JPH06183911A - Microbicidal process - Google Patents

Abstract

(57) [Summary] [Purpose] For molds, yeasts, bacteria or algae that parasitically propagate in industrial water such as water used in papermaking and pulp manufacturing processes, industrial cooling water, lubricating oil for metal processing, and aqueous emulsion. An object of the present invention is to provide a sterilizing method and a sterilizing agent which can deal with a wide range of microorganisms. [Structure] 2,2-dibromo-3-nitrilopropionamide (DBNPA), (a) 2- (thiocyanomethylthio) benzothiazole, (b) 2.3.3-triiodoallyl alcohol, (c) diiodomethyl -P-tolyl sulfone, (d) 3-iodo-2-propynylbutyl carbamate, (e) β-bromo-β-nitrostyrene in combination with at least one compound selected from a sterilizing method and a sterilizing agent. is there.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to molds, yeasts, bacteria or algae that parasitically propagate in water used in papermaking and pulp manufacturing processes, industrial cooling water, cutting oils for metalworking and aqueous emulsions of lubricating oils. The present invention relates to a sterilizing method and a bactericidal agent capable of controlling the above.

[0002]

2. Description of the Related Art In recent years, it has been indispensable to use water in the chemical industry, and its use is increasing. As a problem accompanying this, there are obstacles such as clogging of pipes by slime caused by microorganisms generated in the cooling tower or the like, for example, filamentous fungi or algae, reduction of thermal conductivity, and the like. Further, in papermaking and pulp factories, slime is generated in the pulp white water, the wall of the riffler, the screen and the like, and a part of the slime is dropped off to cause deterioration of the paper quality, and problems such as paper breakage occur. Further, in metal processing, filamentous fungi and bacteria proliferate in the recirculating water system of processed oil emulsions, causing putrefaction of water, corrosion of metal parts, skin damage and the like. In addition to these industrial water systems, for example, paints, pulps, fiber-treated pastes, and rot or mold of industrial materials such as plywood,
Moreover, the obstacles are widespread.

Conventionally, as a control agent for these microorganisms, organic chlorine-based agents (JP-A-61-197413 and JP-A-60-1181), organic sulfur-based agents (JP-B-57-36884), No. 4 Although graded ammonium salts (Japanese Examined Patent Publication No. 49-2268) and the like have been studied, these agents have various drawbacks in use. For example, that the drug is irritating,
Addition of chemicals to the product such as color tone, quaternary ammonium salt causes severe foaming
Many conventional drugs have activity against some bacteria, fungi, and algae, but do not necessarily have high activity against general bacteria. I needed it. It is not preferable to use a large amount of chemicals, as this will increase the cost and cause environmental pollution such as pollution of the water system. Therefore, many complexing agents in which two or more kinds of agents are combined have been proposed for the purpose of expanding the range of application of bacteria, fungi, and algae as much as possible.

[0004]

DISCLOSURE OF THE INVENTION The present invention is a sterilization method for bacteria, fungi, and algae, which improves the drawbacks of conventional industrial bactericides having a limited application range and exhibits a high effect in a wide range. And to provide an industrial fungicide.

[0005]

The present inventors have found that bacteria,
As a result of intensive research to develop an industrial fungicide showing a high effect in a wide range of fungi and algae, 2,2-dibromo-3-nitrilopropionamide (hereinafter abbreviated as DBNPA) and another specific It was found that the object can be achieved by combining the compounds, and the present invention has been completed based on this finding.

That is, the present invention comprises DBNPA, (a) 2- (thiocyanomethylthio) benzothiazole (b) 2.3.3-triiodoallyl alcohol (c) diiodomethyl-P-tolylsulfone (d) 3- TECHNICAL FIELD The present invention relates to a sterilizing method and a sterilizing agent, characterized by containing at least one compound selected from iodo-2-propynylbutyl carbamate (e) β-bromo-β-nitrostyrene in combination.

The agent of the present invention is a combination of DBNPA, which is generally known as a bactericidal / algicidal agent, and at least one compound selected from compounds (a) to (e). The mixing ratio is preferably 9: 1 to 1: 1 by weight.
9, more preferably 4: 1 to 1: 4. Weight ratio 9:
When the ratio is outside the range of 1 to 1: 9, it is close to that when each compound is used alone, and the effect cannot be sufficiently obtained.

[0008] DBNPA and one or more compounds (a) to (e) may be added separately, or they may be dissolved in the same solvent and injected into necessary places. It is more effective to use a surfactant together with a solvent in a state of being easily dispersed in water. Although the solvent used is not particularly limited, for example, polyethylene glycol, propylene carbonate, methyl carbitol, etc. are used, and the surfactant is not limited, but for example, Pluronic L-64 Nonionic surfactants such as [Asahi Denka Co., Ltd. (trade name)] and Nonion NS-210 [Nippon Oil & Fat Co., Ltd. (trade name)] are used.

The sterilizing method and sterilizing agent of the present invention are used for water in papermaking and pulp manufacturing processes, industrial cooling water, cutting oil and lubricating oil for metalworking, aqueous emulsion, paper, wood, plywood, paint, paste, pulp, It is possible to control molds, yeasts, bacteria, algae and the like that parasitically propagate during the production or process of fibers and the like. In particular, the agents of the present invention cannot be controlled by each of them alone and are the main causative bacteria of microbial disorders: Aspergillus sp., Penicillium sp., Trichoderma genus.
sp.), Geotrichum sp., Cladosporium sp., and other filamentous fungi, Pseudomonas sp., Flavobacterium sp., Acinetobacter sp. ), Aerobacteria (Aerobac
ter sp. ), Bacillus sp., And other bacteria, and can effectively suppress the generation of industrially harmful microorganisms with a small amount of drug.

[0010]

[Drugs used in the test]

2,2-dibromo-3-nitrilopropionamide (D
BNPA): "Biobrom C-1" manufactured by Rohm and Haas
03 ”(trade name) (a) 2- (thiocyanomethylthio) benzothiazole:
"KA-1800" (trade name) manufactured by Nippon Kasei Co., Ltd. (b) 2.3.3-Triiodoallyl alcohol: Meiji Seika
"TIAA" (trade name) (c) Diiodomethyl-P-tolylsulfone: San-Apro "AMICAL-48" (trade name) (d) 3-iodo-2-propynyl butyl carbamate:
Troy Chemical's "POLYPHASE P-100"
(Trade name) (e) β-bromo-β-nitrostyrene: “GIVGARD-BNS” (trade name) manufactured by Givaudan

[Test 1] Pseudomonus sp., Which is a typical bacterium that propagates in an industrial water system (paper process, separated from fine machine white water), was shake-cultured for 24 hours in a standard liquid medium. Activated. This was diluted 500 times with sterile water to adjust the pH to 5.5. 100 ml of this diluted solution was dispensed into an Erlenmeyer flask, and each of the chemical agents shown in Table 1 was added in a predetermined amount. After adding the chemicals, the cells were shaken for 30 minutes in a constant temperature bath at 30 ° C., and the number of surviving bacteria was measured. Flavobacterium sp. In the same manner
(Paper process, separated from high-quality machine white water), aerobacter sp. (Aerobacter sp.) (Separated from cooling tower circulating water) were tested. The results are shown in Table 1.

The standard liquid medium used was composed of 5 g of peptone-tryptone, 2.5 g of yeast extract, 1 g of glucose and 1 liter of distilled water, and the pH was adjusted to 7.0 ("Standa").
rdMethods for the Examination of Water and Was
te Waters "., p. 651, American Public health Asso
Published by ciation (1971)).

[0013]

[Table 1]

As is clear from Table 1, for Pseudomonas, Flavobacterium and Aerobacterium,
DBNPA and compounds (a) to (e), when used alone, did not show a significant bacterial effect, but when combined, they showed excellent effects.

[Test 2] The growth inhibitory concentration (abbreviated as MIC value) against fungi of the method of the present invention in a glucose / peptone liquid medium was measured. The microorganisms tested were Aspergillus sp. (Abbreviated as As) (paper process, separated from slime in a medium quality machine), Penicillium spp.
um sp .: Abbreviated as Ps) (separated from slime in paper process and medium quality machine), Trichoderma sp .: Ts
Abbreviated) (paper process, separated from wet pulp sheet)
The results are shown in Table 2 with the MIC values based on the total amount of active ingredients.

Glucose / peptone liquid medium contains 20 g of glucose, 5 g of peptone, 2 g of yeast extract and MgSO _4.
0.5g, KH ₂ PO ₄ 1g, distilled water 1l, pH
Adjusted to 5.7 (Antibacterial and Antifungal Handbook, 119
3 pages, Gihodo Publishing Co., Ltd. (1986)).

The MIC value is a technique widely used as a method of the Japanese Society of Chemotherapy to measure the antibacterial activity of antibiotics and the like (antibacterial and antifungal handbook, page 684, Gihodo Publishing).
Ltd. (1986)). The results are shown in Table 2.

[0018]

[Table 2]

As is clear from Table 2, (a) to (e) each does not show antibacterial activity against molds caused by industrial water systems, but DBNPA and (a) to (e) have no antibacterial activity. The method of the present invention, which is a combination of the above, showed excellent antibacterial properties.

[0020]

EFFECTS OF THE INVENTION The feature of the present invention is that the effect is enhanced by combining two or more kinds of drugs as compared with the single use of each drug. DBNPA has activity against some bacteria, but little activity against fungi and algae. On the other hand, each of the compounds (a) to (e) shows some activity against fungi and algae,
Ineffective against bacteria. However, for industrial use, it is necessary to show high activity over bacteria, fungi, and algae in general, and DBNPA or the compounds (a) to (e) alone are not practically useful. It is a thing. In the method of the present invention, DBNPA and compound (a)
Although each of the agents (e) has drawbacks by itself, the combination of the agents not only widens the application range of the target microorganisms, but a synergistic effect can be obtained by the combination, and it is possible to control with a small amount. . This means that not only can the cost be kept low by reducing the total amount of the drug used, but also the effect on the surrounding environment can be reduced.

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Claims (2)

[Claims] 1. 2,2-Dibromo-3-nitrilopropionamide and (a) 2- (thiocyanomethylthio) benzothiazole (b) 2.3.3-triiodoallyl alcohol (c) diiodomethyl-P- Triyl sulfone (d) 3-iodo-2-propynylbutyl carbamate (e) β-bromo-β-nitrostyrene At least one compound selected from the combination is used, the sterilization method characterized by the above-mentioned. 2. 2,2-Dibromo-3-nitrilopropionamide and (a) 2- (thiocyanomethylthio) benzothiazole (b) 2.3.3-triiodoallyl alcohol (c) diiodomethyl-P- Tolyl sulfone (d) 3-iodo-2-propynylbutyl carbamate (e) At least one compound selected from β-bromo-β-nitrostyrene is contained in combination to contain a fungicide.