JP2785969B2 - Industrial disinfectant and disinfection method - Google Patents

Description

The present invention relates to an industrial disinfectant and a disinfection method. More specifically, papermaking process water in the paper and pulp industry, cooling water and washing water for various industries, heavy oil sludge, metalworking oil, fiber oil, paint, antifouling paint, paper coating liquid, latex, paste, etc. The present invention relates to an industrial bactericide useful for preservatives, sterilization and bacteriostatic purposes.

(B) Conventional technology Conventional papermaking processes in the paper and pulp industries and cooling water systems in various industries have slimes generated by bacteria and fungi, and have obstacles such as reduced product quality and reduced production efficiency. It has been known. In addition, many industrial products such as heavy oil sludge, metalworking oils, fiber oils, paints, various latexes, sizing agents, etc., cause decay or contamination by bacteria or fungi, and contaminate the products to lower their value.

Many fungicides have been used to prevent damage by these microorganisms. In the past, organic mercury compounds and chlorinated phenol compounds were used, but these drugs are highly toxic to the human body and fish and shellfish, and their use is regulated because they cause environmental pollution. Low-toxic organic nitrogen-sulfur compounds, organic bromo compounds and organic sulfur compounds are widely used as industrial germicides.

3,3,4,4-Tetrachlorotetrahydrothiophene-1,1-dioxide, N, 4-dihydroxy-α-oxobenzeneethanimidoyl chloride and 2-bromo-2-nitro- which are the active ingredients of the present invention 1,3-Diacetoxypropane is known as one of such relatively low-toxic organic compound fungicides (U.S. Pat.
No. 57887, JP-B-51-9005 and JP-A-56-1
No. 20603).

Although the above-mentioned various low-toxicity bactericides have low toxicity, it is desirable from the viewpoints of pollution, environment, and reduction of sterilization treatment cost that the use amount is reduced as much as possible.

Accordingly, a fungicide that exhibits a long-term fungicidal effect with a minimum amount of addition is inevitably desired. From this viewpoint, the above-mentioned 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide Studies have been conducted to develop a synergistic bactericidal effect by using other organic fungicides in combination. And specifically, methylene bisthiocyanate, 1,2-dioxide is added to the thiophene-1,1-dioxide derivative.
Benzoisothiazolin-3-one, 5-chloro-2-methyl-isothiazolin-3-one, 2,2-dibromo-2
-Nitroethanol, 2,2-dibromo-3-nitrilopropionamide, 1,2-bis (bromoacetoxy) ethane, 1,4-bis (bromoacetoxy) -2-butene, bistribromomethylsulfone, 4,5- Synergistic agents using dichloro-1,2-dithiol-3-one and the like in combination have been proposed (for example, JP-A-62-148409 and JP-A-59-193808).
No. 61-236706, etc.).

(C) Problems to be Solved by the Invention A synergistic effect using the above-mentioned thiophene-1,1-dioxide derivative and each of the above-mentioned organic fungicides in many industrial water systems is smaller than when using each single component. It has an excellent bactericidal effect and enables a reduction in the amount of drug used.

However, when such an active ingredient is used in combination in an industrial system where a large amount of reducing substances such as sulfite ions are present, the synergistic effect as described above is reduced or not exhibited at all in some cases. Could not be reduced.

The present invention has been made under such circumstances, and even in a system in which a reducing substance such as sulfite ions is present, a thiophene-1,1-dioxide derivative-containing compound that can exhibit an excellent synergistic effect. It is intended to provide a concomitant drug.

(D) Means for Solving the Problems Thus, according to the present invention, (a) 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide,
(B) An industrial disinfectant comprising N, 4-dihydroxy-α-oxobenzeneethaneimidoyl chloride and / or 2-bromo-2-nitro-1,3-diacetoxypropane as an active ingredient is provided. Is done.

The above 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (hereinafter, TCTO) is represented by the following formula: It is a compound shown by these. The above N-4-dihydroxy-α-oxobenzeneethanimidoyl chloride (DHOBC) is represented by the following formula: Is 2-bromo-2-nitro-1,
3-Diacetoxypropane (BNDAP) has the following formula: It is a compound shown by these.

These TCTO, DHOBC and BNDAP are all known compounds as fungicides as described above, but TCTO and DHOBC or BNDAP
The use of AP in combination has not heretofore been performed, and the fact that the combination exhibits a remarkable synergistic effect, especially an excellent synergistic effect even in the presence of a reducing substance, has not been known at all.

The preferred ratio and the more preferred ratio in which a synergistic effect is exhibited in the combination of TCTO and DHOBC in the present invention are 20: 1 to 1:20 and 10: 1 to 1:10 by weight. In addition, in the combination of TCTO and BNDAP, 10: 1 to 1: 2
0 is preferable, and 5: 1 to 1:10 is more preferable. Note that DHOBC and BNDAP combined with TCTO may be used in combination as component (b).

It is preferable that each active ingredient of the present invention is usually used in the form of a liquid preparation in a one-part preparation. However, without being limited to this, it may be used in the form of a powder or the like depending on the use object.

When a one-part preparation is used, a usual organic solvent or dispersant is used. If the target system is various water systems such as process water for the papermaking process or factory cooling water, dissolution of the active ingredient,
In consideration of dispersibility, it is preferable to use water or a solvent using a hydrophilic organic solvent and a dispersant. Examples of the hydrophilic organic solvent include amides such as dimethylformamide, ethylene glycol, propylene glycol, diethylene glycol, glycols such as dipropylene glycol,
Glycol ethers such as methyl cellosolve, phenyl cellosolve, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and tripropylene glycol monomethyl ether; alcohols having up to 8 carbon atoms or methyl acetate; ethyl acetate; 3-methoxydibutyl acetate; 2-ethoxy Esters such as methyl acetate, 2-ethoxyethyl acetate, and propylene carbonate are exemplified.

As the dispersant, a cationic surfactant, an anionic surfactant, a nonionic surfactant or an amphoteric surfactant is appropriate, and a nonionic surfactant is preferable in terms of stability as a preparation.

As the nonionic surfactant, a higher alcohol ethylene oxide adduct (ethylene oxide is as follows)
EO), alkylphenol (EO) adducts, fatty acid (EO) adducts, polyhydric alcohol fatty acid esters (E.
O) adduct, higher alkylamine (EO) adduct, fatty acid amide (EO) adduct, fat (EO) adduct, propylene oxide [abbreviated as PO] · (EO) copolymer, alkylamine (PO) (EO) Copolymer adducts, fatty acid esters of glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and sorbitan, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, and alkylolamides. The mixing ratio of these preparations is such that the total amount of the bactericide active ingredient is 1 to 50 parts by weight, the dispersant is at least 0.01 part by weight relative to the total 1 part by weight of the active ingredient, and the balance is a hydrophilic organic solvent. It is preferred that

Further, when the sterilization target system is an oil system such as heavy oil sludge, cutting oil, or oil paint, it is preferably a one-pack preparation using a hydrocarbon solvent such as kerosene, heavy oil, or spindle oil, as described above. Various surfactants may be used.

Further, the active ingredient of the present invention may be used directly or as a powder diluted with a fixed diluent (e.g., kaolin, clay, benite, CMC, etc.) for a disinfection target system which can be directly dissolved in a solvent or dispersible. Of course, the various surfactants described above may be used. Further, depending on the combination, it may be used as a preparation comprising a combination of only the active ingredient without a solvent or a surfactant.

The addition amount of the bactericide of the present invention varies depending on the object to be sterilized. In particular, when the bactericide is added to the process water system of the papermaking process or the industrial cooling water system, the concentration (bacteriostatic concentration) that suppresses the growth of microorganisms is as follows. , Usually 0.05 as the total concentration of the active ingredient
Addition of about 20 mg / sufficient is sufficient. When used bactericidal, the total concentration of the active ingredient is 0.5 to 50 mg /
Can achieve the purpose.

In the present invention, when two active ingredients (a) and (b) are simultaneously added, it is convenient to use them as the same preparation as described above, but they are separated from each other in terms of long-term storage stability of the preparation. When it is preferable to keep the composition or when added separately, they are used as separate preparations. Therefore, according to the present invention, (a) 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and (b) N, 4-dihydroxy Industrial disinfection method characterized by adding -α-oxobenzeneethaneimidoyl chloride and / or 2-bromo-2-nitro-1,3-diacetoxypropane.

Even in this case, it is convenient to make each preparation into a liquid preparation. For example, such a preparation can be prepared by adding the above-mentioned organic solvent or dispersant. Of course, the active ingredient of the present invention can be directly dissolved or dispersible, respectively.
It can be used separately or as a separate powder.

The active ingredients (a) and (b) of the present invention exert excellent synergistic effects in industrial sterilization target systems based on their synergistic effects. Therefore, even when each of the active ingredients (a) and (b) is used at a concentration that cannot substantially exert a bactericidal effect by itself, the intended bactericidal effect can be exhibited. And, in reducing systems, for example, papermaking systems in paper and pulp mills, especially in industrial target systems in which sulfite ions are often present at 5 mg / min or higher, such as medium paper containing deinked paper (DIP) and newsprint papermaking systems. Has a remarkable synergistic effect, and is particularly useful when used in such a system.

(E) Example This is illustrated by the following test examples of the present invention.

Test Example 1 [Test for Confirming Bacteriostatic Effect] (1) Evaluation Method The synergistic action between two components is measured by a binary dilution method. Both components are diluted to a predetermined concentration, and each is added to the medium in a fixed amount. After inoculating this with a microorganism and culturing it under certain conditions, the concentration at which the growth of the microorganism is not observed is defined as the minimum expression inhibition concentration (MIC) by the binary dilution method.

FIG. 1 is a graph in which the minimum growth inhibitory concentration of each component is set equally on both axes using ordinary scale coordinates.
The region above the curve in the graph, that is, the TDMIC curve, indicates the growth prevention zone, and the region below the curve indicates the proliferation zone. A curve above the diagonal indicates an antagonistic effect, and a curve below the diagonal indicates a synergistic effect.

(2) Synergistic effect on sterilization Pseudomonas fluo, a representative strain of gram-negative bacteria found in process water in the paper and pulp industry, cooling water for various industries, paints, paper coating solutions, latex, and paste The synergistic effect on redness was tested.

Using a bouillon medium as the medium, a certain amount of the bacterial solution pre-cultured overnight was inoculated, and cultured with shaking at 37 ° C. for 2 hours, and the concentration at which no turbidity of the medium was observed was determined. In addition, when no drug was added, it became cloudy after 2 hours. The test results are shown in FIG. 2 and FIG.

Test Example 2 [Test for Confirming Bacteriostatic Effect in the Presence of Reducing Substance] Using Pseudomonas fluorescens, a recognition test of the bacteriostatic efficacy in the presence of a reducing substance was performed.

Sodium sulfite is used as a reducing substance. This is SO
_{As a} medium, a medium added with a bouillon medium so that it becomes 20 ppm as ₃ ^2- is used.After inoculating a fixed amount of the bacterial solution pre-cultured overnight and culturing with shaking at 37 ° C for 24 hours, no turbidity of the medium is observed. The minimum inhibitory concentration was determined. In addition, when no drug was added, it became cloudy after 2 hours.

The test results are shown in FIGS. 6 to 8 are comparative examples.

As is clear from the test results, in the presence of sulfite ion (20
ppm), TCTO and known general-purpose fungicides [methylenebisthiocyanate (MBTC), 2,2-dibromo-3-nitrilopropionamide (DBNPA), 4,5-dichloro-1,
2-Dithiol-3-one (DCDT)], the synergistic effect is not exhibited, and there may be an antagonistic effect in some cases.
(See FIG. 6 to FIG. 8) TCTO, DHOBC and BND which are the active ingredients of the present invention
AP alone is affected by reducing substances and its effect is reduced, but in the case of this invention using TCTO and DHOBC and TCTO and BNDAP together, a remarkable synergistic effect is exhibited and maintained,
It can be seen that there is an advantage that the additive concentration can be reduced to 1/3 to 1/5 of that when used alone.
FIG. 5 and FIG. 5).

Test Example 3 [Test of bacteriostatic effect on white water in papermaking process] White water (pH 5.0, reducing substance: 35 ppm in terms of SO ₃ ^2- , Bacillus spp., Pseudomonas collected from a newsprint machine (acid paper making) at a certain paper mill Genus, Flavobacterium spp.) Was filtered through Oriental paper No. 2, and a test solution was prepared by dissolving 5 g of Ehrlich meat extract and 10 g of polypeptone in 1000 ml of the filtrate. After the drug was added to this test solution and cultured with shaking at 37 ° C. for 24 hours, the minimum growth inhibitory concentration at which no turbidity of the medium was observed was determined. In addition, when no drug was added, it became cloudy after 3 hours.

 Table 1 shows the test results.

(F) Effects of the Invention According to the industrial bactericide and the bactericidal method of the present invention, a significantly higher bactericidal effect is exhibited as compared with the case where each of the active ingredients (a) and (b) is added alone. Can be significantly reduced.

Moreover, such a synergistic effect is clearly exhibited even in a system in which sulfite ions are present in an amount of 5 mg / or more.
Its advantage over the synergistic agent containing TCTO is extremely high.

[Brief description of the drawings]

FIG. 1 is a MIC graph for determining a synergistic effect applied in the present invention, and FIGS. 2 to 5 are MIC graph diagrams showing a synergistic effect exerted in an embodiment of the present invention, and FIGS.
FIG. 8 is a MIC graph for each comparative example.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-102004 (JP, A) JP-A-62-294602 (JP, A) JP-A-59-175406 (JP, A) JP-A-56-294 120603 (JP, A) JP 46-1548 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) A01N 43/10 A01N 37/52 A01N 37/12 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] (1) (a) 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and (b) N, 4-dihydroxy-α-oxobenzeneethanimidoyl chloride and / or (2) An industrial bactericide comprising -bromo-2-nitro-1,3-diacetoxypropane as an active ingredient. 2. The industrial fungicide according to claim 1, wherein the blending ratio of component (a) to component (b) is 10: 1 to 1:10 by weight. 3. The method according to claim 1, wherein (a) 3,3,4,4-
Tetrachlorotetrahydrothiophene-1,1-dioxide and (b) N, 4-dihydroxy-α-oxobenzeneethaneimidoyl chloride and / or 2-bromo-
An industrial sterilization method characterized by adding 2-nitro-1,3-diacetoxypropane. 4. The industrial sterilization method according to claim 3, wherein the addition ratio of component (a) to component (b) is 10: 1 to 1:10 by weight. 5. The industrial sterilization target system contains 5 mg / l of sulfite ion.
The industrial sterilization method according to claim 3, which is a reducing target system containing the above.