JP2891629B2 - Industrial bactericidal and bacteriostatic agents - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an industrial bactericidal / bacteriostatic agent. More specifically, papermaking process water in the paper and pulp industry, cooling water and washing water for various industries, metalworking oils,
The present invention relates to an industrial disinfecting and bacteriostatic agent useful for preserving and disinfecting starch slurries, especially fiber oil agents, paints, antifouling paints, coating liquids for paper, latex, sizing agents and the like.

[0002]

2. Description of the Related Art Conventionally, slime is generated by bacteria and fungi in papermaking processes in the paper and pulp industries and in cooling water systems in various industries, and there are obstacles such as deterioration of product quality and reduction of production efficiency. Are known. In addition, many industrial products such as metalworking oils, fiber oils, paints, various latexes, sizing agents, starch slurries, etc., cause decay or contamination by bacteria or fungi, thereby fouling the products and reducing their value.

[0003] Among these industrial products, starch is known for various uses as a slurry or a size liquid. For example, in a paper mill, it is used in large quantities for surface size, color binder and internal addition. Underground stem starch such as potato starch and tapioca starch, wheat starch, and the like are in a state to which soil bacteria are attached, and there are many Bacillus bacteria having heat-resistant spores.

[0004] These spores survive at 100 ° C,
Proliferates in a starch slurry rich in starch, which is a nutrient source of microorganisms, together with fallen bacteria and the like. When putrefaction progresses due to the growth of microorganisms, obstacles such as putrefaction odor, clogging of strainers, and deterioration of quality due to a decrease in viscosity and a decrease in pH occur.

[0005] Many fungicides have been used to prevent these microbial disorders. In the past, organic mercury compounds, chlorinated phenol compounds and formalin 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. Relatively low toxicity methylene bisthiocyanate, 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazoline-3
Organic sulfur represented by -one, 2,2-dibromo-2-nitroethanol, 2,2-dibromo-3-nitrilopropionamide, 1,2-bis (bromoacetoxy) ethane, 1,4-bis (Bromoacetoxy) -2-
Compounds such as butene and organic bromo compounds represented by bistribromomethyl sulfone and organic sulfur compounds represented by 4,5-dichloro-1,2-dithiol-3-one are widely used as industrial germicides ( (See "Encyclopedia of Fungicides and Fungicides" issued by the Japan Society of Fungicides and Fungi in 1986).

Also, a combination of 4,5-dichloro-1,2-dithiol-3-one with an alkylenebisthiocyanate, 4,5-dichloro-1,2-dithiol-3-one and 2,2- An industrial fungicide has been proposed in which a synergistic effect is exhibited by a combination of dibromo-3-nitrilopropionamide and a combination of 2,2-dibromo-3-nitrilopropionamide and methylenebisthiocyanate (Japanese Patent Publication No. 63-1988). No. 60722, JP-B No. 1-20121 and JP-A-50-117933).

[0007]

The various low-toxicity bactericides described above are effective only for a narrow range of microorganisms in the system to be sterilized, and therefore have a sufficient bactericidal effect in a system containing various microorganisms. In addition to the drawback of not being able to obtain a microorganism, there is a problem that even if it is used for an effective microorganism for a long time, a resistant bacterium appears.

[0008] Fungicides comprising a combination of fungicides for the purpose of exhibiting a synergistic effect also have a remarkable bactericidal activity against bacteria and fungi, but do not have a long-lasting effect. Has the disadvantage that its bactericidal power is not sufficient, especially in target systems that require a long-term bactericidal effect by adding a bactericide batchwise, such as starch slurries. Thus, it was not possible to sufficiently prevent the occurrence of spoilage odor, clogging of the strainer, and deterioration by microorganisms such as deterioration of product quality.

It is an object of the present invention to provide an industrial bactericidal / bacteriostatic agent which has an effective bactericidal activity against a wide variety of microorganisms such as bacteria, molds and yeasts and maintains its effect. .

[0010]

From this viewpoint, the inventors of the present invention have studied the combination and content of various industrial fungicides, and as a result, have found that 4,5-dichloro-1,2-dithiol-3-. By combining ON with 2,2-dibromo-3-nitrilopropionamide and methylenebisthiocyanate at a specific ratio, a remarkable bactericidal effect on a wide variety of microorganisms and its bactericidal effect can be obtained as compared with the combination of the two components. I found a surprising fact that the effect is sustainable.

4,5-dichloro- used in the present invention
1,2-Dithiol-3-one has a bactericidal effect not only on bacteria but also on fungi, but has a particularly strong bactericidal effect on Gram-negative bacteria. Also, 2,2-dibromo-3-nitrilopropionamide has a broad bactericidal spectrum,
Its bactericidal effect is relatively weak, and therefore, when used alone, it must be used at relatively high concentrations. In addition, methylene bisthiocyanate has a strong antibacterial action, but the onset of the action is relatively slow and lasts for a relatively long time. By combining these three components in a specific ratio, it has a strong bactericidal activity against bacteria, mold, and yeast, and can maintain its bactericidal action for a long time.

Thus, according to the present invention, 4,5-dichloro-1,2-dithiol-3-one (hereinafter referred to as DCD
Industrial sterilization and static electricity containing 2,2-dibromo-3-nitrilopropionamide (hereinafter abbreviated as DBNPA) and methylenebisthiocyanate (hereinafter abbreviated as MBTC) as active ingredients. A fungicide is provided.

Although the details of the reason why such a remarkable effect is exerted are not clear, it is considered that the interaction is a combination of specific compounds in specific ratios, that is, a synergistic effect. In the present invention, the weight ratio of DCDTO, DBNPA and MBTC is DBNPA where DCDTO is 1.
Is 0.1 to 50, preferably 1 to 20, DC
Assuming that the total amount of DTO and DBNPA is 1, MBTC
0.03 to 1.5, preferably 0.05 to 1 is preferable because a more remarkable synergistic effect is exhibited.

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

In the present invention, the target system for industrial sterilization includes papermaking process water in the paper and pulp industries, cooling water and washing water for various industries, metalworking oils, fiber oils, paints,
Antifouling paint, coating liquid for paper, latex, starch slurry of sizing agent and the like. In the case where the system to be sterilized is various aqueous systems such as process water or industrial cooling water of a papermaking process, starch slurry, synthetic resin emulsion, etc., in consideration of the dissolution and dispersibility of the active ingredient, water, a hydrophilic organic solvent and It is preferable to use a liquid using 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, Glycol ethers such as tripropylene glycol monomethyl ether, alcohols having up to 8 carbon atoms or methyl acetate, ethyl acetate, 3-methoxybutyl acetate, 2-ethoxymethyl acetate, 2-
Ethoxyethyl acetate, propylene carbonate,
Esters such as dimethyl glutarate and water.

Among these hydrophilic solvents, ethylene glycol, propylene glycol,
Glycols such as diethylene glycol and dipropylene glycol, methyl cellosolve, phenyl cellosolve,
Glycol ethers such as diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether;
Alcohols having up to 8 carbon atoms or esters such as methyl acetate, ethyl acetate, 3-methoxybutyl acetate, 2-ethoxymethyl acetate, 2-ethoxyethyl acetate, propylene carbonate and dimethyl glutarate are preferred.

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 (EO) adduct, alkylphenol EO adduct, fatty acid EO adduct, polyhydric alcohol fatty acid ester EO adduct, Alkylamine EO adduct, fatty acid amide EO adduct, EO adduct of fats and oils, propylene oxide (PO) .EO
Copolymer, alkylamine POEO copolymer adduct, fatty acid ester of glycerin, fatty acid ester of pentaerythritol, fatty acid ester of sorbitol and sorbitan, fatty acid ester of sucrose, alkyl ether of polyhydric alcohol, Alkylolamide and the like. Among them, higher alcohol EO adducts, alkylphenol EO adducts, polyhydric alcohol fatty acid ester EO adducts, fatty acid amide EO adducts, PO.
EO copolymer, alkyl ether of polyhydric alcohol,
An alkylamine POEO copolymer adduct and an alkylolamide or a combination of two or more thereof are preferable, and an alkylamine POEO copolymer adduct (for example, N, N, N It is particularly preferable to use nonionic surfactants of the ', N'-polyoxypropylene, polyoxyethylenediamine and the like) or alkylolamide type. In some cases (for example, when stability of the formulation does not matter), a cationic, anionic or amphoteric surfactant may be used. The mixing ratio of these preparations is
It is preferable that the total amount of the active ingredient is 1 to 50 parts by weight, the dispersant is at least 0.01 part by weight based on 1 part by weight of the total amount of the active ingredient, and the balance is a hydrophilic organic solvent.

When the system to be disinfected is an oil system such as a cutting oil or an oil-based paint, it is preferable to use a liquid agent using a hydrocarbon solvent such as kerosene, heavy oil, spindle oil or the like. You may. Further, for the system to be sterilized in which the active ingredient of the present invention can be directly dissolved or dispersed, the powder may be directly or diluted with a solid diluent (for example, kaolin, clay, bentonite, CMC, etc.),
Various surfactants may be used. Further, depending on the combination, a formulation may be made with only the active ingredient without using a solvent or a surfactant.

The amount of the composition of the present invention varies depending on the object to be sterilized.
About 00 mg / l is sufficient, and when added to a starch slurry, about 1 to 100 mg / l is sufficient.

From this viewpoint, there is provided an industrial sterilization method characterized by adding the above-mentioned active ingredients simultaneously or separately to an industrial sterilization target system. In the method of the present invention, when the above-mentioned active ingredients are added simultaneously, it is convenient to use the same preparation as described above, but the same effect is exhibited even if they are added separately. Again,
The formulations described above are preferred. The invention is illustrated by the following examples, comparative examples and test examples.

[0023]

The following examples are preparations comprising the active ingredients (three compounds) of the present invention. As comparative examples, one or two of the active ingredients of the present invention may be used. This is a preparation prepared by adding a known bactericide. Examples Formulation Example 1 9 parts by weight of DCDTO 4 parts by weight of DBNPA 2 parts by weight of MBTC 85 parts by weight of diethylene glycol monomethyl ether

Formulation Example 2 DCDTO 7 parts by weight DBNPA 7 parts by weight MBTC 1 part by weight Diethylene glycol monomethyl ether 85 parts by weight

Formulation Example 3 DCDTO 3 parts by weight DBNPA 7 parts by weight MBTC 5 parts by weight Diethylene glycol monomethyl ether 85 parts by weight

Formulation Example 4 DCDTO 1 part by weight DBNPA 10 parts by weight MBTC 1 part by weight Diethylene glycol monomethyl ether 88 parts by weight

Comparative Example Comparative Preparation Example 1 DCDTO 7.5 parts by weight DBNPA 7.5 parts by weight Diethylene glycol monomethyl ether 85 parts by weight

Comparative Preparation Example 2 7.5 parts by weight of DCDTO 7.5 parts by weight of MBTC 85 parts by weight of diethylene glycol monomethyl ether

Comparative Preparation Example 3 7.5 parts by weight of DBNPA 7.5 parts by weight of MBTC 85 parts by weight of diethylene glycol monomethyl ether

Test Example 1 [Test for Confirming Sustained Efficacy of Starch Slurry] (Test Method) Slurry prepared from raw tapioca starch slurry using industrial water (pH: 5.4, solid content: 35 watts)
/ w%) plus 1% of spoilage deposits collected from a certain paper mill starch slurry storage tank (species: Bacillus, Pseudomonas, Alcaligenes, viable cell count: 1.6 × 10 ⁶⁾ Pieces / ml). 10 g of the test sample is dispensed into an L-shaped test tube, and various drugs are used as active ingredients at 15 mg /
and the mixture was shaken at 25 ° C. Three days later, the viable cell count of each sample was measured. The results are shown in FIGS.
Shown in

Test Example 2 [Test for Confirming Sustained Efficacy of Starch Slurry] (Test Method) Phosphorylated urea starch slurry used for coating color (pH: 6.5, solid content: 40 w / w)
%, Fungal species: Pseudomonas sp., Alcaligenes sp., Micrococcus sp., Viable cell count: 1.8 × 10 ⁸ cells / ml), and each drug as an active ingredient to a concentration of 15 mg / l, and added at 30 ° C.
For 7 days, and the viable cell count was measured thereafter. Table 1 shows the measurement results.

[0032]

[Table 1]

[0033] Test Example 3 [sustained efficacy confirmatory test for adhesive] (Test Method) vinyl acetate-based adhesive (pH: 4.9, species: Pseudomonas, Alcaligenes, Geotori cam genus, viable cell count: Bacterial 3 0.6 × 10 ⁶ / ml, mold 1.1 × 10 ⁴ / ml, yeast 4.5 ×
(10 ⁵ cells / ml) were added as active ingredients to give a concentration of 30 mg / l, and the mixture was allowed to stand at 30 ° C., and the number of viable bacteria was measured one month later. Table 2 shows the measurement results.

[0034]

[Table 2]

Test Example 4 [Test for confirming sustained efficacy against standard bacteria] (Evaluation method) Usually, 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 no growth of the microorganism is observed is defined as the minimum growth inhibitory concentration by the binary dilution method. FIG. 4 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 of this graph, that is, the TDMIC curve, indicates the growth inhibition 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.

(Measurement method) A bacterial solution of Pseudomonas aeruginosa pre-cultured in a bouillon medium was added to a 10-fold diluted bouillon medium so that the number of viable cells was 10 ⁶ cells / ml or more. And shaken at 37 ° C. for 24 hours. FIG. 5 shows the minimum growth inhibitory concentration (MIC) at that time.

Test Example 5 [Test of sterilization effect on white water in the newspaper acidic papermaking process] White water (pH 4.0) collected from a newsprint machine at a certain paper mill.
7. Reducing substance SO ₃ ^2- converted 10 mg / l , mainly Pseudomonas, Staphylococcus, Alcaligenes, Flavobacterium and Bacillus, initial number of bacteria
(7.5 × 10 ⁶ cells / ml), each drug was added to give an active ingredient concentration of 10 mg / l, the mixture was shaken at 30 ° C. for 1 hour, and the number of surviving bacteria was measured. Table 3 shows the results.

[0038]

[Table 3]

Test Example 6 [Effectiveness test for white water in fine neutral papermaking process] White water (pH 7.
9. Pseudomonas sp., Bacillus sp., Staphylococcus sp., Micrococcus spp., Flavobacterium spp., Initial bacterial count 3.1 × 10 ⁷ / ml), and each drug becomes 15 mg / l as active ingredient concentration. And shaken at 37 ° C. for 1 hour, and then the number of surviving bacteria was measured. Table 4 shows the results.

[0040]

[Table 4]

Further, the above white water was filtered through a No. 2 filter paper, and a broth medium was added to the filtered white water.
Transfer to a test tube. Then, each drug was added to the active ingredient at a concentration of 10 mg / l as an active ingredient, cultured at 37 ° C. with shaking, and the absorbance at 660 nm was measured every hour. The time (t) until the increase in absorbance based on the growth of the bacteria from the start of the measurement exceeded 0.1 was determined. The value of t when no drug is added is t
o, assuming that the value of t at the time of drug addition is tx, the growth suppression time T is obtained by T = tx-to. The values of T for each drug are shown in FIGS.

[Brief description of the drawings]

FIG. 1 shows a bactericide of the present invention (DCDTO: DBNPA =
FIG. 3 is a graph showing the continuity of the bactericidal action of various ratios of MBTC at 1: 1.

FIG. 2 shows the fungicide of the present invention (DCDTO: DBNPA =
The graph figure which shows the continuation of the bactericidal action of various ratios of MBTC) at 1: 5.

FIG. 3 shows the fungicide of the present invention (DCDTO: DBNPA =
FIG. 5 is a graph showing the continuation of the bactericidal action of various ratios of MBTC at 5: 1.

FIG. 4 is a graph for explaining a synergy effect criterion.

FIG. 5 shows the fungicide of the present invention (DCDTO: DBNPA =
FIG. 4 is a graph showing a synergistic effect of MBTC at various ratios at 1: 1.

FIG. 6 shows the fungicide of the present invention (DCDTO: DBNPA =
FIG. 4 is a graph showing the growth inhibition time of various ratios of MBTC at 4: 1.

FIG. 7 shows a fungicide of the present invention (DCDTO: DBNPA =
FIG. 2 is a graph showing the growth inhibition time of various ratios of MBTC at 1: 1.

FIG. 8 shows a bactericide of the present invention (DCDTO: DBNPA =
FIG. 4 is a graph showing the growth inhibition time of MBTC at various ratios at 1: 4.

FIG. 9 shows the fungicide of the present invention (DCDTO: DBNPA =
FIG. 2 is a graph showing the growth inhibition time of various ratios of MBTC at 1:10.

FIG. 10 shows the fungicide of the present invention (DCDTO: DBNPA =
FIG. 9 is a graph showing the growth inhibition time of various ratios of MBTC at 1:20.

FIG. 11 shows the fungicide of the present invention (DCDTO: DBNPA =
FIG. 2 is a graph showing the growth inhibition time of various ratios of MBTC at 1:50.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-91108 (JP, A) JP-A-62-48603 (JP, A) JP-A-57-99507 (JP, A) JP-A 63-91507 225307 (JP, A) JP-A-50-117933 (JP, A) JP-A-57-114502 (JP, A) JP-A-4-320695 (JP, A) (58) Fields investigated (Int. ⁶ , DB name) A01N 47/48 A01N 43/26 A01N 37/44 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)

Claims (3)

(57) [Claims] 1. An industrial sterilizer comprising 4,5-dichloro-1,2-dithiol-3-one, 2,2-dibromo-3-nitrilopropionamide and methylenebisthiocyanate as active ingredients. -Bacteriostatic agents. 2. The amount of 2,2-dibromo-3-nitrilopropionamide is 0.1 to 50 parts by weight based on 1,5 parts by weight of 4,5-dichloro-1,2-dithiol-3-one.
Methylene bisthiocyanate was used in an amount of 0.03 to 1.5 parts by weight based on 1 part by weight of the total amount of 4,5-dichloro-1,2-dithiol-3-one and 2,2-dibromo-3-nitrilopropionamide. 2. The method according to claim 1, wherein
The industrial bacteriostatic / bacteriostatic agent described. 3. A system for industrial sterilization, which comprises 4,5-dichloro-1,2-dithiol-3-one and 2,2-dibromo-.
3. Industrial sterilization / static method wherein 3-nitrilopropionamide and methylenebisthiocyanate are added simultaneously or separately at a ratio according to claim 2 and a total concentration of 0.5 to 200 mg / l. Fungus method.