BBAP, TBAP, DBNPA, BBAP, MA
C, DBNPA and BBAP and DBNE, DBNPA and T
BAP and MAC, DBNPA and TBAP and DBNE, D
BNPA, MAC and DBNE, BBAB and BBAE and B
BAP, BBAB and BBAE and TBAP, BBAB and B
BAE and MAC, BBAB and BBAE and DBNE, BB
AB, BBAP, TBAP, BBAB, BBAP, MA
C, BBAB and BBAP and DBNE, BBAB and TBA
P and MAC, BBAB and TBAP and DBNE, BBAB
And MAC and DBNE, BBAE and BBAP and TBAP,
BBAE, BBAP and MAC, BBAE, BBAP and D
BNE, BBAE and TBAP and MAC, BBAE and TB
AP and DBNE, BBAE and MAC and DBNE and BBA
P, TBAP and MAC, BBAP, TBAP and DBN
E, BBAP, MAC and DBNE, TBAP, MAC and DBNE, among which DBNPA, BBAB and M
AC, DBNPA, BBAB and DBNE are preferred.

The bactericidal / bacteriostatic agent of the present invention is usually used in the form of a liquid, but may be used in the form of a powder or a tablet depending on the intended use. When it is preferable to separate the respective active ingredients from the viewpoint of the long-term storage stability of the preparation, the active ingredients may be separately formulated and used separately.

When a liquid preparation is used, the preparation can be prepared using water, a common organic solvent, and a dispersant. In the case where the target system for sterilization is various water systems such as process water for the papermaking process or industrial cooling water, in consideration of the dissolution and dispersibility of the active ingredient,
It is preferable to use a liquid using a hydrophilic organic solvent and a dispersant.

Examples of the hydrophilic organic solvent include amides such as dimethylformamide, glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol, methyl cellosolve, phenyl cellosolve, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether and tripropylene glycol. Glycol ethers such as propylene glycol monomethyl ether, alcohols having up to 8 carbon atoms or methyl acetate, ethyl acetate, 3-methoxybutyl acetate, 2-ethoxymethyl acetate, 2-ethoxyethyl acetate, dimethyl succinate, dimethyl glutarate, Esters such as dimethyl adipate and propylene carbonate, among which diethylene glycol, diethylene Recall monomethyl ether, propylene carbonate, dimethyl glutarate, dimethyl formamide are preferred.

These solvents are selected depending on the solubility and stability of the active ingredient used, and two or more of them may be used as a mixture. In this case, the mixing ratio of the organic solvent can be appropriately determined depending on the solubility and stability of the active ingredient.

As the dispersant, a cationic surfactant,
Anionic surfactants, nonionic surfactants or amphoteric surfactants are suitable, and nonionic surfactants are preferred from the viewpoint of stability as a preparation.

Examples of the nonionic surfactant include higher alcohol ethylene oxide adducts (ethylene oxide is hereinafter abbreviated as (EO)), alkylphenol (EO) adducts, and fatty acid (EO) adducts A polyhydric alcohol fatty acid ester (EO) adduct, a higher alkylamine (EO) adduct, a fatty acid amide (EO) adduct, an oil / fat (EO) adduct, a propylene oxide (Abbreviated as (PO))] (EO) copolymer, alkylamine (PO) (EO) copolymer adduct, fatty acid ester of glycerin, fatty acid ester of pentaerythritol, sorbitol and sorbitan Examples thereof include fatty acid esters, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, and alkylolamides.

In place of these surfactants or as an auxiliary thereof, water-soluble polymers such as xanthan gum, sodium alginate, polyvinyl alcohol, gelatin, and CMC (carboxymethyl cellulose) may be used.

The mixing ratio of these preparations is such that when the preparation is 100 parts by weight, the total amount of the active ingredients is 1 to 50 parts by weight,
It is preferable that the dispersant is at least 0.002 parts by weight based on 1 part by weight of the active ingredient in total, and the balance is a hydrophilic organic solvent.

When the target system is an oil system such as heavy oil sludge, cutting oil, oil-based paint, etc., it is preferable to use a liquid agent using a hydrocarbon solvent such as kerosene, heavy oil, spindle oil, etc. May be used. Furthermore, the active ingredient is 2-3
In the case of formulating a liquid separately, each active ingredient can be formulated with the above-mentioned solvent, dispersant and compounding ratio.

For a target system in which the active ingredient of the present invention can be directly dissolved or dispersed, a direct or solid diluent (for example, kaolin, clay, bentonite, CMC, etc.)
Or a surfactant diluted with the above-mentioned surfactant. In the same manner as in the case of the liquid preparation, the powder preparation may be divided into active ingredients and formulated. Also, depending on the combination,
The preparation may be made up of only the active ingredient without using a solvent or a surfactant.

In the method of the present invention, when the above-mentioned active ingredients are simultaneously added, it is convenient to use them as the same preparation as described above. However, in view of the long-term storage stability of the preparation, each of the active ingredients is added. When it is preferable to separate them or when they are added separately, they are used as separate preparations. From this viewpoint, the industrial bactericidal / bacteriostatic agent of the present invention is added to the industrial bactericidal / bacteriostatic target system in a total concentration of 0.0
There is provided an industrial sterilization / bacteriostatic method characterized by simultaneously or separately adding 1 to 200 mg / liter.

In the present invention, the target system for industrial sterilization includes papermaking process water and pulp slurry in the paper and pulp industry, cooling water and washing water for various industries, and coating colors, cutting oils, latexes, and synthetic resins. Emulsions, starch slurries, calcium carbonate slurries, muddy water polymers, heavy oil sludge, metalworking oils, fiber oils, paints, antifouling paints, paper coatings, etc. In particular, the industrial bactericidal / bacteriostatic agent of the present invention is effective even when the target system is in a reducing environment, for example, in an environment where the reducing substance is 5 mg / L or more (preferably 5 to 100 mg / L) as sulfite ions. .

The amount of the composition of the present invention varies depending on the type of the target system to be sterilized and the combined active ingredients. Particularly, when the composition is added to the process water system of the papermaking process or the industrial cooling water system, the growth of microorganisms is considered. As a concentration (bacteriostatic concentration) for suppressing the concentration of the active ingredient, it is usually sufficient to add about 0.01 to 100 mg / liter as the concentration of the active ingredient. When used bactericidal, the concentration of the active ingredient is 0.02-200 mg /
A liter can accomplish the goal. Further, the composition of the present invention can be made into an emulsion formulation using water or a surfactant as long as the effects of the present invention are not impaired, and can also contain a known fungicide.

[0029]

The present invention is illustrated by the following formulation examples and test examples. The following Examples are preparations comprising the active ingredients (three compounds) of the present invention, and Comparative Examples are preparations comprising two compounds of the active ingredients of the present invention. Also,
Preparation of the preparation was performed by mixing each bactericidal active ingredient with various hydrophilic organic solvents and stirring and dissolving.

Table 1 shows preparation examples which are examples of the present invention.
Table 2 shows comparative preparation examples that are comparative examples. In addition, the abbreviation of each compound of a formulation is shown below. CBA: α-chlorobenzaldoxime DBNPA: 2,2-dibromo-3-nitrilopropionamide (CN-CBr ₂ —CONH ₂ ) BBAB: 1,4-bis (bromoacetoxy) -2-butene BBAE: 1,2 -Bis (bromoacetoxy) -ethane BBAP: 1,2-bis (bromoacetoxy) -propane TBAP: 1,2,3-tris (bromoacetoxy) -propane MAC: 2-bromo-2-nitro-1,3- Diacetoxypropane DBNE: 2,2-dibromo-2-nitroethanol MBTC: methylenebisthiocyanate DEG: diethylene glycol MDG: diethylene glycol monomethyl ether PC: propylene carbonate GAD: dimethyl glutarate DMF: dimethylformamide

[0031]

[Table 1]

[0032]

[Table 2]

Test Example 1 [Test for Confirming Sustained Efficacy of Adhesive (Evaluation of Efficacy as Preservative)] Vinyl acetate adhesive (pH: 4.9, bacterial species: Pseudomonas, Alcaligenes, Micrococcus, Geotricum) , Candida, viable cell count: 2.8 × 10 ⁶ bacteria / ml, mold 9.2 × 10 ³ cells / ml, yeast 3.9 × 10 ³
Each drug was added as an active ingredient to a concentration of 30 mg / liter, and the mixture was allowed to stand at 30 ° C. for one month, and the viable cell count was measured. Table 3 shows the measurement results.

[0034]

[Table 3]

Test Example 2 [Test for Confirming Bacteriostatic Efficacy of White Water in Neutral Medium Paper Making Process (Determination of Mixing Ratio)] White water (pH: 7.
1. Reducing ions: 10 mg / liter as sulfite ions, bacterial species: Pseudomonas, Staphylococcus,
(Bacillus sp., Alcaligenes spp., Initial number of bacteria: 2.3 × 10 ⁷ bacteria / ml) was filtered through No. 2 filter paper, and a broth medium was added thereto, and the mixture was placed in a previously sterilized L-shaped test tube. I took it. Next, 1 mg /
The mixture was added to a concentration of 1 liter, shake-cultured at 37 ° C. for 24 hours, and the absorbance at 660 nm was measured every hour. The time (t) from the start of the measurement until the increase in absorbance based on the growth of the bacteria exceeded 0.1 was determined. Assuming that the value of t when no drug is added is t ₀ and the value of t when a drug is added is t _X , the growth inhibition time (T) is obtained by T = t _X −t ₀ .

The growth inhibition time (T) of each drug compounded at each ratio is shown in FIGS. In the figures, (a) to (c) show the relationship between the amount of MBTC added and the growth suppression time when the composition ratio of CBA and the bromine-containing aliphatic compound is changed.
As shown in FIGS. 1 to 7, CBA and bromine-containing aliphatic compound
It can be seen that by adding a very small amount of BTC, the growth inhibition time is rapidly increased.

For example, FIG. 1B (CBA: DBNPA)
= 1: 2 + MBTC), two components (CBA: DB)
NPA = 1: 2) and one component (MBTC alone)
While the growth inhibition time by the addition of 1 mg / liter is 0 hour and 1 hour, respectively, MBTC is added to the above two components in only 0.01 to 0.02 mg / liter (1/100 to 1).
/ Concentration), the suppression time was extended to 9 to 22 hours. The details are shown in Table 4.

[0038]

[Table 4]

Test Example 3 [Persistence test as a slime control agent] A plastic wire was attached to the inside of the side of a 500 ml beaker, and white water (pH: 7.5, reducing ion : 5 mg / liter as sulfite ion, bacterial species: mainly Pseudomonas, Flavobacterium, Bacillus, initial bacterial count: 2.2 × 10 ⁷ bacteria / ml). This was mixed with a jar tester equipped with a thermostat at 37 ° C. and 60 rpm (per minute). Here, the drug of each formulation example was added as a stock solution at 1-3 mg / liter per active ingredient. Thirty minutes after the addition of the drug, the white water was discarded and replaced with fresh white water (returned to the state where no drug was added). Were repeated twice a day in the morning and evening, and the plastic wire was visually observed, and the slime adhesion amount and the adhesion area were each evaluated on a five-point scale. The evaluation criteria and results are shown in Tables 5 and 6, respectively.

[0040]

[Table 5]

[0041]

[Table 6]

The conventional single preparations or two-component composites show good results for several days after the start of papermaking, but after that the efficacy gradually decreases, and when the papermaking period becomes longer (especially during neutral papermaking), slime is obtained. In many cases, spots and paper cuts frequently occur. In such a case, countermeasures such as reselecting and changing the drug or increasing the amount of addition are taken. However, there are many cases in which the operation cannot be stopped without any action.

From the conventional experience, it is estimated that each evaluation stage corresponds to the following state. Evaluation 1 and 2: Stable operation state with almost no machine dirt Evaluation 3: Machine dirt but operable state Evaluation 4 and 5: Large amount of machine dirt and operation impossible The number of days of slime suppression at an additive concentration of 1 mg / liter in each test example was determined. This is shown in FIGS. However, the case of 3 mg / liter is shown only for the comparative example.

In this test, in Comparative Examples 1 to 8, a large amount of slime adhered on the 2nd to 3rd days at an addition concentration of 1 mg / liter, resulting in soil equivalent to the inability to operate. At the added concentration of 3 mg / liter, the number of days until the soil adhered was slightly increased, but in all cases, the soil became inoperable within 5 days. On the other hand, in the test using the preparation of the present invention (Preparation Examples 1 to 7), at an addition concentration of 1 mg / liter, there was almost no slime contamination for 19 days or more, and the state was equivalent to operable. This shows that the three-component composite agent is effective for a long period of time at a lower concentration than the one- and two-component preparations.

Test Example 4 [(I) Comparison of minimum inhibitory concentration against white water isolate, and (II) Comparison of slime formation rate of white water isolate] (I) Plate culture from white water of Test Examples 2 and 3 Each of the isolated bacteria was cultured at 30 ° C. in a bouillon medium. Take the bouillon medium into a pre-sterilized L-shaped test tube,
Was added to adjust the initial viable cell count to about 10 ⁵ cells / ml. Each drug was added thereto, and cultured with shaking at 37 ° C. for 24 hours, and the absorbance at 660 nm was measured every hour. The minimum inhibitory concentration MIC (mg / liter) of each drug was determined so that the increase in absorbance based on the growth of the bacteria after 24 hours did not exceed 0.1. Table 7 shows the MIC of each drug against white water isolates.

(II) A plastic wire was attached to the inside of the side of a 500 ml beaker, and 500 ml of sterilized water adjusted to pH: 7.0 was charged. Use a jar tester with thermostat at 30 ° C, 60
Mix at rpm. Each bacterium isolated by plate culture from the white water of Test Examples 2 and 3 was cultured at 30 ° C. in a bouillon medium. To the initial viable cell count of about 10 ⁶ cells /
Adjust to 30ml with a jar tester with thermostat,
Mix at 60 rpm. On the fifth day, visually observe the plastic wire,
The slime adhesion amount and the adhesion area were each evaluated on a five-point scale. In addition, evaluation criteria were based on Table 5. Table 7 shows the results of the slime formation rate for the white water isolate.

[0047]

[Table 7]

From Table 7, it can be seen that the preparation examples of the present invention are effective against any of the isolated white water bacteria at an addition amount of 1/2 or less as compared with the two-component comparative preparation examples. . In particular, the comparative preparation example had a high MIC against the slime-forming bacteria Pseudomonas sp. And Bacillus sp., Causing a decrease in efficacy as a slime control agent. On the other hand, the preparation examples of the present invention show a particularly remarkable effect, and it can be seen that the preparation examples are effective at 1/10 or less as compared with any comparative preparation examples.

[0049]

The industrial bacteriostatic / bacteriostatic agent of the present invention has an α-
Since chlorobenzaldoxime, a specific bromine-containing aliphatic compound, and methylene bisthiocyanate are combined, a so-called synergistic enhancement of the bactericidal effect against a wide variety of microorganisms, compared to the combination of the two components, its effect Industrial disinfectant / bacteriostatic agent exhibiting the effect of improving the sustainability of the microorganism and prolonging the growth inhibition time.

Further, it is possible to provide an industrial bactericidal / bacteriostatic agent which does not decrease in the above-mentioned effect even in a reducing environment, for example, an environment in which a reducing substance of 5 mg / l or more is present as sulfite ion. The industrial disinfectant / bacteriostatic agent of the present invention is particularly useful as a disinfectant / bacteriostatic agent for water used in the papermaking process in the paper and pulp industries where slime damage directly affects products.

[Brief description of the drawings]

FIG. 1: Fungicides of the invention, CBA and DBNPA
[(A) 5: 1, (b) 1: 2, (c) 1:10] and M
It is a graph of the growth inhibition time which shows the synergistic effect with BTC.

FIG. 2 shows the fungicides of the present invention, CBA and BBAB [(a)
5: 1, (b) 1: 2, (c) 1:10] and MBTC showing the synergistic effect of MBTC.

FIG. 3 shows the fungicides of the present invention, CBA and BBAE [(a)
5: 1, (b) 1: 2, (c) 1:10] and MBTC showing the synergistic effect of MBTC.

FIG. 4 shows the fungicides of the present invention, CBA and BBAP [(a)
5: 1, (b) 1: 2, (c) 1:10] and MBTC showing the synergistic effect of MBTC.

FIG. 5: Fungicides of the present invention, CBA and TBAP [(a)
1:10, (b) 1: 2, (c) 5: 1] and MBTC showing the synergistic effect of MBTC.

FIG. 6: Fungicides of the present invention, CBA and MAC [(a) 1
0: 1, (b) 1: 1, (c) 1: 5] and MBTC showing the synergistic effect of MBTC.

FIG. 7: Fungicides of the present invention, CBA and DBNE [(a)
5: 1, (b) 1: 1 and (c) 1: 5] and MBTC showing the synergistic effect of MBTC.

FIG. 8 is a graph showing the slime suppression days of the fungicide of the present invention.

FIG. 9 is a graph showing days of slime suppression of a conventional fungicide.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI A01N 47:48)

Claims (6)

[Claims] (1) α-chlorobenzaldoxime, (b) 2,2-dibromo-3-nitrilopropionamide, 1,4-bis (bromoacetoxy) -2-butene, 1,2-bis (Bromoacetoxy) ethane, 1,2-bis (bromoacetoxy) propane, 1,2,3-tris (bromoacetoxy) propane, 2-bromo-2-nitro-1,3-diacetoxypropane and 2,2- 1 from dibromo-2-nitroethanol
An industrial bactericidal / bacteriostatic agent comprising, as active ingredients, a bromine-containing aliphatic compound selected from at least one species and (c) methylenebisthiocyanate in a ratio that exhibits a synergistic effect. 2. An α-chlorobenzaldoxime and 2,2
-Dibromo-3-nitrilopropionamide, 1,4-
At least one selected from bis (bromoacetoxy) -2-butene, 1,2-bis (bromoacetoxy) ethane, 1,2-bis (bromoacetoxy) propane and 1,2,3-tris (bromoacetoxy) propane Ratio (as a weight ratio) with the bromine-containing aliphatic compound is 1: 0.1
And the combined amount (as a weight ratio) of methylene bisthiocyanate and the total amount of α-chlorobenzaldoxime and the bromine-containing aliphatic compound is 1: 0.0.
The industrial bactericidal / bacteriostatic agent according to claim 1, which is 1 to 1.5. 3. The combination ratio (by weight) of α-chlorobenzaldoxime and 2-bromo-2-nitro-1,3-diacetoxypropane is from 1: 0.05 to 10; Chlorobenzaldoxime and 2-bromo-
The industrial use according to claim 1 or 2, wherein the combined amount (as a weight ratio) of 2-nitro-1,3-diacetoxypropane and methylenebisthiocyanate is 1: 0.01 to 1.5. Sterilizing and bacteriostatic agents. 4. An α-chlorobenzaldoxime and 2,2
The combination ratio (as a weight ratio) with dibromo-2-nitroethanol is 1: 0.1 to 10, and the total amount of α-chlorobenzaldoxime and 2,2-dibromo-2-nitroethanol The industrial bactericidal / bacteriostatic agent according to any one of claims 1 to 3, wherein a combination ratio (as a weight ratio) with methylenebisthiocyanate is 1: 0.01 to 1.5. 5. The industrial bactericidal / bacteriostatic agent according to claim 1, which is used in an industrial water system in which a reducing substance of 5 mg / liter or more is present as a sulfite ion. 6. An industrial sterilization / bacteriostatic target system, comprising:
The industrial disinfecting and bacteriostatic method, wherein the industrial disinfecting and bacteriostatic agent according to any one of the above is added simultaneously or separately so as to have a total concentration of 0.01 to 200 mg / liter.